EPA-450/3-75-027
March 1975
          FIELD SURVEILLANCE
   AND  ENFORCEMENT  GUIDE:
    WOOD PULPING  INDUSTRY
    U.S. ENVIRONMENTAL PROTECTION AGENCY
       Office of Air and Waste Management
                                   t
    Office of Air Quality Planning and Standards
    Research Triangle Park, North Carolina 27711

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                                EPA-450/3-75-027
    FIELD SURVEILLANCE
AND ENFORCEMENT GUIDE:
 WOOD PULPING  INDUSTRY
     Environmental Science and Engineering, Inc,
             2324 SW 34th Street
           Gainsville, Florida 32601
            Contract No. 68-02-0618
        EPA Project Officer: H.G.Richter
               Prepared for

      ENVIRONMENTAL PROTECTION AGENCY
        Office of Air and Waste Management
     Office of Air Quality Planning and Standards
       Research Triangle Park, N. C. 27711

                March 1975

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This report is issued by the Environmental Protection Agency to report  .
technical data of interest to a limited number of readers.  Copies are
available free of charge to Federal employees, current contractors
and grantees, and nonprofit organizationss - as supplies permit - from
the Air Pollution Technical Information Center, Environmental Protection
Agency, Research Triangle Park, North Carolina  27711; or, for a
fee, from the National Technical Information Service, 5285 Port Royal
Road, Springfield, Virginia 22161.
This report was furnished to the Environmental Protection Agency by
Environmental Science and Engineering, Inc. ,  Gainsville, Fla, in fulfill-
ment of Contract No. 68-02-0618.  The contents of this report are reproduced.
herein as received from Environmental Science and Engineering, Inc.
The opinions, findings, and conclusions expressed are those of the author
and not necessarily those of the Environmental  Protection Agency.  Mention
of company or product names is not to be considered as an endorsement
by the Environmental Protection Agency.
                      Publication No. EPA-450/3-75-027
                                   11

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                         TABLE OF CONTENTS
LIST OF FIGURES

LIST OF TABLES

CHAPTER 1.   -  INTRODUCTION

       1.1   -  OBJECTIVES AND SCOPE

       1.2  -  ROLE OF FIELD INSPECTION IN AN ENFORCEMENT PROGRAM

CHAPTER 2.   -  THE CHEMICAL WOOD PULPING INDUSTRY

       2.1   -  INTRODUCTION

       2.2  -  ECONOMIC POSITION

       2.3  -  PRESENT GEOGRAPHIC DISTRIBUTION

       2.4  -  FORECASTS

       2.5  -  REFERENCES

CHAPTER 3.   -  PROCESS DESCRIPTIONS

       3.1   -  DEFINITIONS

       3.2  -  THE KRAFT PROCESS

       3.3  -  DESCRIPTION OF THE NSSC PROCESS

       3.4  -  DESCRIPTION OF SULFITE PROCESS

       3.5  -  SULFITE RECOVERY SYSTEMS, PRESENT AND FUTURE
               PROSPECTS

       3.6  -  SUMMARY OF AIR POLLUTION PROBLEMS

CHAPTER 4.  -  MONITORING PROCESS AND CONTROL EQUIPMENT VARIABLES

       4.1   -  KRAFT PROCESS INSTRUMENTATION

       4.2  -  INSTRUMENTATION FOR EMISSION MONITORING
                                -i-

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                        TABLE OF CONTENTS
                          ^(Continued)



       4.3  -  CONTINUOUS SULFUR DIOXIDE MONITORS

       4.4  -  GAS/LIQUID CHROMATOGRAPHIC ANALYSIS OF REDUCED
               SULFUR COMPOUNDS

       4,5  -  ELECTROLYTIC TITRATION OF SULFUR COMPOUNDS

       4.6  -  PARTICULATE MONITORS

       4.7  -  LITERATURE CITED

CHAPTER 5.  -  AIR POLLUTION CONTROL SYSTEMS SUMMARY

       5.1  -  INTRODUCTION

       5.2  -  GENERAL DESCRIPTION OF CONTROL EQUIPMENT

       5.3  -  POWER AND COMBINATION BOILERS

       5.4  -  SULFITE SOURCES

       5.5  -  NSSC SOURCES

       5.6  -  REFERENCES

CHAPTER 6.  -  FIELD ENFORCEMENT EQUIPMENT

       6.1  -  BASIC EQUIPMENT REQUIRED

       6.2  -  RECORDS AND FORMS REQUIRED

       6.3  -  PROCEDURES AND EQUIPMENT FOR SOURCE SAMPLING

CHAPTER 7.  -  UTILIZATION OF FIELD DATA AND RECORDS

       7.1  -  GENERAL INFORMATION

       7.2  -  FILE OF FIELD DATA

       7.3  -  ADDITIONAL SOURCE INFORMATION

       7.4  -  AGENCY RECORD KEEPING REQUIREMENTS
                                -11-

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                      .   TABLE OF CONTENTS
                            (Continued)



CHAPTER 8.  -  SITE INSPECTION-ENFORCEMENT PROCEDURE

       8.1  -  GENERAL.

       8.2  -  OFF SITE OBSERVATIONS

       8.3  -  INTERVIEW WITH PLANT PERSONNEL

       8.4  -  IN-PLANT OBSERVATIONS

       8.5  -  CRITIQUE AND MEETING WITH PLANT MANAGEMENT

       8.6  -  SAFETY PRECAUTIONS

       8.7  -  SPECIAL PROCEDURES FOR KRAFT MILLS

       8.8  -  SPECIAL PROCEDURES FOR SULFITE MILLS

       8.9  -  SPECIAL PROCEDURES FOR NSSC MILLS



APPENDIX
                              -m-

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                            LIST OF FIGURES



FIGURE

  2-1.   REGIONAL DISTRIBUTION OF KRAFT PULP MILLS IN THE U.S.

  2-2.   REGIONAL DISTRIBUTION OF SULFITE AND NSSC PULP MILLS IN THE U.S.

  2-3.   PROJECTION OF PRODUCTION OF CHEMICAL PULPS IN THE U.S.

  3-1.   KRAFT PULPING AND RECOVERY PROCESS

  3-2.   TWO STAGE VENTURI EVAPORATION-SCRUBBING SYSTEM

  3-3.   CASCADE PRECIPITATOR SYSTEM

  3-4.   VENTURI EVAPORATOR-SCRUBBER SYSTEM

  3-5.   SINGLE STAGE VENTURI SCRUBBING SYSTEM

  3-6.   SECONDARY VENTURI SCRUBBING SYSTEM (FOLLOWING RECIPITATOR)

  3-7.   SECONDARY VENTURI SCRUBBING SYSTEM (FOLLOWING EXISTING  VENTURI
         SYSTEM)

  3-8.   COMPARISON OF C.E. AND B&W RECOVERY BOILERS

  3-9.   LAMINAIR AIR HEATER USED IN C.E. DESIGN

 3-10.   SCHEMATIC ARRANGEMENT OF THE COMMERCIAL OXIDATION SYSTEM

 3-11.   OXIDATION SYSTEM FOR STRONG BLACK LIQUOR

 3-12.   S-F VENTURI SCRUBBER

 3-13.   LIME KILN VENTURI SCRUBBER SYSTEM

3-13A.   TOTAL REDUCED SULFUR VERSUS EXCESS OXYGEN

 3-14.   SCHEMATIC DIAGRAM OF NSSCa PROCESS WITH NO CHEMICAL RECOVERY

 3-15.   SCHEMATIC DIAGRAM OF CROSS RECOVERY SYSTEM FOR REGENERATING
         NSSC COOKING CHEMICALS

 3-16.   FLOW SHEET OF TAMPELLA PROCESS

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                            LIST OF FIGURES
                             (Continued)

FIGURE

 3-17.   COPELAND RECOVERY SYSTEM

 3-18.   MEAD PROCESS SIMPLIFIED FLOW SHEET

 3-19.   INSTITUTE PROCESS SIMPLIFIED FLOW SHEET

 3-20.   WESTERN PRECIPITATION PROCESS SIMPLIFIED FLOW SHEET

 3-21.   SULFUR DIOXIDE REDUCTION WITH INCREASE IN Na/S RATIO

 3-22.   SULFITE PULPING FLOW SHEETS

 3-23.   EFFECTS OF AMMONIA-BASE LIQUOR SOLIDS CONTENT OF FLAME
         TEMPERATURE

 3-24.   VISCOSITY OF AMMONIA AND MAGNESIUM LIQUORS

 3-25.   SECONDARY RECOVERY SYSTEM PERFORMANCE

 3-26.   SECONDARY RECOVERY SYSTEM PERFORMANCE

 3-27.   WEIGHT RATIO, NaOH:S02

 3-28.   JENSSEN EXHAUST SCRUBBER PROCESS FLOW

 3-29.   SULFITE PULPING PROCESS, MAGNESIUM BASE RECOVERY  .

 3-30.   MAGNESIUM BISULFITE PROCESS FLOW

 3-31.   DIRECT OXIDATION RECOVERY

 3-32.   BISULFITE SULFITATION RECOVERY

 3-33.   FLUID BED PYROLYSIS RECOVERY

 3-34.   SOLID CARBONATION RECOVERY

 3-35.   GREEN LIQUOR CARBONATION RECOVERY

  4-1.   PICTORIAL INSTRUMENTATION SYMBOLS

  4-2.   BASIS INSTRUMENT DESIGN

  4-3.   INSTRUMENTATION FOR KRAFT BATCH DIGESTER
                                    -v-

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                            LIST OF FIGURES
                             (Continued)

FIGURE

  4-4.   INSTRUMENTATION FOR A CONTINUOUS DIGESTER

  4-5.   HOT STOCK SCREENING INSTRUMENTATION

  4-6.   PULP WASHER INSTRUMENTATION

  4-7.   FOUR STAGE BLEACH PLANT.INSTRUMENTATION

  4-8.   SODIUM HYPOCHLORITE BLEACH LIQUOR PREPARATION INSTRUMENTATION

  4-9.   CHLORINE DIOXIDE BLEACH LIQUOR PREPARATION INSTRUMENTATION

 4-10.   INSTRUMENTATION FOR MULTIPLE-EFFECT EVAPORATOR SYSTEM

 4-11.   INSTRUMENTATION TO CONTROL COMBUSTION IN THE LIME RECOVERY
         PROCESS

 4-12.   INSTRUMENTATION OF HIGH CAPACITY RECOVERY FURNACE

 4-13.   INSTRUMENTATION FOR LIQUOR CAUSTICIZING IN ALKALINE COOKING

 4-14.   GAS CHROMATOGRAPHY SYSTEM

 4-15.   PROBE FOR SOURCES CONTAINING ENTRAINED WATER

 4-16.   BATCH SAMPLING SYSTEM

 4-17.   CONTINUOUS SAMPLING SYSTEM

 4-18.   BARTON SAMPLING SYSTEM

 4-19.   DIAL READ OUT BOLOMETER

 4-20.   CONDUCTIVITY MONITOR

  5-1.   PRECIPITATOR FOR RECOVERY BOILER

  5-2.   VENTURI SCRUBBER WITH CYCLONIC SEPARATOR

  5-3.   CYCLONIC SCRUBBER

.  5-4.   IMPINGEMENT SCRUBBER

  5-5.   PACKED TOWER SCRUBBER AND PACKINGS

  5-6.   LARGE DIAMETER CYCLONE COLLECTOR
                                  -VI-

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                            LIST OF  FIGURES
                             (Continued)

FIGURE

 . 5-7.   MULTI-TUBE COLLECTOR

  6-1.   GAS SAMPLING SYSTEM

  6-2.   BARTON SAMPLING SYSTEM

  7-1.   ASEXTUPLE EFFECT EVAPORATOR

  7-2.   TYPICAL CONDITIONS FOR RECOVERY  UNIT  MATERIAL AND HEAT
         BALANCE
                                 -vn-

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                           LIST OF TABLES


TABLE

•2-1.  SUMMARY CHEMICAL PULP MILL CAPACITIES

 2-2.  PRODUCTION OF TEN LEADING PULP PRODUCING NATIONS

 2-3.  ANNOUNCED AND ESTIMATED EXPANSION AND PHASING OUT PLANS
       THROUGH 1980

 3-1.  SUMMARY OF MAJOR SOURCES AND TYPES OF CHEMICAL LOSSES

 3-2.  CHEMICAL EMISSIONS FROM THE RECOVERY FURNACE

 3-3.  OPERATING AND PERFORMANCE CHARACTERISTICS OF SYSTEMS
       FOLLOWING RECOVERY FURNACE

3-3A.  OPERATING PERFORMANCE OF SECONDARY SCRUBBING SYSTEMS .

 3-4.  LIME KILN EMISSIONS RELATED TO OPERATIONAL VARIABLES

 3-5.  EMISSIONS FROM NSSC PULPING

 3-6.  AMMONIA-BASE LIQUOR BURNING TESTS

 3-7.  RECOVERY UNIT PERFORMANCE

 3-8.  RECOVERY UNIT PERFORMANCE

 3-9.  JENSSEN TOWER GAS ANALYSIS

3-10.  'SUMMARY OF EMISSION DATA SULFITE PROCESS

 4-1.  KRAFT MILL INSTRUMENT SYMBOLS

 4-2.  LETTER INSTRUMENTATION SYMBOLS

 5-1.  TREATMENT EQUIPMENT CHARACTERISTICS

 5-2.  PARTICLE SIZE DISTRIBUTION OF FLY ASH FROM VARIOUS BOILERS

 7-1.  WOOD PULPING DIRECTORY EXAMPLE

 7-2.  OPERATING CONDITIONS  IN A SEXTUPLE-EFFECT EVAPORATOR




                                 -viii-

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                           LIST OF TABLES
                             (continued)


TABLE

. 7-3.  COMBUSTION OF BLACK LIQUOR

 7-4.  DUST COLLECTOR EFFICIENCY TEST

7-4A.  CYCLONE EFFICIENCY VERSUS TUBE SIZE, AND SIZE DISTRIBUTION
       OF BARK CHAR

 7-5.  POWER BOILER EMISSION DATA

7-5A.  POWER BOILER EMISSION DATA (PARTICLE SIZE)

 7-6.  SUMMARY OF TESTS ON BARK BOILER COLLECTORS

 7-7.  VENTURI SCRUBBER SPECIFICATIONS

7-7A.  VENTURI SCRUBBER EFFICIENCY TEST
                                 -IX-

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                          C H A P T E R   1

                           INTRODUCTION

   OBJECTIVES AND SCOPE

  •This manual provides guidelines and background information for use
   by personnel of state and local air pollution control  agencies in
   their surveillance and enforcement activities related  to the major
   types of chemical pulp mills.  The three  major types of mills dis-
   cussed are Kraft, Sulfite, and Neutral.Sulfite Semi-Chemical (NSSC).
   For each type of mill, the process is described;  the emissions,.
   both gaseous and particulate, are characterized;  and the types of
   applicable control equipment are delineated.   Field enforcement
   inspection, reporting and enforcement procedures  to be followed in
  . each type of mill by control agency personnel are suggested.

2  ROLE OF FIELD INSPECTION IN AN ENFORCEMENT PROGRAM

   In any size control  agency, it is necessary frequently to determine
   whether sources are in compliance with applicable regulations.
   This is the role of the field enforcement officer (FEO) in an air
   pollution control program.  It is his responsibility,  also, to carry
   out the functions of field inspection and enforcement. "

   One of the most important aspects of a control agency's enforcement
   activity is frequent and direct contact with  the  owners and opera-
   tors of processes which emit air pollutants.   Frequently, the FEO
   is the person to whom this task falls.

   The FEO also may be involved in a variety of  assignments depending
   on the size and organization of the agency and the regulations which
   are involved.  In all approved state implementation plans, a permit
   or registration system is required.  These programs assure that no
  .new sources of air pollution are constructed, reconstructed, or
   altered without the knowledge of the agency.   They also have provi-
   sions for the review of plans for construction or modification to
   insure that a proposed system is capable  of operating  in compliance
   with the regulations and makes it possible to develop  and maintain
   emission inventories.

   To insure that operating sources continue to  comply with air pollu-
   tion regulations, implementation plans provide for the audit of all
   sources periodically.  The interval may range from once every six
   months to once every five years, although the usual time period is
   once each year.  During these periodic checks, the FEO determines
   that the source is in compliance with permit  requirements, reviews
   the emission data and inspects the site to insure good operating
   and maintenance practices.

   Surveillance of a source may be conducted in  a number of ways.  The
   FEO may detect observable violations of the regulations from out-
   side the source premises, by on-site inspections, and by emission
   measurements.  The FEO has primary responsibility for the success of
   a source surveillance program even though he  may  not conduct the
   monitoring himself.

                                  -1-

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                          CHAPTER2

                  THE CHEMICAL HOOD PULPING INDUSTRY

2.1   INTRODUCTION

     The pulp and paper industry is the ninth  largest  manufacturing  indus-
     try in the United States.   This industry  accounts for nearly four
     percent of the value of all  manufacturing.

     Although paper is one of the oldest manufacturing industries,  it
     is an industry that is expanding faster than the  general  economy.
     Consumption of paper rises with increased affluence.   The per  capita
     consumption of paper in the U.S. is now over 550  pounds  per year
     compared to about 412 pounds only 12 years  ago.   There are no  signs
     that per capita consumption is leveling off.

     The pulp and paper industry is comprised  of three distinct segments:
     (1) pulp, (2) primary paper and paperboard  (cardboard, etc.),  and
     (3) converted, paper and paperboard products.

     Pulp—Most pulp is made by integrated companies and consumed cap-
     tively without moving through the marketplace.  About ten percent
     of the total pulp produced is, however, made by independent pulp
     producers without their own paper making  facilities or by integrated
     companies producing surpluses for market.  About  three percent  of
     all pulp produced is consumed outside the industry for such products
     as cellophane, rayon, cellulose esters and  ethers, and their deri-
     vatives.  Eighty percent of the pulp used for making paper comes
     from wood and 20 percent is made from waste paper or such fibers
     as cotton and bagasse.

     Primary Paper and Paperboard--This s.egment  of the industry produces
     paper, paperboard, and building paper and board.   A portion of  this
     production is sold directly to industrial users such .as  newspapers,
     book publishers, and printers, or to building and other  users.

     Converted Paper and Paperboard Products—About 70 percent of the
     primary paper production is further processed by  paper converters
     into such products as containers, bags, sanitary  tissue  products,
     and stationery.

     Wood pulp is prepared either mechanically or chemically.   In the
     mechanical processes (groundwood, defibered and exploded) wood  is
     shredded or separated by physical means.   In the  chemical processes--
     kraft, sulfite, neutral sulfite semi-chemical (NSSC), soda, and
     dissolving—wood is treated with chemical reagents which form  solu-
     ble compounds with the noncellulosic materials, thus leaving resi-
     dual cellulose.  The NSSC process involves  treating the  wood first
     with a mild chemical and then mechanically  separating the fibers.
                                    -2-

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     Data are presented in Table 2-1  which show the number of mills and
     total mill capacities for the five chemical pulping processes.  In
     Table 2-1, all capacities are based on air dried tons of pulp;
     annual capacities are based on operating at rated capacity for 350
     days per year, allowing for normal maintenance and scheduled shut-
     downs.  It is emphasized that these figures represent production
     capability and do not portray actual production data.

     Three of the chemical wood pulping processes display a potential
     to cause air pollution.  These are the kraft, sulfite, and NSSC
     processes.  Collectively, these three processes account for about
     80 percent of the total wood pulp produced in the United States.

     To define the air pollution problem posed by the chemical  wood
     pulping industry, it is necessary to establish the geographical
     distribution of existing production capacity and to identify trends
     which might cause a redistribution of production capacity in the
     future.

2.2  ECONOMIC POSITION

     The United States pulp and paper industry includes more than 400
     pulp mills of all types, mechanical and chemical.  Estimates for
     1967 indicate 37 companies, each with pulp and paper sales at the
     manufacturer's level of at least $100 million, accounted for $10.24
     billion in sales, or 49 percent of the industry's total of $20.88
     billion.

     Table 2-2 shows the wood pulp production in 1971 for the ten lead-
     ing pulp producing nations of the world (]_).  The other 60 pulp
     producing nations individually produced less than one million tons
     of pulp and collectively produced 14,441,000 tons of pulp in 1971.
     From these data, it can be determined that the U.S. and Canada
     produced 52 percent of the world's wood pulp in 1971.  This massive
     capacity, coupled with the contiguous features of the U.S. and
     Canada, place these countries in a leading position in terms of
     production.

     It is reported (2J that North American industry is planning to
     build 65 new pulp mills in the 1970's--39 in the U.S. and 26 in
     Canada.  It seems reasonable to conclude, therefore, that the U.S.
     and Canada will remain the dominant nations in wood pulp produc-
     tion at least for the next two or three decades.

2.3  PRESENT GEOGRAPHIC DISTRIBUTION

     A compilation of data on current wood pulping practice in the U.S.
     was made by searching available published reports, such as Lock-
     wood 's Directory of the Paper and Allied Trades, Post's Pulp and
     Paper Directory, and Southern Pulp and Paper Manufacturer's Southern
                                   -3-

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                      TABLE    2-1

                       SUMMARY -  U.S.A.
          CHEMICAL PULP MILL  CAPACITIES  (UNBLEACHED)
                    AS OF DECEMBER 31, 1971
Process
Kraft
Sulfite
NSSC
Dissolving
Soda
TOTALS
Number
of
Mills
128
44
48
9
4
233
*
Capacity
ADT/Day
93,600
6,650
11,300
5,100
920
117,570
Annual*
Capacity
Tons
32,800,000
2,324,000
3,950,000
1,780,000
322,000
41,176,000
1972
Production
Tons
.30,250,000
2,150,000
3,650,000
1,650,000
300,000
38,000,000
These figures represent capacity and not actual  production.   ADT stands

for air-dried tons of unbleached pulp per day; air-dried pulp contains

10 percent moisture.
                               -4- .

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     TABLE   2-2

  PRODUCTION OF TEN LEADING
PULP PRODUCING NATIONS - 1971
Nation
United States
Canada
Sweden
Japan
Finland
USSR
Norway
Mainland China
France
West Germany
Million Short Tons
45.20
20.70
9.20
9.00
7.72
6.78
2.59
2.30
1.77
1.73
              -5-

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       Mill  Directory.  Information originally tabulated included plant
       location, owner, pulping process employed,  rated mill  capacity,
       type  of wood pulped, and age of original  mill.   These  data were
       brought up to date based on in-house information, available NAPCA -
       NCASI reports, and communications with industry representatives.
       Using these data as a base, two maps have been  prepared to illus-
       trate geographically the distribution of chemical wood pulping mills
       throughout the United States.   These maps are presented here as
       Figures 2-1 and 2-2.

  2.4  FORECASTS

2.4.1  6ROHTH AND PROCESS TRENDS

       The United States and Canada produce more than  52 percent of the
       world's supply of pulp, with the U.S. in 1972 furnishing nearly  46
       million short tons.  Of this amount, 38 million tons were chemical
       pulp.  Approximately 75 percent of this was produced by the kraft
       process, nine percent by the sulfite, and ten percent  by neutral
       sulfite semichemical (NSSC).           .

       A number of forecasts have been made which  attempt to  portray the
      . future demand for wood pulp (all grades)  in the United States.
       These forecasts range from a low of 61 million  tons per year in
       1985  as given by Forest Research Report No. 17, 1965 (3), to a
       high  of 89 million tons per year in 1985 as given by Resources in
       America, 1963 (4_).  A middle of the road forecast has  been made  by
       the American Paper Institute.   Based on these data, plus numerous
       other sources, H. W. Meakin of the J. E.  Sirrine Company has pro-
       jected chemical pulp production through 1985.  These projections
       are reproduced here as Figure  2-3.

       Viewed together, these data show that through 1985, the production
       of soda pulp and dissolving pulps will remain reasonably constant;
       sulfite pulp production will decrease slightly; NSSC production  will
       nearly double, and kraft pulp  will increase to  approximately 2-1/2
       times the 1968 amount.

       In 1985, kraft and NSSC processes are expected  to dominate chemical
       pulping in the United States.   Kraft production is projected to
       account for-about 85 percent of the chemical  (about 70 percent of
       total wood pulp, all grades, production), and NSSC for about 9 per-
       cent  of the total chemical pulp production.  The total production
       of chemical pulp is expected to slightly more than double.  Regional
       distribution of pulping capacity is expected to remain in the same
       relative proportions as it is  today.

       Table 2-3 has been included to summarize announced and estimated
       expansion and phasing-out operations through 1980.
                                      -6-

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              REGION I

              REGION n

              REGION m

              REGION IV

              REGION I
REGIONAL DISTRIBUTION
  OF KRAFT PULP MILLS
       IN THE U. S.
        FIGU";

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NSSC MILLS



  O- 200 TPO

 200 - 300 TPD

  >. - 300 TPD
 SULFITE  MILLS

A   0- 100 TPD

A  100-200 TPD

   200-400 TPD

   > -400 TPD
                                                                                                                            REGION  I

                                                                                                                            REGION  H

                                                                                                                            REGION  ffl

                                                                                                                            REGION  IS

                                                                                                                            REGION  Z
                                                                                                          REGIONAL DISTRIBUTION
                                                                                                     OF SULFITE AND NSSC  PULP MILLS
                                                                                                                  IN THE U. S.
                                                        2-8
                                                                                                                    FIGURE 2-2

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                     FIGURE  2-3

              PROJECTION  OF  PRODUCTION

           OF CHEMICAL  PULPS-IN  THE  U.  S.
                                                  TOTAL
                                                  KRAFT
 o -•-"-•t-
1960
1965
1970
1980
                                             _-*NSSC

                                                 ISULFITE
                                                r> DISSOLVING
1985
                        YEAR
                            -9-

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Detailed breakdowns of Table 2-3 may be found in Appendix A
(Tables A-4, A-5, A-6, and A-7).
                             -10-

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                        T A B L E   2-3

            1  ANNOUNCED AND ESTIMATED  EXPANSION
             AND PHASING OUT PLANS  THROUGH  1980


 I.   Current and Planned New Plant  Construction  as  of  December  31,  197P  '

                           .	CAPACITY APT/DAY	

                         Kraft               Sulfite      NSSC
New
Expansion
5,866 (12)
2,135 (5)
830 (2)
0
750 (3)
568 (2)
     TOTAL             8,001  (17)              830  (2)    1,318  (5)


II.   Estimate of Phased Out Operations

                     	CAPACITY  ADT/DAY

     Time Period

     In 1968
     In 1969-70
     In 1970-80

     TOTAL



     (b)   Figures in (  ) indicate  number of mills
Kraft
205 (1)
85 (1)
209 (2)
Sulfite
835 (5)
503 (3)
1,562 (17)
2,900 (25)
NSSC
235 (1)
235 (1)
Soda
60 (1)
140 (2)
200 (3)
     In addition to the current and planned  new plant  construction
     shown above, there are at least twelve  proposed or  tentative
     mills in the talking stage of development.   These twelve mills
     would, if brought to production,  supply in excess of  an addi-
     tional 3,000 tons per day of pulp.
                               -11-

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2.5  REFERENCES

     1.  Staff, "19th Annual  Horld Review," Pulp and Paper.  43^(7),
         7- , .(June 25, 1969).  .

     2.  Staff, "Expansion/Modernization/Acquisition Report,"  Pulp
         iand Paper. 42^(51), 43- ,  (December 16,  1968).

     3.  "Timber Trends in the  United States,"  Forest Service  Report
         No. 17, U.S. Department of Agriculture, Washington, 1965.

     4.  "Resources in America's Future," Landsberg, Fishman and
         Fisher, -New York, 1963.

     5.  Josephson, H.R.  (Director, Division of  Forest Economics
         and Marketing Research, Forest Service, USDA),  "Availability
         of Wood Supplies for the  Pulp and Paper Industry,"  Paper.
         presented at 1968 Annual  Meeting of Pulp and Raw Materials
         Division of American Paper Institute,  New York,  February 20,
         1968.

     6.  Slatin, Benjamin (Economist, API), "Future Demands  for Pulp
         and Paper as They Influence Pulp Wood  Requirements,"  Paper
         presented at fall meeting of the Southeastern Technical
         Division of the  American  Pulp Wood Association,  Atlanta,
         November 21, 1968.

     7..  Staff, "U.S. New Capacity Additions Will  be Modest  Through
         1975," Paper. Trade Journal, Vol. 156,  No. 46, pp.  50-54,
         November 6, 1972.

     8.  Slatin, B., "The Paper Industry in the  South:   Running Full,"
         Southern Pulp and Paper Manufacturer,  Vol. 35,  No.  .10, pp.
         11-16, October 1, 1972.
                              -12-

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                         CHAPTER  3

                        PROCESS DESCRIPTIONS
•3.1  DEFINITIONS

     The following definitions are provided for the benefit of those
     not intimately familiar with the chemical  wood pulping industry.
     In some instances definitions are given because of special
     meanings which a term may have in this report.

     Particles - Any material which exists as a solid in a gas steam
     at duct conditions and is collected in accordance with EPA sampling
     procedures.

     Trace - A quantitative expression of emissions which is less  than
     0.01 pounds per ton of air dry unbleached  pulp.

     Standard Conditions - 29.92 inches of mercury and 70 degrees  F.

     Sulfidity - An expression of the percentage makeup of chemicals  in
     kraft cooking liquor obtained by the formula
                           Na2S + NaOH       X 10°

     where the sodium compounds are expressed as  Na20.

     Yield - The percentage of a specific weight  of bone  dry wood  that is
     converted to bone dry pulp.

     Weak Hash - A liquid stream in the kraft process  which results  from
     washing of the lime mud.   It is used mainly  for dissolving  smelt.

     Smelt - The molten chemicals from the kraft  recovery furnace  con-
     sisting mostly of sodium sulfide and sodium  carbonate.

     Oxidation Efficiency - The percentage of sodium sulfide in  the  kraft
     black liquor which is oxidized by air introduced  into the  liquor.
     The Na2S is usually expressed in grams per liter  of  black  liquor.

     Roundwood - Logs as delivered to the mill  with bark  attached  and  cut
     to specified lengths (up to 10 feet).

     Board - A heavy sheet made with single or multiple plies of pulp
     formed on a board machine such as a fourdrinier.

     Linerboard - A laminated container board usually  made of kraft  pulp.
     It consists of a base sheet which is coarse  strong pulp and a top
     liner sheet which is fine pulp.   The top liner gives the container
     board a more finished exposed surface than the base  sheet.


                                  -13- •

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      Top  Liner  -  A  sheet,  usually produced from kraft pulp, which is
      added  as a laminate to the base sheet to produce linerboard.  The
      pulp may in  some cases be bleached.

      Base Stock - A sheet, usually produced from unbleached kraft pulp,
      formed into  linerboard on a fourdrinier machine.

      Corrugating  Medium -  A sheet, usually made from NSSC pulp, which is
      corrugated to  form a  cushioning layer when attached to a single sheet
      or between two boards.  The corrugating sheet is usually 0.009 inches
      thick  and  traditionally is referred to as "9 point."

      Bark Boiler  -  A combustion unit used to produce steam for process
      or electrical  energy  which is designed to burn mainly bark and wood
      residues.

      Combination  Boiler -  A combustion unit used to produce a steam for
      process or electrical energy which is designed to burn bark and at
      least  one other fuel.

      Power  Boiler -  A combustion unit used to produce steam for process
      or electrical  energy which is designed to burn oil, coal, or gas.

      Recovery Boiler - A combustion unit used to produce steam for pulping
      and recovery operations, and to recover the chemicals from the spent
      cooking liquor.
3.2  THE KRAFT PROCESS

     The kraft process produces a dark colored fiber.   Therefore,  the
     market for the unbleached pulp is usually limited  to  its use  in board,
     wrapping, and bag papers.  If kraft pulp is to be  used  in  the manu-
     facture of fine white papers, its fibers must be treated additionally
     in a bleach plant.

     The presence of caustic soda in the cooking liquor permits the pulp-
     ing of practically all wood species.   The other active  chemical,
     sodium sulfide, creates a chemical  reaction during cooking that im-
     parts the strength characteristics to kraft fibers, producing fibers
     that are stronger than those made from NSSC or sulfite  processes.
     Small  amounts  of sodium sulfide  react  with  lignin  and carbohydrates
     in the wood to form odorous  compounds  which may  cause a reduction
     of air quality.

     In the kraft pulping process,  shown  in Figure  3-1,  the white liquor
     --a solution of sodium sulfide and sodium hydroxide  in water—is
     utilized  to dissolve the  lignin  from wood and  render cellulose fibers
     usable for  pulp manufacture.   The white  liquor is  mixed with wood
     chips  in  a  digester where the  chips  are  cooked for about three hours
     with 110  psig  steam.   During the cooking period, the digester is
                                    -14-

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             Steam
             1
          ©          ©
                  t
Recovery
Boiler
Smelt 1
60-70%
Evaporator
BL

i


- 1


Oxida-
tion
C.,_4-_
    To Stack
       *
-i      I
 t	!_
Weak Wash
Dissolving
  Tank
           1
                        Scrubber
                                       System
                        ©
               Green Liquor
          Causti-
          cizing
              White Liquor
                        „©
                      I
                       To  Stack
             |Lime Kiln
                   CaO
     Ca(OH),
                           Scrubber
                Slaking
                System
                    7
                    To
                                    ta
                                  Lj
Scrubber 1
J *

m

H
—
L_, 45-55% BL
Chips Steam
-xl 1 r*
It 1 !

Digester
Pulp f
20 and \
~a rLiquor
Washer

M.E. Evaporator
\G
vl
Conden-
sate
5a)
Weak
Liquor
)
•*
Oxi-
dizer

^
*
1
)xidation
System

}
i

k
Ox
We
.i<
                                                                                         Condensate
                 Mud  Washer
Pulp
                                                                          Air
*Refer to Table  3-1  for
 explanations.

_____ _>v    Indicates
             Gas  Streams
                         FIGURE 3-1. KRAFT PULPING AND  RECOVERY PROCESS

-------
relieved periodically to reduce the pressure buildup of various gases
generated within.   When cooking is complete, the digester contents  are
forced into a blow tank where a major portion of the spent cooking
liquor containing the dissolved lignin is drained.   The pulp passes
through the knotter, goes through various stages of washing and
bleaching, and is then pressed and dried into the finished product.

The kraft recovery process essentially consists of the following major
operations:

       1.  Concentration of weak black liquor from approximately
           17 to 50 percent solids, in multiple effect evaporators.

       2.  Further concentration to 65 to 70 percent solids in an
           additional effect known as a concentrator or using the
           heat content of the recovery furnace flue gases in a
           direct contact evaporator.

       3. .The burning of the combustible concentrated black liquor
           in the recovery furnace to recover a portion of the heat
           by oxidation of the dissolved lignin and to recover the
           inorganic chemicals in the form of molten smelt.

       4.  The preparation of green liquor by dissolving the smelt
           (a mixture of sodium sulfide and sodium carbonate) with
           water and weak wash from the causticizing plant.

       5.  The preparation of white liquor in a causticizer where
           the sodium carbonate (from green liquor) is converted to
           sodium hydroxide by the addition of calcium hydroxide.

       6.  The conversion of the precipitated calcium carbonate
           to calcium hydroxide for reuse in the causticizer by
           burning the calcium carbonate in a lime kiln and then
           slaking the product calcium oxide.

In the kraft process, chemicals in the form of solids, mists, odorous
and nonodorous gases may be emitted into the atmosphere, as summarized
in Table 3-1.  The recovery furnace potentially is the largest source
of emission of solids and sulfur bearing gases.  Digester relief gases,
blow  gases, and off  gases from the evaporators represent a considerably
smaller  volume, but  have a potentially higher nuisance value.  Not only
are these chemical losses costly, but they are air pollutants as well.
The recovery furnace, multiple effect evaporator,  lime kiln, and blow
gases  are the major  source of heat loss.

In the following sections, the sources of emission, the theoretical
explanation for the  emissions, and the various processes and equipment
used  to  reduce the chemicals and heat losses will  be discussed in
greater  detail.
                              -16-

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                             TABLE 3-1

                   SUMMARY OF MAJOR SOURCES AND
                     TYPES OF CHEMICAL  LOSSES
       Source

1.   Recovery Furnace
2.   Direct contact
    evaporator

3.   Lime kiln
4.  Dissolving tank
5.  Multiple effect
    evaporator

6.  Digester
                                        Type of Chemical  Loss
                                                         Odorous  and
     Solids

Sodium carbonate
Sodium sulfate
Carbon
Same as recovery
furnace

Lime dust
Soda dust

Sodium carbonate
Sodium sulfate

None
None
7.  Blow Tank
None
 Nonodorous Gases

Carbon monoxide
Carbon dioxide
Sulfur dioxide
Hydrogen sulfide
Methyl mercaptan
Dimethyl sulfide
Dimethyl disulfide

Same as digester
Sulfur dioxide
Hydrogen sulfide

Hydrogen sulfide
Same as digester
Sulfur dioxide
Hydrogen sulfide
Methyl mercaptan
Dimethyl sulfide
Dimethyl disulfide

Same as digester
                               -17-

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                             TABLE 3-2


           CHEMICAL EMISSIONS FROM THE RECOVERY FURNACE
Chemical
Sodium salts
Na2SO, Na2C03
Hydrogen
sulfide
Methyl
mercaptan
Dimethyl
sulfide
Sulfur
dioxide
Emission
4.5 -
SCF
900 -
200 -
60 - 1
300 -
6.0 grains/
dry
1000 ppm
1000 ppm
50 ppm
500 ppm
Ib/ton
of pulp
150 - 200
25 - 28
8 - 40
3 - 7.5
25 - 40
Ib/day*
75,000 -
100,000
12,500 -
14,000
4,000 -
20,000
1,500 - 3,750
12,500 -
20,000
*
 For 500 tons/day pulp mill
                                 -18-

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3.2.1    DIGESTER AND BLOW TANK

         During  the cooking period,  the  digester  is  relieved  periodically to
         reduce  the pressure buildup of  various gases within.  These  relief
         gases essentially contain  steam,  hydrogen sulfide, methyl mercaptan,
         dimethyl  sulfide, and  dimethyl  disulfide.   When  cooking  is completed,
         the digester contents  are  forced  into the blow tank  where a  major
         portion of the  spent cooking liquor  containing dissolved lignin is
         drained.      Gases similar in  composition  to the digester relief
         gases are released.

         The formation of mercaptan  and  dimethyl  sulfides in  the  digester re-
         sult from reactions between sulfide  and  hydrosulfide ions and methoxyl
         group of lignin in the wood being pulped.   During the digester relief
         when the pressure is suddenly released,  mercaptan and sulfides will
         be carried off  with the steam.  Hydrogen sulfide will also be released
         due to  a stripping reaction.

         The quantity of dimethyl sulfide  formed  depends  on the quantity of
         methyl  mercaptide ion  present.  In long  cooks at high temperature and
         sulfidity, the  amount  of dimethyl  sulfide may exceed the methyl mer-
         captan.  The quantity  of mercaptan and sulfide formed is directly
         proportional  to the digestion temperature and the sodium sulfide con-
         centration in the cooking  liquor.  The quantity  of mercaptan and sul-
         fide is higher  when pulping hardwoods than  softwoods.

         Various sulfur  compounds of digester relief in Ibs/ton of pulp include:
         Hydrogen sulfide, 0.01  to  0.05; Methyl mercaptan, 0.02 to 0.04; Di-
         methyl  sulfide, 0.5_to_1.0; and Dimethyl disulfide,  0.1  to 0.51  Blow
         tank Ibs/ton  of pulp figures  for  the same gases  are:  Hydrogen sulfide,
         0.1  to  0.5;  Methyl  mercaptan, 0.5 to 1.5; Dimethyl sulfide,  1.0 to 1.5;
         and Dimethyl  disulfide,  0.5 to  2.0.

         Various processes used in  the industry to reduce and recover the sulfur
         loss and the odor include:

                  1.   Oxidation of  the noncondensible gases by burning in the
                      recovery  furnace,  lime  kiln, or other suitable  devices.

                  2.   Absorption by suitable  alkaline solution such as white
                      liquor using  a venturi  or packed tower  type absorber.

                  3.   Destruction of sulfur compounds by  chlorination.

         As the  batch digester  is relieved intermittently to  avoid surging condi-
         tions,  some mills collect  the.gases in  a suitable container  and  then  feed
         continuously to either a lime kiln or a  recovery furnace.  When a con-
         tinuous digester is used,  the surges are largely eliminated  and no con-
         tainment vessel is required.  When burning  these sulfur  bearing gases
         at or above 1,400°F, complete combustion occurs  of the organic sulfides
         and hydrogen sulfide to sulfur  dioxide,  carbon dioxide and water vapor.
         Since the firing end of the lime  kiln operates at a  temperature above
                                        -19-

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2,000°F, combustion of these gases in the lime kiln is most suitable.
The sulfur dioxide generated will  be efficiently absorbed in the venturi
type lime kiln scrubber.

Chlorination, followed by caustic  absorption, is a less effective means
for treating the noncondensible sulfur compounds.   Chlorine, being a
powerful oxidizing agent, readily  oxidizes organic sulfides and hydrogen
sulfide to free sulfur, sulfonyl  or sulfoxy compounds.  The gases leaving
the chlorination stage are then absorbed in a caustic solution.

These methods of treatment effectively eliminate the odor caused by
sulfur bearing gases.  Where combustion is practiced, a suitable scrubber
will efficiently recover the sulfur compounds formed as a result of
combustion products.

Where wood with a turpentine content is cooked, there is a loss of tur-
pentine whenever a digester is relieved.  The resinous materials in
certain pulpwoods, particularly the southern pines, give off turpentine
vapor.  The heat and turpentine are recovered simultaneously by con-
densing the. digester relief gases  in a condenser.
                                 -20-

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 3.2.2  BROWN-STOCK WASHING

        Two  types  of washing  equipment  used  for  removal of black liquor are
        the  diffuser and  the  rotary-drum  vacuum  filter.   In comparing the
        advantages of the vacuum  washer and  diffuser  systems,  some pulp mill
        operators  consider that the  time  involved  in  the  use of diffusers  is
        a  distinct advantage  not  present  with  vacuum  washers in that the
        longer period of  contact  with wash water permits  removal of soda from
        the  pulp by leaching  or diffusion.

        The  rotary-drum vacuum filter arranged'for multistage  countercurrent
        washing has become standard  equipment  in most of  the pulp mills in
        the  United States and Canada.   Diffusers were generally used until
        about 1935; previously, vacuum  washers had been considered unsatis-
        factory for washing pulp  from resinous woods  because of the serious
        foaming conditions which  resulted.   Foaming trouble was overcome by
        improvement in filter design, which  prevented air from becoming en-
        trained with the  liquor.

        For  some time there have  been no  installations of diffusers, adoption
        of the rotary washer  being general.  Two,  three,  or four washers are
        used in series for multistage countercurrent  washing,  which reduces
        the  amount of wash water  required for  the  desired pulp cleanliness.
        The  rotary vacuum filter  with multiple port valves has been designed
        for  two and even  more stages of washing  on the same drum.  These sys-
        tems are more complex and require close  and accurate control owing
        to the splitting  of the filtrate  and the time element  required for
        the  liquor to pass through the  sheet and reach the valve.  These
        washers have met  with success where  the  throughput is  maintained within
        an extremely limited  range.

3.2.2.1  The  Washing Operation

        A  typical  brown-stock operation is made  up of a series of rotary-drum
        vacuum filters with  intermediate  repulpers for redilution and agita-
        tion of the pulp  sheet.   Almost all  the  systems in the United States
        use  a single liquor displacement  on  each washer.  Although the wash-
        ing  system and its operation may  be  complex,  the  fundamentals are  as
        simple as  those of the age-old  washing of  clothes.  When a limited
        amount of  water is available, washing  is best accomplished by scrub-
        bing the clothes  in part  of  the water, wringing thoroughly, and re-
        peating several times.  In pulp washing, this is  the essential process,
        except that it is on  a continuous basis, with a small  amount of water
        added in the final stage  and a  like  amount flowing countercurrent  to
        the  middle stage, or  stages, and  then  to the  first stage.  The liquid
        entering the system with  the blow and  the  amount  of water entering at
        the  last stage minus  the  water  in the  sheet then  carry the soluble
        solids out of the first  stage to  the evaporating  system, and the washed
        pulp is discharged from  the  final washer,
                                      -21-

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The vacuum filter is excellent for this soluble solids reduction be-
cause it allows the liquid entering each stage to be displaced through
the thin mat of stock as it travels over the exposed area of the fil-
ter.  A uniform application of wash liquor will achieve a higher degree
of displacement of the vat liquor in the sheet and result in a higher
displacement ratio.  Although the displacement of wash liquid in the
sheet is important, essential work is done in the intermediate repulp-
ers between the stages where the thickened sheet of pulp is diluted
and scrubbed with the weaker liquor of the subsequent stage.  Here
fibers are agitated in as low a consistency of slurry as possible in
order to achieve the minimum concentration of dissolved solids prior
to the extraction on the following vacuum filter.  Low vat consistency
promotes diffusion of the strong liquor at the fiber wall.

Emissions from brown stock washers consist of H2S and TRS ranging
from 0.01 to 0.08 and 0.12 to 0.45 Ibs/air dry ton respectively.  Con-
trol methods consists of those alternatives employed for other relief
and non-condensable gases.
                               -22-

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  3.2.3  BLEACH PLANT
         Bleaching of chemical  pulps is,  in a sense,  the continuation  of diges-
         tion.   The placement of the dividing line is sometimes  a matter of
         relative costs.   Thus, a pulp mill with high wood costs but cheap
         power and chemicals (some of which may be of mill manufacture)  may
         decide— within  limits-- to end  the cooks while the pulp retains a
         relatively high  portion of lignin and to complete the delignification
         with the more selective bleaching chemicals  as a means  of achieving
         higher yield.  A pulp mill with  low wood costs and expensive  bleach-
         ing chemicals will sacrifice some pulp yield and cook to the  lowest
         Kappa number which still gives the desired pulp qualities.  Whatever
         the situation, digestion must be properly and uniformly conducted,
         and in most cases the aim is to  remove in cooking as much of  the
         lignin as feasible.

         Our commercial cooking processes, most of whicTTproceed in  a  reducing
         system at rather high  temperature, cannot be pushed to  complete delig-
         nification without serious damage to the fibers.   All the lignin can,
         however, be eliminated by some oxidizers (as for instance chlorine
         dioxide), but reaction time is long and costs are high  and  even in
         this case there  is always the danger of carbohydrate degradation.
         Thus,  the production of white wood fibers depends on a  combination
         of cooking and bleaching.
3.2.3.1   Basic Principles
         The discovery of chlorine by Scheele  in  1774 and  the subsequent  pre-
         paration of calcium hypochlorite by Tennant initiated the  use  of
         chemicals in the bleaching of cellulose  fibers.   Initially,  equipment
         and process were rather crude, and it was only about 150 years later
         that a measure of control was established and reproducible results
         were obtained.  During all this time  the mills endeavored  to do  on
         chemical pulps with one bleaching agent  (calcium  hypochlorite) a job
         which, as we know today, cannot be done  efficiently ine  one  operation.
         There is at present no single chemical  substance  which answers all
         the requirements of a commercial  pulp-bleaching agent, so  that it is
         necessary to resort to a number of chemicals, which in turn  recommends
         the division of the process into a series of separate treatments.
         Experience gained and studies made since about 1925 furnish  a  good
         foundation for the chemical bleaching of cellulose, and  although many
         details are still obscure, enough knowledge has been developed to
         build bleach plants which yield the desired product.

         A bleaching stage normally consists of equipment  to bring  the  stock
         to the desired consistency, a mixer that will blend chemical,  fibers,
         and steam, a retention vessel wherein the reaction  may proceed,  and
         a washer for the separation of the treated fibers from the waste pro-
         ducts.  A series of such stages is called a bleaching sequence.
                                       -23-

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Unfortunately, none of the chemicals at our disposal  is  absolutely
specific, which means that in every case there  is  some unwanted  action
upon the pulp fibers.  It is, therefore, necessary to find  out how
much of the respective agent can be efficiently applied, and experi-
ence has confirmed the expectation that smaller amounts  are better
than larger ones.   On that basis, one would conclude  that the more
stages used the better the results.  This is quite true, as long as
each stage provides sufficient reaction time for the  lenient condi-
tions then existing.  However, it will  be found that  capital, main-
tenance costs, and operating costs put a low ceiling  on  the number
of stages, and a compromise must be made between academic goals  and
practicality.

Elemental chlorine is universally used for lignin  fragmentation.   It
measures up well to the above requirements.  Its specificity for
lignin is excellent, and the reaction proceeds  so  fast and  completely
that any attack upon the carbohydrates can be prevented. Chlorine
dioxide is also suitable in some respects—and  is  perhaps even su-
perior—so that it may be used in substitution  if  its present cost
differential with chlorine can be reduced.

The products of pulp chlorination and of the oxidative bleaching
stages are more soluble in an alkaline medium than in water, and
they are generally taken out of the system by an alkaline extraction.
For good efficiency, temperature and pH of these extractions must be
high, the latter at least above 10 and frequently  above  11. Such
high values are not, however, compatible with those of the  bleaching
reactions, so that separate extraction stages are  recommended for
all bleaching agents except peroxides.  In many cases these extrac-
tion stages also serve the removal of resin and hemicelluloses.
Caustic soda is the preferred agent, but other  alkalis have been used.
                              -24-,

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  3.2.4  MULTIPLE EFFECT EVAPORATORS

         In a multiple effect evaporator, black liquor is  concentrated  from 16%
         solids to about 50 to 55% solids in several  successive stages.   The
         dilute black liquor that enters  the evaporator contains some methyl
         mercaptan dissolved in the alkaline solution.   Douglass and co-workers
         (16) reported that about 0.38 pounds of methyl  mercaptan per ton of
         pulp production and only a negligible quantity of dimethyl sulfide
         enter the evaporator.  The concentrated black liquor contains  less
         residual mercaptan than the amount that entered with weak liquor.

         This means most of the original  mercaptan is stripped off daring evap*
         oration.  During the final evaporation stage, there is appreciable
         formation of methyl mercaptan.  This may be a result of the high con-
         centration of chemical reactants and the high temperature that exists
         in the final evaporation stage.   A small quantity of dimethyl  sulfide
         is also formed.  Douglass (16) concluded that most of the mercaptan
         found in the vapor and condensate from the multiple effect evaporator
         is the same as that present in the black liquor entering the evapora-
         tor.

         Hydrogen sulfide and methyl mercaptan are the major constituents found
         in the noncondensible gases and the condensate leaving the evaporators.
         The hydrogen sulfide emission may vary between 1  to 3 Ibs/ton  of pulp  ,
         whereas the mercaptan emission may be as high as  0.5 Ibs/ton of pulp.
         The condensate also carries the same odorous compounds.

3.2.4.1  Effect of Oxidation

         Weak black liquor oxidation has  been found effective in significantly
         reducing the release of odorous  compounds.  Almost 90% reduction can
         be attained with essentially 100% oxidation efficiency.  In recent
         findings, Shah and Stephenson (8) reported that condensate from the
         multiple effect evaporators, including both the condensate from the
         liquor vapors and the jet condensers, had very little noticeable odor.
         The biochemical oxygen demand was reduced by almost 28% and the pH  .
         was alkaline.  As a result, the condensate is suitable for reuse in
         the process as hot water.

         Chiorination is another means for treating the noncondensible  sulfur
         compounds.  In some cases, the waste hypochlorite bleach liquor is
         used to treat these gases.  Dimethyl sulfide is oxidized in the pres-
         ence  of chlorine to a water soluble and essentially odorless  compound
         dimethyl sulfoxide.
         The complex reactions between methyl mercaptan and chlorine result in
         high boiling, hence, less volatile compounds.  In most cases, the
         chlorination stage is followed by caustic absorption.   Packed and plate


                                         -25-

-------
      towers and low pressure drop venturi type absorbers are widely used""	""
      as chlorine caustic scrubbers.  This treatment results in essentially
      complete absorption of sulfur compounds, but the sulfur recovered will
      be a loss for the pulping process as the resulting solution will  be
      discharged to the sewer.

      In some cases, the malodorous gases are collected and then burned in
      either a lime kiln or other suitable furnace.   This is a more economical
      and more effective means  of disposal and/or recovery than bv chlorinatinn,
      The chemical reaction are:

                                2H2S + 302
                                -> 2S02 + 2H20

                                2CH3SCH2 +.902
                                -> 4C02 + 2S02 + 6H20

                                CH3SH + 302
                                ->• C02 + S02 + 2H20
     " »       . ••*                     ». '
       This method of recovery  has limited application  potential  due  to certain
       explosion dangers.   For  safe handling, it is  recommented these gases be
       diluted with large volumes of air.   In case these gases  are burned  in
       the lime kiln, the sulfur dioxide produced will  be efficiently absorbed
       in a venturi type lime kiln scrubber.   It these  gases  are  burned in
       a separator reactor, a caustic or carbonate scrubber will  be most ef-
       fective for sulfur dioxide recovery.
3.2.5  BLACK LIQUOR OXIDATION (BLO)            	

       The release of malodorous gases, such as hydrogen sulfide, mercaptan's,
       methyl sulfides  and disulfides, and sulfur dioxide can be reduced sig-
       nificantly if the black liquor is oxidized.  In recent years, black
       liquor oxidation has become an integral part of the kraft recovery pro-
       cess because of its high potential for reducing odor and sulfur losses
       from conventional boilers.  Black  liquor is oxidized either prior to
        the  recovery boiler or multiple effect evaporation, depending on the
        specific application.


       The development of various  oxidation systems is a direct result of con-
       tinuing  research to reduce  the emission of odorous gases which contri-
       bute to  the typical characteristic odor associated with kraft pulping.
       The black liquor oxidation  (BLO)  not only reduces odor and chemical
       losses from the recovery furnace  and the direct contact evaporator, but
       also reduces the chemical losses  from multiple effect evaporators if
       weak black liquor is oxidized.

        In the  kraft pulping  industry, both weak and strong black liquor oxida-
        tion are practiced.   The  oxidation of weak black  liquor offers more
        benefits such  as  lower operating  costs, reduction in  sulfur  loss from
        multiple effect  evaporators,  increased soap yield, etc. than strong
        black  liquor oxidation.   The  weak black liquor is the  liquor at 12 to
                                      -26-

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18% solids concentration entering the multiple effect evaporators,
whereas the strong liquor is 45 to 55% solids concentration leaving
the multiple effect evaporators.

The strong black liquor oxidation is practiced greatly in the southern
U.S. mills using southern pine as wood furnish.   The weak black liquor
resulting from the pine resinous woods has the tendency to foam ex-
cessively.  The soap content of the black liquor essentailly determines
the extent of the foam formation.  The foam has  been found to be very
difficult to handle.  Recently, a successful  operation of the commercial
weak black liquor oxidation plant handling 60% pine wood furnish has
been reported.

The oxidation of black liquor and its advantages have been described
in detail.  Figures 3-8 and 3-9   show typical weak and strong black
liquor systems showing the various equipments, i.e. oxidation tower,
foam tank, foam breakers and cyclones.  The arrangement of the equip-
ment may vary from one supplier to another.  The oxidation tower may
be a plate tower, packed tower or other suitable type, and the liquor
and air flows may be cocurrent or countercurrent.

Black liquor oxidation application to southern pine liquors has mainly
been restricted to the compressed air sparger -  retention tank system
because of the inherent foam problem.  Recently, there have been a few
successful attempts at oxidizing southern kraft weak black liquor in
conventional mass transfer systems.

In  the black  liquor oxidation,  the  liquor  and oxidizing agent,  such as
air, are  brought  into  intimate  contact.  The oxidized liquor, air, and
foam then enter the foam tank where  oxidized  liquor  is separated from
air and foam.  The  air  and  foam then  enter the  foam  breakers where foam
is  converted  to liquor  which is returned to oxidized  liquor  storage
tanks.  The clean air  is discharged  into the  atmosphere after  separa-
tion of entrained liquor in a cyclone.  The objective of BLO  is to pro-
duce a liquor in  which  the  sulfides  are less  than  0.1 gram per  liter.

The chemical  reactions involved in black liquor oxidation  are complex
 since  the organic material  as  well as the sulfur  bearing compounds
 react  with  the oxygen content  of the air.  The  overall  oxidation  reac-
tions  are:

                          2Na2S + 202 + H20
                         + Na2S203 + ZNaOH


                         4CH3S Na + 02 +  2H20
                         -* 2CH3S SCH3 + 4NaOH
                                -27-

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                       To Atmosphere
      Four Stage
      Oxidation
      Tower
Stack
                                                         Motor

                                                         Foam Breaker
           Black
           Liquor Pump
                                          Foam Tank
FIGURE 3-8    THE SCHEMATIC ARRANGEMENT OF THE
              COMMERCIAL OXIDATION SYSTEM
                      -28-

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    t
   I—I
                 Clean
                 Exit Air
  Cyclone
                    Foam
                   Breaker
             Liquor Sparger
               Air Sparger
                                   Air
                       Oxidation Tank
Black Liquor   Oxidized
  Feed Pump    Black Liquor
                                                                       o
                                                         Air Compressor
FIGURE 3-9    OXIDATION SYSTEM FOR STRONG BLACK LIQUOR
              CHAMPION PROCESS
                            -29-

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         In  the  case  when  black  liquor  is  oxidized at too low a temperature,
         elemental  sulfur  instead  of  thiosulfate will be formed.  This should
         be  avoided because  during evaporation of the liquor, the elemental
         sulfur  reacts  with  hydroxide at higher temperatures, reverting par-
         tially  to  sulfide ions.
3.2.5.1   Effect  of  BLO
         The value of black  liquor  oxidation  for  a  kraft mill  operating under
         the overload conditions  of a  recovery  furnace  really  depends upon the
         operation of the  direct  contact  evaporator or  scrubber  installed for
         recovering the  heat and  chemicals  from the flue gases.   Black liquor
         oxidation cannot  control hydrogen  sulfide  emission  from  the recovery
         furnace under the overload conditions, as  the  hydrogen sulfide emission
         is  primarily affected  by the  ratio of  air  to black  liquor  solids at the
         furnace hearth  and  the method of air distribution.

         To  reduce the concentration of hydrogen  sulfide in  the flue gases
         leaving the stack,  the direct contact  evaporator  or  scrubber play a
         very prominant  role.   The  oxidized black liquor contains sodium thio-
         sulfate and essentailly  no sodium  sulfide.  The carbon dioxide and
         sulfur dioxide  gases do  not react  with sodium  thiosulfate.  Thus, hy-
         drogen sulfide  generation  does not take  place.  Also, the  sodium hy-
         droxide formed  during  oxidation  reacts with sulfur  dioxide and hydro-
         gen sulfide in  the  flue  gas,  and thus  increases the absorption of both
         gases.   This clearly indicates that  oxidation  of  black liquor reduces
         the concentration of sulfur dioxide  and  hydrogen  sulfide in the flue
         gases leaving the stack  of conventional  boilers.

         The following explains what happens  in the recovery furnace when oxi-
         dized liquor is fired.

         The sodium thiosulfate will decompose  in the furnace  to  sodium sulfite
         and sulfur.  In an  oxidizing  atmosphere, the elemental sulfur is con-
         verted to sulfur dioxide which reacts  with sodium carbonate to form
         sodium sulfite  and  is  further oxidized to  sodium  sulfate.

         The overall reactions  are  as  follows:

                                Na2S203
                                       +  Na2S03 + S

                                S + 02
                                       -*•  so2'

                                Na2C03 +  S02
                                             + Na2S03  + C02

                                Na2S03 H
                                         -30-

-------
      The amount of sulfur dioxide emission from the recovery furnace is pro-
      portional to the concentration of sodium thiosulfate in the black liquor.
      Theoretically, for every mole of sodium sulfide oxidized, \ mole of sul-
      fur dioxide should be emitted.  However, due to high availability of
      sodium carbonate in the recovery furnace, the actual emission is less.
      It is observed that for a mill practicing oxidation, the sulfur dioxide
      concentration in the flue gases leaving the recovery furnace increases.
      But in the case of mills using the venturi type evaporator and scrubber,
      this sulfur dioxide will be efficiently absorbed.   If the reducing at-
      mosphere exists in the recovery furnace, then the elemental sulfur will
      be converted to hydrogen sulfide instead of sulfur dioxide.

      With the oxidation of black liquor, the hydrogen sulfide concentration
      leaving the recovery furnace stack can be reduced by 90 to 98%, and a
      significant reduction of odor can be attained.  With black liquor oxida-
      tion efficiency essentially 100%, and by proper operation of the recovery
      furnace, it is possible:  to reduce concentrations of hydrogen sulfide
      to 1 to 2 ppm; methyl mercaptan to 1 to 3 ppm; and dimethyl sulfide to
      1 to 2 ppm.  Even with these low concentrations, the typical  kraft mill
      odor can still be detected since these compounds can be sensed down to
      the range of a few parts per billion.


3.2.6  THE RECOVERY FURNACE

       Potentially, the major source of chemical and  heat loss in the kraft
       pulping process  is  the recovery furnace which  is the  heart of the re-
       covery  process.  Since the  inception of the  kraft  recovery process,
       significant  progress  has  been made in  reducing the loss of heat and
       chemicals from the  recovery  furnace.

       The flue gases leaving the  recovery  furnace  contain not only 90 to 200
       pounds  of sodium compounds  (mainly sodium sulfate  and  sodium carbonate)
       per ton of pulp  production,  but also 35 to 50  pounds  of sulfur bearing
       malodorous gases such  as  hydrogen  sulfide, sulfur  dioxide, methyl mer-
       captan, dimethyl sulfides,  and disulfides.

       In  the  recovery  furnace,  heat  is obtained from the combustion of  the
       organic constituents  of  the  black  liquor, and  the  inorganic constituents
       are recovered as a  molten  smelt.   The  concentrated black  liquor at 65
       to  70 percent solids  content  is sprayed  into the furnace where the water
       content is flashed  off.   As  a result of pyrolysis, the organic matter
       forms volatile products  which burn in  presence of  oxygen.  The combus-
       tion products, sulfur  dioxide and  carbon dioxide,  react with sodium com-
       pounds  to form sodium  sulfite and  sodium carbonate.   The  hot carbon from
       the pyrolized organic  matter  reduces the sulfur  sodium compounds  to
       sodium  sulfide.  The  smelt  that leaves  the furnace essentially contains
       sodium  sulfide and  sodium carbonate.

       While the black  liquor is  burned in  the furnace, an appreciable quantity
       of  sodium compounds are  sublimed.  As  the combustion  gases cool,  the
       sublimate condenses and  is  entrained in  the  gas  stream as a  very  finely


                                        -31-

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 dispersed  fume  (essentially  sodium  sulfate" and  sodium carbonate).  Most
 of  this  is reclaimed  by  deposition  on the  heating  surfaces of  the re-
 covery furnace  and  on the  wetted  surfaces  of  the direct contact evap-
 orator if  one is  used.   The  remainder,  in  suspension in the flue gas
 as  very  fine solid  particles,  passes from  the unit.  The quantity of
 sodium (largely as  sodium  sulfate)  in the  flue  gas, depends upon service
 conditions and  operating care  of  the recovery furnace.  It will vary
 from  90  to 200  pounds with an  average of about  150 Ibs/ton of  pulp.  For
 a 1000 ton/day  pulp production, this abounts  to 75 tons/day of dust
 entrained  in the  flue gases.   This  chemical loss in not only costlv
 but it is  also  a  nuisance  as an air pollutant.

 The sulfur bearing  malodorous  gases, such  as  hydrogen sulfide, sulfur
 dioxide, methyl mercaptan, dimethyl sulfides  and disulfides, represent
 another  source  of chemical loss and air pollution.  Large volumes of
 hydrogen sulfide  may  be  formed in the recovery  furnace and, unless opti-
 mum combustion  conditions  exist,  it will be discharged to the  atmosphere.

 The hydrogen sulfide  emissions from a kraft recovery furnace is primari-
 ly  affected by  the  ratio of  air to  black liquor solids at the  furnace
 hearth and the  method of, air distribution.  If  a proper balance is main-
 tained between  the  black liquor feed and the  air input, a complete com-
 bustion  of all  pyrolysis products can be attained  and all reduced sul-
 fur gases  will  be converted  to sulfur dioxide.  The theoretical air
 requirements for  complete  combustion of a  typical  kraft black  liquor
 and production  of smelt  of the desired  composition are of the  order of
 four  to  six pounds  of air  per  pound of  black  liquor solids.  As the
 kraft recovery  furnace is  overloaded, the  amount of air and its dis-
 tribution  become  limited by  the forced  draft  and induced draft fan capa-
 cities.  The forced draft  fan  "pushes"  the  combustion air into the
 furance, and the  induced draft fan  "pulls"  the combustion from the
 furnace.  Consequently,  reducing  conditions in  the hearth or char bed
 become more pronounced,  thereby generating  increased quantities of
 hydrogen sulfide.  This  increased hydrogen  sulfide generation  is a
 function primarily  of gas  composition in equilibrium with the  liquid
 solid phase at  the  furnace hearth.  The air to  solids ratio has a very
 promounced effect on  the concentration  of  hydrogen sulfide and sulfur
 dioxide  in the  flue gases  leaving the recovery  furnace.

 In  present day  practice, the recovery furnace functions as both a
 chemical reactor  and  steam generator—the  steam generation function tends
 to  predominate  with older  mills.  The recovery  furnace can be  over-
 loaded to  achieve increased  pulp  productions  and increased steam re-
 quirements.  Increased pulp  productions mean  increase in the firing rate
 of  black liquor.  As  the amount of  black liquor solids fired increases,
 the ratio  of air  to solids decreases, which results in the increased
 generation of hydrogen sulfide.   To obtain  increased quantity  of steam,
 the flue gas temperature entering the superheater section of the furnace
.has to be  maintained  at  maximum.  This  can  be attained by using the
 minimum  quantity  of air  practicable or  by  using auxiliary fuel.  This
 results  in a decrease in the ratio  of air  to  solids and hence  an in-
 crease in  generation  of  hydrogen  sulfide.
                                -32-

-------
       Table  3-2  summarizes  the  type  and quantity of chemical losses occurring
       at  the_recovery  furnace.   The  gaseous emissions_are based on the assump-
       tion that  the mill does not practice any black liquor oxidation.  The
       quantities may vary from  mill  to mill.  It can be seen that the chemical
       losses  from the  recovery  furnace can vary from 53 to 80 tons per day.


3.2.7  DIRECT CONTACT EVAPORATOR

       In  the classic kraft  process,  flue  gases  leaving the  recovery  furnace
       pass  through  the direct contact evaporator  (DCE), where  as  a result of
       heat  and mass transfer, the concentrated  liquor  from  multiple  effect
       evaporators  is further concentrated to  65  to 70  percent.  Some  mills
       built  since about 1968 do not  utilize direct contact  evaporators,  but
       provide the additional concentration by an  additional  stage of  multiple
       effect.  In general,  four types of  direct  contact evaporators  are  used:
       the cascade,  the cyclone, the  P-A  venturi,  and  the  two-stage venturi
       scrubber.   In all four evaporators, the sensible heat content  of the
       flue  gas leaving the  recovery  furnace  is  utilized to  further concentrate
       the black liquor from multiple effect evaporators prior  to  firing  in
       the recovery  furnace.  The carbon  dioxide  (16 to 17  percent by  volume)
       and sulfur dioxide (300 to 500 ppm) present in  the  flue  gas react  with
       the sodium sulfide content of  black liquor  and  release hydrogen sulfide
       according to  the following reactions:

                               Na2S + C02 + H20
                               -*• Na2C03 + H2S

                               Na2S + S02 + H20
                               + Na2S03 + H2S

       Depending upon the sulfide ion concentration and the  pH  of  the  black
       liquor and the mixture of gases in  the  incoming  gas  stream, the direct
       contact evaporator may either  emit  hydrogen sulfide  or absorb  sulfur
       dioxide and hydrogen  sulfide.   Some of  the  sulfur dioxide in the furnace
       flue  gas is absorbed  by reacting with  sodium carbonate,  thus forming
       sodium sulfite:
                             .  Na2C03 + S02
                               -»• Na2S03 + C02


       The extent to which sulfur dioxide  is absorbed  largely depends  upon the
       type  of direct contact evaporator  that  follows  the  recovery furnace.
       The venturi type evaporators provide the  best absorption efficiency as
       compared to the cascade and cyclone types.

3.2.8  RECOVERY FURNACE SYSTEM

       In  recovery  furnaces  which utilize  any  type of  DCE}  it is yery  dif-
       ficult to distinguish the emissions evolved from the  furnace alone


                                      -33-

-------
          as opposed to the combined emissions  exiting the DCE  and  into  the
          stack.   In a case such as  this,  the equipment combination may  be
          referred to as the recovery furnace system.


3.?.8.1   Control of Particulate Emissions From the Conventional Recovery
         Furnace System

         For the recovery of chemicals in paniculate form (sodium sulfate and
         other salts) from the flue gas leaving the recovery furnace, there are
         four systems offered to the kraft pulping industry:

                   1.  The two-stage evaporator-scrubber system.

                   2.  The cascade-precipitator system.

                   3.  The cyclone-precipitator system.

                   4.   The P-A (Pease-Anthony)  venturi  evaporator-
                       scrubber system.

         The cascade-precipitator and cyclone-precipitator systems  are very
         similar in performance and  operation.

         The two-stage evaporator-scrubber system  shown  in Figure 3-2 consists
         of a venturi  evaporator and venturi scrubber.   The flue gas  from the  re-
         covery  furnace enters the venturi  evaporator  and  contacts  the liquor
         to be concentrated.   As a result  of simultaneous  heat  and  mass  transfer,
         the liquor is concentrated  to the desired solids  concentration  for  firing
         in the  recovery furnace.  The make up  liquor  to evaporator is either
         liquor  from the multiple effect evaporator or a mixture of such liquor
         and bleed from the second stage scrubber, depending  on what  liquor  is
         being used in the second stage as a scrubbing  medium.  The gas  then
         enters  the venturi  scrubber where all  the energy  (pressure drop) is
         essentially utilized  for scrubbing and optimum dust  collection  efficiency
         is attained.

         The cascade-precipitator system shown  in  Figure 3-3  consists of a cascade
         evaporator and an electrostatic precipitator.   Further concentration  of
         black liquor from a multiple effect evaporator is  accomplished  in a cas-
         cade evaporator using the recovery furnace flue gases.  The  modern  cascade
         evaporator consists of from one  to four wheels in parallel and/or  series
         configurations.  The  arrangement  and amount  of heating surface  required
         depend  upon the weight and  temperature of gas and the  desired final
         concentration of black liquor. The gas temperature leaving the cascade
         and cyclone evaporators is  normally maintained at 300°F or higher.   If
         the gas temperature entering the  precipator  is less  than 300°F, local
         cold spots develop and result in  condensation, fouling and rapid cor-
         rosion  of the precipitator.
                                        -34-

-------
U1
I
                                        ventun
                                      Evaporator
                Recirculating
                         Pump
  To. Cooling
 - Tower

Separator
& Cooler
                                                                  Make-up
                                                                  Liquor
                                            Recirculating pump
                  FIGURE  3-2.  TWO STAGE VBJTURI EVAPORATION - SCRUBBING SYSTEM

-------
I
oo
cr>
i
                                                                                To  Stack
                                                 Cascade  Evaporator
Precipi-
 ta tor
             Black
             Liquor
             45-55%
                                  Black  Liquor  60-70%
                  Smelt
                              FIGURE 3-3.  CASCADE PRECIPITATOR SYSTEM

-------
The flue gas leaving the contact evaporator then enters  the electrostatic
precipitator where the sodium compounds--in dust form—are collected.   The
precipitator is operated on the principle that a particle suspended in
the flue gas, if subjected to a sufficiently strong electrostatic  field,
becomes charged electrically and tends to migrate toward and adhere to
an oppositely charged electrode.  The collection electrodes are mechani-
cally rapped periodically to shake the particles loose into a hopper or
a vat of liquor.  To energize the precipitator, potentials of 75,000 to
100,000 volts are necessary.  The important factors for  efficient  pre-
cipitator operation are the gas temperature, moisture content, velocity
and the retention time within the area subject to electrical  charge.
In the P-A venturi evaporator-scrubber system shown in Figure 3-4, both
the collection of dust from the flue gas and concentration of liquor by
evaporation are accomplished simultaneously in a venturi type device.
The system's operating principle is the collision of dust particles with
liquid droplets formed by atomization and high velocity gas impact with
liquor.  The liquid droplets, with their dust particles entrapped, are
then separated from the flue gas in a cyclonic separator.

The operating and performance characteristics of the three systems are
summarized in Table 3-3.  With the use of a two-stage evaporator-scrubber
system, the chemical loss in the form of dust can be reduced by more than
90%.  The total particulate matter loss can be reduced  to  750 to  1,000  Ibs/
day for a 500 tons/day pulp production.  Similar performance can be ob-
tained by combining a cascade evaporator or cyclone evaporator with
secondary scrubbing.

The secondary scrubbing systems shown in Figures 3-5 and 3-6, namely
cyclonic and venturi, offer a solution to upgrade the dust collection
and/or thermal efficiencies of the existing cascade-or cyclone-precipi-
tator system.  Table 4 summarizes the operating performance of the
secondary scrubbing systems.  The cyclonic scrubber system eliminates
precipitator snow out problems land provides efficient heat and chemical
recovery.  This system's performance is excellent as a backup scrubber
after an efficient precipitator.  When the precipitator is down for
major overhaul or for replacement, and when its performance has deter-
orated, a cyclonic scrubber alone cannot provide .adequate dust col-
lection efficiency.  However, if a venturi type scrubber system is
used following the precipitator, and should it become necessary to take
the precipitator off line for some period of time, the venturi scrub-
ber with proper static energy applied may perform adequate emission
control alone.  Many mills do not have nor need a secondary scrubber on
this source.

With a precipitator efficiency of only 80 percent, the (secondary) cyclonic
scrubber can provide 90 percent efficiency on emissions  leaving the  pre-
cipitator, for a  total of 88 percent efficiency, at a pressure drop  of
4 to 6 inches W.G.  Likewise, a (secondary) venturi scrubber system  can
                               -37-

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                                                         Venturi
                                                       Evaporator
                                                        Scrubber
oo
c»
                                                           Separator
                                                                                   To  Stack
                                           Recirculating  Pump
                    FIGURE 3-4.   VENTURI EVAPORATOR-SCRUBBER SYSTEM

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                             TABLE 3-3

             OPERATING AND PERFORMANCE CHARACTERISTICS

               OF SYSTEMS FOLLOWING RECOVERY FURNACE
Gas temperature
  °F In
  °F Out
Liquor concentration
  % Solids In
  % Solids Out

Dust loading
GR/SCF dry
  In
  Out

Na2SOi+ Ib/ton of pulp
  In
  Out

Efficiency %

Pressure drop "WG"

Snow Out problem

Maintenance

Thermal efficiency

Space requirement

Equipment cost

Operational
  (Availability)

Secondary
  Scrubber requirement
Two Stage
Evaporator
Scrubber System
600
150
Evap-45 Scrub-! 7
60 - 70 -30
4.0
0.04
150
1.5
99,0+
30 - 35
No
Very little
Very high
Less
Higher
Continuous
Cascade
Precipitator
System
600
300
45 - 50
60 - 70
4.0
0.08 - 0.4
150
3-15
90 - 98
8-10
Yes
High
Low
More
Highest
Non
continuous
P-A Venturi
Scrubber
System
600
190
45 - 50
60 - 65
4.0
0.4 - 0.8
150
15 - 30
80 - 90
35 - 40
No
Low
High
Less
Low
Almost
continuous
No
Yes
Yes
                                 -39-

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Cascade or
Cyclone Evap-
orato/*



Bleed
                                     =i To Cooling
                                     ^~ Tower

                                      Separator
                                      & Cooler
Make-up
Liquor
  Recirculating  Pump
FIGURE 3,5.   SINGLE STAGE VBMJRI  SCRUBBING SYSTEM

-------
Cascade
Cyclone
orator

or
Evap-
)

                          Precipitator
                     Bleed
                                 Venturi
                                 Scrubber
                                                Separator
                                                          Make-up
                                                          Liquor
                       Recirculating Pump
FIGURE  3-6.  SECONDARY VENTURI SCRUBBING  SYSTEM
                      (FOLLOWING PRECIPITATOR)

-------
Recovery
 Boiler
  Venturi
Evaporator-
 Scrubber
**To Stack
                                                      .».»«
                                          Recirculating Pump
                                                                    Separator
                                                                    & Cooler
                                                                  To  Process
                                                                       To  Cooling
                                                                         Tower
                                                                   Make-up
                                                                   Liquor
     Recirculating  Pump
  FIGURE 3-7.   SECONDARY VENTURI  SCRUBBING SYSTEM
               (Following Existing Venturi  System)

-------
                             TABLE 3-8 A

                      OPERATING  PERFORMANCE OF

                    SECONDARY SCRUBBING SYSTEMS
Gas temperature
  °F In
  °F Out
Dust loading
  GR/SCF Dry In
  GR/SCF Dry Out

Efficiency %

Pressure Drop "WG"

Liquor Concentration
  % Solids In
  % Solids Out
                                    Cyclonic
                                    Scrubber
   300
160 - 170
0.5 - 1.0
0.05 - 0.1

    90

   1-3
  0 - 10
    15
                            Venturi
                           Scrubber
   300
160 - 170
0.5 - 1.0
  0.04

 90 - 98

 10 - 15
  0 - 18
    30
                              -43-

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         provide 98 percent efficiency at a pressure drop  of 12  to  15  inches
         W.G., thus an overall  efficiency of 98 to 99 percent can be  attained.

         When  the  precipitator  is taken out,  the gases from  the evaporator can
         be  diverted  to the  venturi system.   An overall efficiency of  95 %,  plus "
         can be  attained  at  a pressure drop of 25  in. w.g. across the scrubber.

         When  the  P-A venturi evaporator-scrubber  system is  providing only 85
         to  90%  efficiency at a pressure  drop of 35  to 40  in. w.g. and has to
         be  upgraded  to obtain  an overall efficiency  of 99%  plus, it should be
         upgraded  by  conversion into a two-stage system, as  shown in Figure 3-7.
         The existing separator and fan could be utilized  in  the converted two-
         stage system, by transferring the  majority  of available static  pressure
         to  the  second stage with only a  minimum applied to  the first (evaporation)
         stage.  This way, performance equivalent  to  a two-stage evaporator-scrub-
         ber system can be achieved.
3.2.9   RECOVERY  FURNACE  SYSTEMS  WHICH  ELIMINATE  DIRECT CONTACT BETWEEN
        BLACK LIQUOR AND  FLUE  GASES

        In the past  five  years, there have  been several applications of the
        "odor free"  recovery boiler  in  the  industry,  as manufactured by the
        two major boiler  companies,  Babcock and Wilcox  (B &  W) and Combustion
        Engineering  (C-E).   Essentially,  the modification developed by both
        companies avoids  direct contact of  black  liquor with boiler flue gases,
        as formerly  required to achieve liquor concentrations in  the 70% solids
        range.
        By eliminating the D-C evaporator,  the B & W approach  puts  more  emphasis
        on the multiple effect evaporator train, which heretofore has  been  only
        marginal  in raising the solids  concentration of weak black  liquor.   B  & W
        says its  improved design can reach  60 to 65% solids, well above  the usual
        minimum of 55% that is required for steady, safe operation  of  the boiler.

        B & W's three main design changes are: additional indirect  evaporation
        stages which uses forced circulation of liquor through the  exchangers
        (due to the higher viscosity of strong black liquor);  a revised  tube-
        survace., arrangement to offset scaling and poorer rates of heat transfer;
        and a steam pressure limit of 35 psig. coming into the multiple  effect
        train, so that maximum steam pressure in the first effect (where vis-
        cosity is highest) to 8 psig.  (Usual practice has been to  employ  60
        psig. steam, but the lower pressure, notes the company, brings the
        temperature down to a point where scaling is substantially  reduced).
        To recover heat from the flue gases, and also to cool  gases before ad-
        mitting them to the electrostatic precipitator, B & W outfits the
        economizer with approximately three times the surface area of a compar-
        able unit feeding 50% liquor to a direct contact evaporator.   The gas
        temperature at the exit of the enlarged economizer is about 50°F higher
        than with a direct contact unit.  The only advantages claimed for the
        higher temperatures are reduction of corrosion in the precipitator and
        less steam plume.

                                         -44-

-------
         provide 98 percent efficiency at a pressure drop of 12  to 15  inches
         W.G., thus an overall  efficiency of 98 to 99 percent can  be attained.
        When  the  precipitator  is taken out, the gases from the evaporator can
        be diverted  to  the venturi system.  An overall efficiency of  95 %,  plus"
        can be  attained at a pressure drop of 25 in. w.g. across the scrubber.

        When  the  P-A venturi evaporator-scrubber system is providing only 85
        to 90%  efficiency at a pressure drop of 35 to 40 in. w.g. and has to
        be upgraded  to  obtain  an overall efficiency of 99% plus, it should be
        upgraded  by  conversion into a two-stage system, as shown in Figure 3-7.
        The existing separator and fan could be utilized in the converted two-
        stage system, by transferring the majority of available static  pressure
        to the  second stage with only a minimum applied to the first (evaporation)
        stage.  This way, performance equivalent to a two-stage evaporator-scrub-
        ber system can  be achieved.


3.2.9   RECOVERY FURNACE SYSTEMS WHICH ELIMINATE DIRECT CONTACT BETWEEN
        BLACK  LIQUOR  AND FLUE GASES

        In the past five years, there have been several applications of  the
        "odor  free" recovery boiler in the industry, as manufactured by  the
        two major  boiler companies, Babcock and Wilcox (B & W) and Combustion
        Engineering (C-E).  Essentially, the modification developed by both
        companies  avoids direct contact of black liquor with boiler flue gases,
        as formerly required to achieve liquor concentrations in the 70% solids
        range.
        By eliminating the D-C evaporator,  the B & W approach  puts  more  emphasis
        on the multiple effect evaporator train, which  heretofore has  been  only
        marginal  in raising the solids concentration of weak black  liquor.   B  & W
        says its  improved design can reach  60 to 65% solids, well above  the usual
        minimum of 55% that is required for steady, safe  operation  of  the boiler.

        B & W's three main design changes are: additional indirect  evaporation
        stages which uses forced circulation of liquor through the  exchangers
        (due to the higher viscosity of strong black liquor);  a revised  tube-
        survace arrangement to offset scaling and poorer rates of heat transfer;
        and a steam pressure limit of 35 psig. coming into the multiple  effect
        train, so that maximum steam pressure in the first effect (where vis-
        cosity is highest) to 8 psig.  (Usual practice has been to  employ  60
        psig. steam, but the lower pressure, notes the company, brings the
        temperature down to a point where scaling is substantially  reduced).
        To recover heat from the flue gases, and also to cool  gases  before ad-
        mitting them to the electrostatic precipitator,  B & W  outfits  the
        economizer with approximately three times the surface  area of  a compar-
        able unit feeding 50% liquor to a direct contact evaporator.   The gas
        temperature at the exit of the enlarged economizer is  about  50°F higher
        than with a direct contact unit.   The only advantages  claimed  for the
        higher temperatures are reduction of corrosion in the  precipitator and
        less steam plume.

                                        -44-

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   C-E ACE System  	
       B&W System  	                 ^
   *In B&W Design, economizer is enlarged
Gas To Stack
     •^	
         Air
                              Gas
         Ljunstrom-Type
           Air Heater
                          Cascade
                          Evapora
             Liquor From Multiple-
             Effect Evaporators
Air
i fc
*
ie
~ator
F

••
urnace
FIGURE 3-10. COMPARISON OF C-E AND B&W RECOVERY BOILERS
             SHOWS DESIGN DIFFERENCES WITH OR WITHOUT
             THE DIRECT-CONTACT EVAPORATOR
Flue Gas Outlet
                                 Heating
                                 Surface
   FIGURE 3-11. DETAIL SHOWS THE LAMINAIRE AIR HEATER
                USED IN THE C-E DESIGN
                            -46-

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3.2.11    LIME KILN
         The lime kiln is a major source of chemical  loss  in  the  form  of  particu-
         late emissions.   The gaseous emissions  are  not  so pronounced.  In  the
         lime recovery process, lime is usually  lost at  various points—some with
         grits or impurities removed by the slaked  lime  classifier  and  some at
         storage facilities for reburned lime.   The  major  source  of loss  is the
         exit gases leaving the kiln.  The lime  dust escaping with  the  flue gases
         is more objectionable than the calcium  carbonate  and lime  lost at  the
         other end of the kiln because it is reactive lime.   The  major  loss of
         particulate matter from this source is   alkaline  earth oxides.

         The other minor chemical loss which creates an  odor  problem,  is  the  re-
         lease of sulfur bearing compounds through  exit  flue  gas.   The quantity
         of odor from lime kiln gases is very, small  as  compared with other
         sources in the pulp mill.  To understand and develop an  odor  control
         system or to minimize the formation and release of odorous compounds,
         it is necessary to evaluate the sources contributing to  odor  emission.
         The possible sources of sulfur compounds are:

                   1.  The degree of washing of  lime mud and  the  filter cake
                       dryness determines the amount of  sodium sulfide in the
                       lime sludge.  In cases where liquor sulfidity is high
                       and washing poor, as much as 5 pounds  of sodium sul-
                       fide per ton of pulp production may be present  in  lime
                       sludge fed to the kiln.   The high carbon dioxide and
                       high temperature atmosphere  may favor  release of hydro-
                       gen sulfide and sulfur dioxide according to  the follow-
                       ing reactions:

                                  Na2S +  S02+ H20
                                  + Na2C02 + H2S


                                  2H2S + 302
                                  -> 2S02 + 2H20

                       The hydrogen sulfide emissions will increase with  lower-
                       ing of kiln exit temperature or oxygen content.

                   2.  A   high sulfur content fuel oil  used  in the kiln  as a
                       fuel source results in the release of  sulfur dioxide.

                   3.  Where the water supplies  are  limited and a mill  has  a
                       tight water balance, the  evaporator condensate  is  used
                       as makeup to the kiln scrubbing system.  If  the  mill
                       does not practice weak black  liquor oxidation or strip-
                       ping of the condensates,  this  may become a significant
                       odor source.
                   4.
Some mills practice burning of the noncondensible gases
released in the digester and evaporation process  in  the
kiln.  These gases with high sulfur content are efficiently
burned in the high temperature zone.
                                         -47-

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The use of wet scrubbers, of low sulfur content fuel,  and the efficient
control of combustion and the proper washing of lime mud will  definitely
reduce the odorous gases and chemical  losses in the form of sulfur diox-
ide and hydrogen sulfide.

The flue gas leaving the kiln carries an appreciable quantity of dust.
The chemical composition of the dust is essentially carbonates and
oxides of sodium, calcium and magnesium, sodium sulfate and acid in-
solubles (consisting of aluminium oxide, iron oxide, silica and others).
The amount of chemicals leaving the kiln in the flue gases may range
from 5 to over 20 grains/cubic foot.  This represents  a loss of 10 to
20 tons/day.

To recover these chemicals, the wet scrubber is very widely used.   Of
the various types, the venturi scrubber in Figure 3-12 has proven to
be most efficient.  There are about 100 installations  throughout the
industry.  The lime kiln scrubber should be considered as an essential
and integral part of kraft chemical and heat recovery  process, just as
a lime kiln constitutes an integral part of the causticizing and chemi-
cal recovery process.

With the use of the efficient venturi scrubber, these  chemical losses
are reduced by 99% plus.  The collection of lime dust  is not as diffi-
cult as the collection of soda dust.  The soda is in the form of very
fine fume and requires higher energy for collection.  At a total pres-
sure drop of 15 to 17 in. w.g. across the scrubber system, essentially
all the lime dust can be recovered whereas only 70 to  80% soda fume is
recovered.  The sulfur dioxide and hydrogen sulfide will be absorbed
efficiently in the venturi type scrubbers.  It is believed that better
mud washing methods and improved control of lime, kiln  operation,
coupled with the efficient scrubber operation,  can  result in a totally
satisfactory solution to this problem.

The lime kiln scrubber system as in Figure 3-12 consists of a venturi
flooded elbow and a cyclonic separator.  In the venturi, the scrubbing
liquor enters tangentially into the shelf section and  swirls down the
converging walls.  It then hits the lip section in the throat which
throws11 the liquor toward the center thus creating a curtain of liquor
across the throat.  The dust laden gas enters the venturi through a
thimble, accelerates through the convergent section, impacts with the
liquor curtain thus shattering it into droplets into which the particu-
late matter imbeds and is collected.  The cleaned gas  and liquor enter
the flooded elbow.  The gas then tangentially enters the cyclonic
separator where any entrained liquor is separated.  For efficient
separation, both the spin height and the vertical velocity are important
factors for design.  If the separator is not properly  designed, carry
over of liquor droplets will occur and will result in  increased dust
loss to the atmosphere.
                                -48-

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FIGURE 3-12.   S-F VENTURI SCRUBBER






                -49-

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The venturi scrubber has also been found to  be an  effective  device  for
the removal of malodorous gases.   The scrubbing solution  used  in  the
lime kiln scrubber is alkaline, and the acidic gases  such as hydrogen
sulfide, sulfur dioxide, etc., will be efficiently absorbed, provided
solution pH is maintained in proper range.
                              -50-

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  3.2.12  THE EFFECT OF PROCESS AND CONTROL EQUIPMENT VARIABLES ON PULP
          PRODUCTION AND EMISSIONS

          The following sections describe process and emission  control  equip-
          ment variables which affect pulp production rates and attendant
          emission levels for the kraft pulping process.

3.2.12.1  Recovery Furnace System

          In the kraft process the more conventional  chemical recovery  complex
          consists of the recovery boiler and the direct  contact evaporator(s).
          In the more recent "low odor" recovery systems, the acidic  products
          of combustion from the furnace  are not directly contacted with the
          strong black liquor, thus eliminating the stripping of malodorous
          reduced sulfur compounds from this unit process.

          NCASI studies (18) have identified black liquor solids firing rates,
          available oxygen supply, adequate residence time in the combustion
          zone, and turbulence to be important factors in controlling reduced
          substances lost from the smelting zone of recovery furnaces.   In
          other studies, Thoen et.al.  (,19) reported that in addition  to the above
          factors, the ratio of primary to secondary air  and liquor spray
          firing patterns were significant factors in controlling emissions
          from recovery furnaces.   In another detailed study, Murray  (20)
          further related the ratio of available  air to  liquor flow  and sul-
          fide content of the fired liquor to reduced sulfur concentrations
          in recovery furnace exit gases.  Smelt bed depths, although not
          considered to be as important as the previously described variables,
          can have some effect on both particulate and gaseous  emissions from
          the furnace.  In general, the deeper the smelt  bed, the greater the
          loss of both particulate and gaseous materials  from the smelting
          zone.

          Black liquor firing rates are directly proportional  to pulp
          production and also have a profound effect on both particulate
          and gaseous sulfur emissions from the furnace itself.  High
          flue gas velocity, normally attendant to increased liquor firing
          rates, may cause the carry-up of small droplets of black liquor
          which have been sprayed into the furnace.  The  increased flue
          gas velocity may also entrain additional quantities of the  inor-
          ganic sodium salts, primarily sodium sulfate and sodium carbon-
          ate, which are present in recovery complex emissions.
                                       -51-

-------
The direct contact evaporator(s) receiving the furnace gases
effectively serves as participate reduction devices, thus
minimizing particulate loadings to the subsequent emission
control equipment.  Normally, direct contact evaporators will
remove approximately 40 to 60 percent of the particulate
emissions from the recovery furnace.  Particulate emissions
from the direct contact evaporator(s) are dealt with most
effectively by employing such control devices as electrostatic
precipitators and Venturi scrubbers.  It is normally more ad-
vantageous to control furnace operating conditions to minimize
gaseous emissions rather than particulate emissions.  However,
as a general rule, most operating conditions which result in
reduced gaseous emissions also serve to reduce particulate
emissions.

Particulate levels in kraft recovery furnace flue gases, prior
to reaching a reduction device, normally range from 8.0 to
12.0 grains per standard dry cubic foot of flue gas.  The
atmospheric emission levels are a function of control device
efficiency which is dependent upon the system design.  In con-
ventional recovery furnace systems (those with direct contact
evaporators), particulate emission control consists of:  (a)
the contact evaporator; (b) a primary unit which is either a pre-
cipitator or a Venturi recovery unit; and (c) in some cases,
secondary scrubbers.  In newer systems where no flue gas direct
contact evaporators are employed, high efficiency (99+%) elec-
trostatic precipitators are used for particulate control almost
exclusively.  This does not, however, preclude the addition
of secondary scrubbers to solve special "snowing" problems.
Particulate collection efficiencies for the previously described
recovery furnace complex generally range from 85-99+ percent
with the higher percentages applying to systems installed within
the past few years.

In conventional recovery complex systems, malodorous reduced
sulfur compounds may be present in the furnace exit gases and
also "stripped" from the black liquor in the direct contact
evaporators.  Generally, in  the absence of black liquor oxi-
dation, the contact evaporators are the major source of malodor-
ous sulfur gas emissions.  Sulfide and available alkali content
of the black liquor entering the contact evaporators are the
major variables in controlling the loss of reduced sulfur com-
pounds from this unit process.  Numerous studies have shown that
inorganic and organic sulfide stripping is minimized when the
measurable sulfide and mercaptide content of the black liquor
is below 0.1 grams per liter.  Hydrogen sulfide accounts for
most of the reduced sulfurs emanating from this operation, al-
                          -52-

-------
          though there can be methyl  mercaptan,  dimethyl  sulfide,  and
          dimethyl  disulfide present.   These  organic  sulfur  compounds
          seldom exceed ten percent of the  h^S present  and normally  are
          not measurable at all.

          In well  controlled recovery complex systems,  atmospheric
          emission levels of reduced sulfur compounds may be as  low  as
          1.0 parts per million  (ppm)  by volume  to  several hundred ppm.
          The wide range of emission levels is a function of the afore-
          described process and  control  equipment variables.

           Historically, there has been little concern  for the S02
          generated in a kraft recovery furnace.   In  conventional  kraft
          recovery furnace system designs concentrations  are substan-
          tially reduced when furnace exhaust gas passes  through the
          contact evaporator.  After the contact evaporator  they are
          characteristically below that existing from the combustion
          of fossil fuels containing 0.5 percent sulfur,  i.e.  less than
          300 ppm, usually between 50 and 150 ppm.  Concentrations of
          S02 in recovery furnace exhaust gas range from  less than 50
          to as high as 700 or 800 ppm.   The factors  responsible for this
          range of concentration are not well identified. Blue  and
          Llewellyn (21) as well  as results of currently  unpublished
          studies indicate that  S02 generation in kraft recovery furnaces
          is a function of several variables. One  is cooking liquor
          sulfidity, and indirect measure of the soda and sulfur ratio
          in black liquor fed to the furnace. Others include smelt  bed
          depth, manner in which liquor is  sprayed  into the  furnace,
          ratio of primary to secondary combustion  air  and possibly
          temperature within the furnace itself.  As  previously  stated,
          the higher concentrations are of  limited  practical  concern
          except in those recovery system designs which eliminate  the
          contact evaporator.
3.2.12.2  Lime Kilns
          The lime kiln is a major source of chemical  loss in the form of
          particulate emissions.  The gaseous emissions are not so pro-
          nounced.  In the lime recovery process, lime is usually lost at
          various points—some with grits or impurities removed by the
          slaked lime classifier and some at storage facilities for re-
          burned lime.  The major source of loss is the exit gases leaving
          the kiln.  The lime dust escaping with the flue gases is more
          objectionable than the calcium carbonate and lime lost at the
          other end of the kiln because it is reactive lime.
                                    -53-

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The other minor chemical  loss which creates an odor problem, is
the release of sulfur bearing compounds through exit flue gas.
The quantity of odor from lime  kiln gases is very small as com-
pared with other sources  in  the  pulp mill.  To understand and
develop an odor control system  or  to minimize the formation and
release of odorous compounds, it is necessary to evaluate the
sources contributing to odor emission.  The possible sources of
sulfur compounds are:

          1.  The  degree  of  washing of lime mud and the filter
             cake dryness determines the amount of sodium sul-
             fide in  the lime sludge.  In cases where liquor
             sulfidity is high  and washing poor, as much as
             5  pounds of sodium sulfide per ton of pulp produc-
             tion may be present  in lime sludge fed to the kiln.
             The  high carbon dioxide and high temperature at-
             mosphere may favor release of hydrogen sulfide and
             sulfur dioxide according to the following reactions:

                            Na2S + C02 + H20
                            -> Na2C03 + H2S

                               2H2S  +  302
                               + 2S02  +  2H20

              The  hydrogen sulfide emissions will  increase with
              lowering of kiln  exit  temperature  or oxygen  content.

          2.   The  high sulfur content  fuel  oil  used in the kiln
              as a fuel source  results  in  the  release  of  sulfur
              dioxide.

          3.   Where  the water supplies  are  limited and a  mill  has
              a tight water  balance,  the  evaporator condensate is
              used as makeup to the  kiln  scrubbing system.   If
              the  mill does  not practice weak  black liquor oxida-
              tion,  this  may become  a  significant  odor source.

          4.   Some mills  practice  burning  of the noncondensable
              gases  released in the  digester and evaporation  pro-
              cess in the kiln.  These  gases with  high sulfur
              content are efficiently  burned in  the high  tempera-
              ture zone.
                          -54-

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The use of wet scrubbers, of low sulfur content fuel  and the
efficient control  of combustion and the proper washing of lime
mud will definitely reduce the odorous gases and chemical losses
in the form of sulfur dioxide and hydrogen sulfide.   A typical
lime kiln scrubbing system is shown in Figure 3-13.

The flue gas leaving the kiln carries an appreciable  quantity
of dust.  The chemical composition of the dust is essentially
carbonates of sodium, calcium and magnesium, sodium sulfate
and acid insolubles (consisting of aluminum oxide, iron oxide,
silica and others).  The amount of chemicals leaving  the kiln
in the flue gases may range from 5 to over 20 grains/cubic
foot.  This represents a loss of 10 to 20 tons/day (for a 400
TPD mill).            	

Factors which affect reduced sulfur emissions from the kiln
proper have been identified as stack gas oxygen content, design
dimensions, operating temperature, and effectiveness  of the
lime mud washer.  Those operating parameters which have been
identified as being responsible for the reduced sulfur contri-
bution from the scrubbing system include make-up water source
and recirculation rate, pH of the scrubbing solution, and the
sulfide content of the particulate matter.

Minimum emission rates which can be consistently obtained
through the optimum control of these variables have not yet
been fully established.  Current findings indicate the emission
concentration can be maintained at less than 50 ppm or 0.25
pounds of sulfur per ton of air dried pulp.  While kiln operating
variables which affect the emission of hydrogen sulfide have
been identified, minimum emission rates which can be consis-
tently attained through controlled operation have not been fully
established.

Hydrogen sulfide can be emitted from two distinct and separate
points which are:

         1.  the lime kiln proper

         2.  the particulate control scrubber

Factors which affect the concentration of reduced sulfur in the
exit gas from the lime kiln include:

         1.  oxygen content of the exit gas,

         2.  length to diameter ratio of the kiln,

         3.  sulfide content of the lime mud,
                          -55-

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Lime  kiln     venturi scrubber system.
                    FIGURE  3-13
                                                        FRESH
                                                        WATER OR
                                                        KILN COOLING
                                                        WATER
                                                         LIME
                                                         SLUDGE
                                                         WASHERS
                               -56-

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         4.   cold-end operating temperature,

         5.   burning of green liquor dregs.

Operating variables of the particulate control  scrubber which
govern the contribution of hydrogen sulfide  include:

         1.   source of scrubber make-up water,

         2.   recirculation rate,

         3.   pH of the scrubbing solution,

         4.   acid liberated sulfide content  of  the particulate
             collected.

Minimum hydrogen sulfide concentrations in the  stack  gas of
individual kilns have been measured at oxygen contents of 3.5
to 4.0 percent for units operated under stable  conditions.
The hydrogen sulfide values recorded have varied from 10 ppm
to about 100 ppm for properly operated kilns.  The higher con-
centrations were associated with "so-called"  long kilns operated
on lime mud of high sulfide content.  A typical hydrogen sulfide
vs. oxygen content curve is shown in Figure  3-13 A.

Long kilns are characterized as units with lengths of 25 diameters
or more and short kilns as units with lengths of 20 diameters or
less.

The gross effect of lime mud sulfide content on kiln  proper
hydrogen sulfide emission rates is presented in Table 3-4 (22).
Operating conditions during intervals II and III on two separate
trials on one kiln were similar, as was the  hydrogen  sulfide
emitted.  During interval IV, the only operating variable
changed was the removal of green liquor dregs from the kiln
lime mud feed.  The corresponding reduction  experienced in the
hydrogen sulfide emission was about 40 percent.

Particulate emissions from the lime kiln consist of the sodium
salts, calcium carbonate, calcium sulfate, calcium oxide, and
insoluble ash.  The presence of the sodium salts may be accounted
for by the sublimation-condensation process, and by dust entrain-
ment within the kiln.  However, neither calcium carbonate, nor
calcium oxide will vaporize at temperatures  within the kiln and
the presence of calcium carbonate and calcium sulfate must be
explained by the entrainment of the calcium carbonate and calcium
oxide.  The particles of calcium oxide may react with either
                           -57-

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                                    FIGUREW-13 A


                    TOTAL .REDUCED SULFUR VS. EXCESS OXYGEN

                                  LIME  KILN
           100
en
CO
       CL
       r>
cr.

2

ID
CO

Q
L-J
       Q
       UJ
       CC

       -J
       <
       J—
       o
       h-
90 h


80


70


GO


50


40


30


20


 10


 0
                                                        o
              0
1.0
                      2.0     3.0
                                4.0
5.0
6.0
7.0
8.0
                                EXCESS OXYGEN

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                        TABLE 3-4

LIME KILN EMISSIONS (Prior to Particulate Control Device)
         AS RELATED TO OPERATIONAL VARIABLES (22)
Interval
i
I
II
III
IV
V
Stack Gas
S0? Content
%
0
2.8
2.4
2.8
4.0 - 7.0
Burnings
Dredge
Yes
Yes
Yes
No
No
H?S
ppm
804
506
463
243
60 - 86
Lbs S/Ton
2.9
1.7
1.5
0.9
0.2 - 0.3
                              -59-

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          carbon dioxide or sulfur dioxide within  the  kiln  to  yield  the
          appropriate calcium salt.   Calcium carbonate may  react with
          the sulfur dioxide and then oxygen to  yield  calcium  sulfate.
CaO +
CaO +
CaC03
CaS03
co2 +
+ so2
+ 1/20
CaC03
CaS03
-> CaS03
2 -»• CaSO
4
          The particulate emissions from the lime kiln (before the  control'
          equipment)  are about one-fourth the emissions from the  recovery
          furnace but are still  significantly large.   However, the  relative-
          ly low gas  flow rates through the lime kiln allow installation
          of moderately priced high efficiency wet scrubbers which  can  re-
          duce. particulate emissions to low levels.   At the present time,
          most lime kilns are equipped with wet scrubbers whose efficiencies
          range from  80 to 99 percent on the calcium  salts.  The  particu-
          late emissions from the lime kilns whose scrubber efficiencies
          are in the  lower part of the range may be  significant.

          Other than  controlling the rate of material  output there  appears
          to be no well defined method of controlling the particulate
          emission for the lime kiln through manipulation of operating
          variables.

          The previously described particulate control system employed
          on most lime kilns can be a source of reduced sulfur losses
          dependent upon the source of scrubbing water and the recircula-
          tion rate.   Although the collected particulates are alkaline,
          the kiln exit gases are rich in carbon dioxide and, therefore,
          caused a pH drop in the scrubbing medium.   In these cases, soluble
          sul fides in the scrubbing liquid may be evolved as hydrogen
          sulfide.  This potential condition then dictates the necessity
          of utilizing sulfide free source water for  the scrubbing  system.

3.2.12.3  Smelt Dissolving Tank

          Both particulate material and reduced sulfur compounds  are
          present in  the vented gases from smelt dissolving tanks.   Parti-
          culates are primarily caused by the entrainment of large  parti-
          cles in the vent gases.  Because of the violent reactions taking
          place when  the molten smelt from the furnace is discharged into
          the tank, the turbulence created will "splash" water droplets
          which contain both dissolved and undissolved inorganic  salts
                                      -60-

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          above  the  liquid  surface of  the  tank.  Therefore, due to the
          high temperature  of  the offgases, the small particles, now in
          suspension,  are carried out  with the gas stream.

          Some reduced sulfur  compounds  are formed by reactions in the
          tank and others are  distilled  from  the make-up water, usually
          weak filtrate from the  lime  mud  washer, added to the dissolving
          tank.

          Operational  variables most influential on  these emissions are
          (a) rate of  molten smelt discharge  from the recovery furnace and
          (b) source o»f make-up water  utilized.  The shatterjet system utilized
          on the furnace smelt spouts  can  also have  a significant effect
          on particulate emissions from  this  source.

          Wire mesh  mist eliminators are currently the most used emission
          control devices employed on  smelt tank vents.  However, more re-
          cently, wet  scrubbing systems, including packed columns, are now
          being  installed in many places.  These scrubber/absorption sys-
          tems can be  effective on both  particulars and reduced sulfur
          emissions  when the proper scrubbing medium is used.

3.2.12.4  Multiple  Effect Evaporators

          The kraft  process utilizes multiple effect evaporation  to  con-
          centrate weak black  liquor   (spent  cooking  liquor) washed from
          the pulp.   Removal  of large  amounts of water  from the  liquor  is
          necessary  to facilitate combustion  of  the  dissolved organic
          material  in the recovery furnace.   The liquor is  concentrated
          in the multiple effect  evaporators  from  a  solids  content of
          12-18% to  40-55%   (25).

          Most kraft mills  utilize long-tube  vertical shell-and-tube type
          evaporators.  The weak  black liquor is fed to the tube  side  of
          the latter evaporation  effects and  steam is  supplied to  the
          shell  side of the first effect.   The liquor  proceeds through  the
          tube side  of each effect from last to  first,  being  heated  in
          each by condensation of the  vapor driven off  the  boiling  liquor
          in the tube side  of each preceding  effect.

          Evaporated water  vapor  from  the  last effect  of the  set  is  con-
          densed in  one of  two types  of condensers:   (a)  direct  contact
          barometric condensers,  and   (b) surface condensers with  steam
          ejectors.   The condenser must remove vapor fast enough  to  create
          a vacuum in the vapor space  of the  last  effect.   Each  type of
          condenser  is equipped with  a small  steam ejector  to remove non-
          condensibles.
                                         -61-

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  The emissions from the multiple effect evaporators are non-con-
  densible reduced sulfur gases which are vaporized or stripped
  during  the boiling.  These non-condensible gases, with vapors
  created during boiling, pass to the heating element of the follow-
  ing effect.  The reduced pressure  in the later effects will re-
  sult in a higher evolution of the reduced sulfur compounds.  This
  increased evolution and the steam stripping of the reduced sulfur
  compounds are responsible for the emissions from this source.

  In order to eliminate an accumulation of non-condensible gases in
  the heating element each heating element is provided with a gas
  vent.   The vents from the heating elements that are under a pres-
  sure greater than atmospheric are vented to its vapor head.  The
  vents from the heating elements under a vacuum are usually valved
  to a common header going directly to either a barometric or sur-
  face condenser.  The condenser type influences the relative
  emissions of TRS compounds from this source as indicated in the
  following table (limited data):
                           	Emissions  (Ib/ADT)
   Condenser Type

Surface

Barometric (with loss at
 noncondensible jet)

Barometric (losses from
 hot well)
 H2S     Methyl      Di-methyl
 	   Mercaptan    Sulfide
 4.80    1.44

'0.04    0.03


 0.13    0.20
0.35

0.04


0.14
Di-methyl
Di-Sulfide

  0.62

  0


  0.02
   Sulfidity and pH of the liquor tend to be controlling factors in
   the quantity of reduced sulfur compounds emitted.   Although black
   liquor oxidation can reduce the TRS emissions significantly, the
   residual concentrations are such that further processing of non-
   condensibles is desirable.

   The most common practice, in cases where treatment of these
   non-condensibles is employed, is to combine these non-condensible
   gases with the digester blow and relief gases and treat in the
   same manner as described in section 3.2.12.5.
                            -62-

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3.2.12.5  Digester-Relief and Blow

          Digester systems employed in the kraft process  consists  of the
          batch and continuous types previously described.


          Although no particulates are generated from these operations,
          the relief and blow gases can be the largest potential source
          of reduced sulfur emissions within the kraft mill.  This is
          mainly due to the fact that most of the malodorous organic
          sulfur compounds from the kraft process are primarily formed
          during the digestion of the wood chips.  Further, their  first
          opportunity to "escape" comes during the cooking  cycle via
          the relief gases and at the end of the cooking  cycle through
          the blow gases.

          Where turpentine recovery is employed, the relief gases  are
          normally passed through turpentine recovery systems where the
          condensible fractions of the gases are removed.  The non-
          condensible fractions may then be vented to the atmosphere or
          a control system for further treatment.  These  non-condensible
          gases are mainly made up of methyl mercaptan, dimethyl sulfide
          and dimethyl  disulfide.

          Blow gases are released at the end of the cooking cycle  and, in
          batch systems, normally pass through a blow-heat recovery sys-
          tem which is relatively ineffective insofar as  removal of organic
          sulfur compounds is concerned.  In batch digester systems, the
          blow-heat recovery tank can be an intermittent, but significant
          source of malodorous sulfur emissions.

          Several operating variables affect both production and sulfur gas
          emissions from these operations.  The most important of these
          as they relate to emissions are (a) cooking liquor sulfidity
          (b) duration of cook (c) wood species and (d) degree (severity)
          of the cook which is related to a,b, and c and  the desired yield.

          Treatment methods utilized to dispose of the malodorous  non-
          condensible blow and relief gases include thermal oxidation,
          chemical oxidation and chemical absorption.  The most prevalent
          methods currently in use are a combination of chemical absorption
          followed by thermal oxidation, most commonly in the lime kiln.
          As previously stated in section 3.2.12.2 thermal  oxidation in
          the lime kiln virtually eliminates malodors produced by these
          reduced sulfur compounds.  Burning the gases is accomplished
                                     -63-

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          in  the  lime  kiln,  or  a  special  separate  incinerator  (23).   In
          burning,  care  must be taken  to  avoid  the occurrence  of explosive
          mixtures.   In  a  batch digestion system,  the problem  of preventing
          large surges of  gas to  the burning  device  arises.  Gas surge
          capacity  is  provided  by using large spherical  tanks  equipped with
          a movable non-porous  diaphram (24), or conventional  gas  holders.
          Burning can  be a very effect!veTechnique  for disposal of these
          gases.   Data in  the section  on  lime kilns  illustrate this  point.

          Scrubbing the  gas  stream with a sodium hydroxide solution offers
          a  partial  control  method for digester emissions.  Effectiveness
          is  limited to  h^S  and methyl mercaptan.   Some mills  use  such
          scrubbers for  preliminary treatment of gases  before  burning
          them.  Three objectives are  achieved:  (a) some  sulfur is re-
          covered,  (b) steam is condensed, and  (cj  turpentine  vapors and
          mists are removed, mitigating an explosion hazard.

          Scrubbing with chlorine solutions is  practiced in some mills.
          In  the  case  of bleached kraft mills,  chlorine-containing efflu-
          ent from  the bleach plant may be used to scrub the gases.   It
          is  necessary that  residual chlorine be present at all times in
          these effluents  to maintain  the effectiveness of this technique,
          which is  of  limited effectiveness at  best.


3.2.12.6  Brown Stock Washer Systems

          Brown stock washer systems are  commonly  characterized as high
          volume-low concentration sources of reduced sulfur compounds.
          No particulate material is generated  from these sources.

          Operational  variables which  affect production and atmospheric
          emissions include  (a) liquor sulfidity  (b) pulp flow rate (c)
          wood species (d) wash water  source and  (e) storage time  in blow
          tanks (26.).

          Emissions from the brown stock  washers  arise primarily from the
          vaporization of the volatile reduced  sulfur compounds.   No chemi-
          cal reactions are believed to take place.   However,  there is  a
          shift in the equilibrium for hydrogen sulfide and methyl mercap-
          tan.  Since the washer water normally has approximately a neutral
          pH,  the dilution of the liuqor  by  the water will cause a lowering
          of the liquor pH to approximately  10.0.. This pH is below the
          equilibrium point  for methyl mercaptide  ion and results in a
          corresponding shift to  methyl  mercaptan  gas.   The lower pH will
          also cause an increase in the concentration of dissolved hydro-
          gen  sulfide.  However,  the equilibrium point of H2S (8.0) will
          not  be reached.
                                         -64-

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The composition of these sulfur gases is almost exclusively
organic sulfur compounds made up of methyl  mercaptan, dimethyl
sulfide and dimethyl disulfide.

Control of these emissions is not commonly practiced at the
present time stemming primarily from the difficulty and expense
of treating the high volume-low concentration sources.  However,
newer installations are venting these gases to the recovery
furnaces for utilization as a source of combustion air.  There
is a scarcity of available data regarding the effectiveness of
this practice in the overall odor reduction of kraft pulp mill   -
operations.

Measured emissions from these sources range between 0.01 and 0.6
with a mean of 0.1 pounds of total reduced sulfur (as H2S) per
ton of air dried pulp (26).
                           -65-

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3.2.13  REFERENCES
        1.   Douglass,  I.B.  and  L.  Price, Abstracts, 52nd Annual Meeting of
            TAPPI,  p.  40  (1967).
        2.   Brink,  D.L.,  J.F. Thomas,  and D.L.  Feuerstein, TAPPI, 50 (6),
            p.  276  (1967).
        3.   Shah,  I.S.  and  L. Mason, TAPPI,  50  (10), p. 27A  (1967).
        4.   Shah,  I.S., Chemical  Engineering, 74  (7), p. 84  (1967).
        5.   West,  P.H., H.P.  Markant,  and J. H. Coulter, TAPPI, 44 (10),
            p.  710  (1967).
        6.   Shah,  I.S.  Paper  Trade Journal.  152 (11) p. 65 (1968).
        7.   Shah,  I.S.  Paper  Trade Journal.  152 (12) p. 58 (1968).
        8.   Shah,  I.S.  and  W.D.  Stephenson,  Abstracts,  53rd  Annual Meeting of
            TAPPI,  (1968).
        9.   Landry, J.E., TAPPI,  46 (12), p. 766,  (1963).
       10.   Hawkins, G.,  NCSI Technical  Bulletin  No. 153.
       11.  Hendrickson, E.R.,  and C.J. Harding, Journal  of  APCA,  14  (12),
            p. 487  (1964).
       12.  Trobeck, K.G.,  W. Lenz, and A.  Tirade, TAPPI,  42 (6),  p. 425
            (1950).
       13.  Collins, T.T.,  Jr., TAPPI, 38 (8),  p. 172A, (1955).
       14.  Stuart, H.H., and R.E. Bailey,  Southern Pulp  of  Paper  Manufacturing.
            p. 46,(September 10, 1965).
       15.  Navaree, J.,  NCSI Technical Bulletin No.  26.
       16.  Douglass,  I.B., R.L.  Weichman,  and  L. Price.   Unpublished  paper,
            "Odor Formation in  Black Liquor Multiple  Effect  Evaporator."
       17.  Tomlinson, G.H.,  Pulp and  Paper Manufacturing, Vol.  1, 3rd  Edition,
            p. 416, McGraw-Hill, N.Y.  (1950).
                                        -66-

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18.  "Factors Affetting Reduced Sulfur Emissions from the Kraft
     Recovery Furnace and Direct Contact Evaporator."  Technical
     Bulletin No. 44, National Council of the Paper Industry for
     Air and Stream Improvement, Inc., New York, December 1969.

19.  Thoen, G.N., DeHaas, G., Tallent, R., and Davis, A., "The
     Effect of Combustion Variables on the Release of Odorous
     Sulfur Compounds from a Kraft Recovery Process," TAPPI jj]_
     (8) 329 (1968).

20.  Murray, F.E., and Rayner, H.B., "The Emission of Hydrogen
     Sulfide from Kraft Recovery Furnaces," Pulp and Paper Maga-
     zine of Canada, 69 (5) 71 (1968).

21.  Blue, J.D., and Llewellyn, W.F., "Operating Experience of a
     Recovery System for Odor Control," TAPPI, 54_, 7, 1143-47.

22.  Franklin, M.E., and Caron, A".L., "Factors Effecting Lime
     Kiln Reduced Sulfur Emissions," NCASI Southern Regional
     Meeting, July 1971.

23.  Blosser, R.D., Cooper, B.H., "Current Practices in Thermal
     Oxidation of Non-condensible Gases in the Kraft Industry,"
     NCASI Atmospheric Pollution Technical Bulletin No. 34
     (November 1967).

24.  Morrison, J.L., "Collection and Combustion of Non-condensible
     Digester and Evaporator Gases."  TAPPI, 52-51, December 1969,
     pp. 2300-2301.

25.  Britt, Kenneth W., Handbook of Pulp and Paper Technology.
     Reinhold Publishing Corporation, New York, 1964.

26..  "Factors Affecting Emission of Odorous Reduced Sulfur Compounds
     from Miscellaneous Kraft Process Sources," Technical Bulletin
     No. 60, NCASI, New York, March 1972.
                               -67-

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3.3  DESCRIPTION OF THE NSSC PROCESS

     This process is mainly used for the production of a high yield  pulp
     having a high crush strength, important for making corrugated  board.
     In addition, it utilizes hardwood species that are not readily  adapt-
     able to the other processes.  Coniferous woods are considered  less
     desirable for the NSSC process because of a higher chemical  comsump-
     tion during cooking, high lignin content for a given yield,  and high
     energy requirements for refining.

     Recovery of chemicals from the spent liquor is not practiced at the
     majority of mills and, therefore, may create a water pollution  prob-
     lem.  Incineration of the liquor may, in turn, create an emission
     problem because of sulfur dioxide emission from the incinerator and
     will depend on the degree of sulfur dioxide recovery.

     Neutral  sulfite semi chemical pulping is basically a two-stage process.
     It involves:

               1.   A mild chemical treatment of the wood chips in the
                   presence of a neutral  chemical  solution within a
                   digester and followed by

               2.   A mechanical  treatment, called defibering, to
                   disintegrate the wood chips into pulp.

     It derives its name "neutral sulfite" from the fact that the solution
     containing the cooking chemicals, consisting of sodium sulfite  and
     sodium carbonate, is maintained above a pH of 7.0.   Aqueous  solutions
     of sodium sulfite are basic but during digestion wood chips  release
     organic acids which if not neutralized will  acidify the cooking liquor.
     Alkali, usually sodium carbonate, is added to the cooking liquor to
     neutralize the organic acids, primarily to reduce the corrosiveness of
     the liquor.   The higher pH retards hydrolysis of carbohydrates, pro-
     ducing higher yields of stronger pulp; but increases bleaching  costs
     because a darker pulp is produced.  The name "semichemical"  is  given
     because all  of the cementing material is not completely removed by the
     chemical  reaction and some mechanical disintegration is required to
     separate the fibers.   Because some of the cementing material  remains
     with the fibers it follows that the "yield" for this process is higher
     than for a conventional full-chemical pulping process.   Semichemical
     pulping may produce yields of 60 to 80 percent.
                                    -68-

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       Various types of semi chemical  pulps  are  produced  by  the  acid  sulfite,
       neutral sulfite, kraft,  soda and cold  soda  pulping processes.  The
       major process difference from conventional  chemical  pulping lies  in
       the use of lower temperatures, more  dilute  cooking liquor  or  shorter
       cooking time and mechanical  disintegration.   Semichemical  processes
       can be categorized as  alkaline or acid.

       The NSSC process varies  somewhat from  mill  to mill.   Some  mills recover
       heat and chemicals from  the  spent liquor, others  dispose of spent
       chemicals through ponding or other means, including  blending  with kraft
       black liquor.  This chapter  will  contain discussions relative to  the
       most pertinent operations currently  utilized.

       The cooking process is carried out in  either batch or continuous
       digesters.  Steam maintains  the temperature and pressure of the cook
       within certain limits  depending on the end  use of the pulp.   During
       this cooking stage odorous gases are created within  the  digester.  The
       digester may be partially vented continuously throughout the  cook.
       This serves to remove  carbon dioxide from the system and thus helps
       maintain a high pH in  the cooking liquor.   At the completion  of the
       cooking cycle, residual  pressure within  the digester is  used  to dis-
       charge the entire contents of the batch  digester  into a  blow  tank.
       Waste gases, containing  the  odorous  compounds formed in  the digester,
       are usually vented to  the atmosphere.

       At the completion of the cooking cycle,  the internal pressure within
       the reactor is used to discharge the softened chips  to a holding
       vessel known as the blow tank.  The  waste gases are  usually passed
       through a condenser to remove steam  and  other condensible  vapors.

       After excess liquor is separated by  draining, pressing,  or washing,
       the softened chips are reduced to pulp through mechanical  treatment
       in equipment such as rod mills or rotating  disc refiners.  The pulp
       is then diluted and usually  pumped to  multistage  drum filters where
       counter-current washing  with water is  carried out to remove the spent
       liquor from the pulp.  Other means for washing the pulp  are available
       and are used by some mills.   The resultant  filtrate  is termed weak
       black (spent) liquor.  The washed pulp is then upgraded  to the degree
       desired in subsequent  processing steps and  ultimately utilized in the
       production of paper products.


3.3.1   CHEMICAL RECOVERY OR DISPOSAL METHODS

       Over the years and up  to the present,  five  different methods  have been
       utilized in disposing  of or recovery of the spent liquors  from NSSC
       pulping operations.  These five methods  consist of 1) dumping the
       effluent with no recovery, 2) mixing with kraft black liquors for sub-
       sequent processing, 3) cross-recovery  integrated  with a  kraft mill,
                                         -69-

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         4) partial or complete recovery utilizing a kraft type recovery boiler
         or smelter, and 5) fluidized bed recovery system.  The first method
         is obviously no longer considered because of pollution abatement laws
         and operating economics.   For this reason, this method will  not be
         further discussed.  A schematic diagram of this operation is depicted
         in Figure 3-14.


3.3.1.1  Disposal  By Mixing With Kraft Liquors

         If a kraft system is adjoining, the NSSC spent liquor can be mixed with
         the spent kraft liquor, up to a limiting percentage, and burned in the
         recovery furnace.  Formerly, the ideal  ratio was about three parts
         kraft pulp to one part NSSC pulp.  However, increasingly stringent
         emissions controls have reduced the salt cake losses from kraft mills
         to the point that the chemicals recovered from one ton  of NSSC pulp
         production will provide sufficient make-up for eight tons of kraft
         production.  The recovered chemicals are used entirely in the kraft
         system.  Emissions of both sulfur dioxide and hydrogen sulfide may be
         increased from the kraft recovery furnace when NSSC liquor is added.
         This is primarily due to the fact that the NSSC liquor is more acid
         than kraft liquor.  Most of the increased hydrogen sulfiide losses are,
         therefore, from the direct contact evaporator.


3.3.1.2  NSSC Cross Recovery With  Kraft Recovery Operation

         A second class of process involves recovery of NSSC cooking liquor
         via a cross recovery system in conjunction with a kraft mill, as indi-
         cated in Figure 3-15.  There are several processes in this class
         (Tampella, Olinkraft, e.g.).  These systems generally recover sodium
         carbonate from kraft green liquor by crystallization and add sulfur
         by absorbing sulfur dioxide produced by a sulfur burner.  The economics
         of this process depend upon efficient recovery of gases and liquors at
         each stage in the operation and usually air emissions from these de-
         vices are minimal.

         NSSC black liquor from the pulp mill is accumulated in a large storage
         tank, from where it is processed through a triple-effect evaporator.
         The heavy liquor, at 52 percent solids, is mixed with strong black
         liquor from the kraft mill, and the combined stream is run through the
         existing oxidation system (if available) followed by burning in the
         existing recovery boiler.  The semichemical liquor preparation system
         functions as follows.  Clarified green liquor from the causticizing
         plant is sent to aocrystallizer, where it is cooled to promote crys-
         tallization of Na2C03.  A centrifuge recovers the carbonate crystals,
         while the filtrate is sent back to the kraft green liquor system.  This
         basic scheme is illustrated in Figure 3-16.
                                          -70-

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                                Digester
                                  Vent
                       Digester
                       (Batch)
                                               Pulp  To  Machine
                                              Spent  Cooking  Liquor
                                                                                  Flash Tank
—i
i
                        Liquor
                      Preparation
Na2S03


Na2C03
                                               Spent Cooking  Liquor
                                    Spent Liquor
                                       Storage
                                                                           To  Sewer
                                  FIGURE 3-14.
  SCHEMATIC DIAGRAM OF NSSC PROCESS
  WITH NO CHEMICAL RECOVERY

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              Kraft
            Digesters
ro
i
         Kraft
         Pulp
White
Liquor
           Causticizing
                                  Green
                                  Liquor
                              Cross
                            Recovery
                             Process
              Kraft
              Pulp
            Washing
Black
Liquor
                         Recovery
                         Boilers
              Cooking
              Liquor
    NSSC
  Digesters
(Continuous)
                                            Green
                                            Liquor
                                                                                                              Digester
                                                                                                              Vent
                                                                                          Blow  lank
   Kraft
Evaporators
                                                                                        NSSC
                                                                                        Pulp
   NSSC
Evaporators
                                                                        Blow Tank
                                                                        Off Gases
   NSSC
   Pulp
  Washing
                                FIGURE  3-15.
                    SCHEMATIC DIAGRAM OF CROSS RECOVERY SYSTEM
                    FOR REGENERATING NSSC COOKING CHEMICALS

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                                             Sulfur
                                             Burner
                                       High Sulfidity Li
                                                     Kraft
                                                 Causticizing
FIGURE 3-16.
FLOWSHEET OF THE TAMPELLA PROCESS OF SODIUM SULFITE
CHEMICALS RECOVERY, WHICH CONVERTS GREEN LIQUOR
CHEMICALS INTO SULFITE COOKING LIQUOR
                                   -73-

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         Subsequently, molten sulfur is burned in an appropriate system to
         produce S02.  The S02 is combined with the Na2C03  solution in an
         absorption tower.  Gas emissions from the liquor preparation and
         recovery system are run through a fume scrubber before discharge
         to the atmosphere.

         The above processes are convenient where the NSSC mill is operated
         in conjunction with a kraft mill.  In cases where the NSSC mill
         exists alone, the spent cooking liquor (after evaporation) may be
         oxidized in a fluidized bed reactor.   The product (a mixture of .
         Na2C03 and Na2S04) of this patented process is not suitable for
         re-use by the NSSC mill and in fact it usually must be enriched
         with sulfur before it is suitable for use in the kraft process.
         This is accomplished by adding sulfur to the fluidized bed unit
         along with the feed liquor.


3.3.1.3  NSSC Fluidized Bed Recovery Process

         Figure 3-17 shows the fluidized bed system for treatment of neutral
         sulfite pulping waste liquors.  In these mills, a pulping liquor
         containing sodium sulfite (Na2S03) and sodium carbonate (Na2C03) is
         used as the pulping medium.  During pulping, .lignin and other organic
         matter is extracted from the wood and the spent pulping liquor con-
         tains sodium-sulfur compounds of varied degrees of oxidation in
         association with the organic matter extracted from the wood.  The
         total solids in the spent pulping liquor have a gross heating value
         of about 5,500 BTU per pound  (dry), contain about 30 percent carbon
         and 3 percent hydrogen.

         The spent pulping liquor is received from the pulp washing operation
         at about 10 percent total solids.  In order to support autogenous
         combustion of the liquor in a fluidized bed reactor, it is necessary
         to concentrate the waste liquor to about 35 percent total solids, at
         which point the fuel values in the waste can sustain combustion with-
         out addition of external fuel.  This concentration is accomplished
         in multiple-effect vertical-tube  forced-circulation evaporators of
         a special design to minimize tube fouling.  Nominally, a three-body,
         three-effect evaporation unit is employed at a steam economy of about
         2.6.  The concentrated liquor, at about 35 percent total solids, is
         pumped to a storage facility before introduction into the fluidized
         bed reactor.

         The temperature of the fluidized bed reactor is maintained at about
         1,325°F.  The concentrated liquor is introduced as a liquid disper-
         sion into the freeboard area of the reactor.  This method has several
         advantages over introduction of the liquid feed below the level  of
         the fluidized bed.  As the liquid feed contacts the heated exhaust
         gases rising from the fluidized bed, a portion of the water content
         of the feed is evaporated and the remainder of the feed falls into
                                         -74-

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                 MUTIPLE EFFECT FORCED
                 CIRC. EVAPORATORS
01
I
      CONCENTRATED
      LIQUOR STORAGE
           PELLET STORAGE
               TANK
                            METERING
                            SCREW -
                              FIGURE 3-17.   COPELAND RECOVERY SYSTEM FOR  NSSC PULP  MILLS

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           the fluidized bed.  In the bed, the organic portion of the fe~ed is oxi-
           dized to carbon dioxide and water vapor and the residual  inorganic
           chemicals are oxidized to their stable oxidation state; i.e., sodium
           sulfate and sodium carbonate.  Oxidation of the organic matter provides
           •sufficient thermal energy to maintain the reaction temperature.  The
           product of the inorganic chemicals, sodium sulfate and sodium car-
           bonate, deposits in the bed and forms the bed material.  The chemical
           product can be made to pelletize or agglomerate in the fluidized bed,
           and the product is discharged as a nearly perfect sphere in the size
           range of 20 to 65 mesh.

           The exhaust gases, containing entrained particulate material, are
           passed through a cyclone separator where entrained material is separated
           from the exhaust gases and returned through a screw conveyor or steam
           ejector directly to the fluidized bed.  The exhaust gases are scrubbed
           with weak waste liquor to remove any remaining entrained particles and
           to recover a portion of the sensible heat content of the exhaust gases..
           Analysis of these exhaust gases, for the presence of offensive gaseous
           compounds, indicates that the effluent contains little if any compounds
           that might contribute to air pollution.  There are no reduced or par-
           tially oxidized gaseous sulfur compounds.              .    ._•...,
  3.3.1.4  Direct Sulfitation in Recovery Boilers or Smelters

           Another cclass of NSSC process is that which recovers sulfite cooking
           liquors directly.  The I.P.C.,Mead and Western Precipitation processes
           are typical of this group.  The process essentially is a recovery
           boiler (smelter) modified to produce sodium sulfite rather than sodium
           sulfide.   Some of these are conversions of old kraft recovery boilers,
           others may be new equipment designed for this service.


3.3.1.4.1  Spent Chemical Recovery Cycle

           The black liquor filtrate separated from the softened chips and mechani-
           cal pulp is concentrated in multiple effect and/or direct contact
           evaporators to the desired solids concentration.  The concentrated black
           liquor is sprayed into a furnace, usually with an auxilliary fuel such
           as oil.  The furnace is maintained at 1,000°F to 1,300°F.

           In the furnace, the sprayed liquor droplets flash dry.  The carbonaceous
           material  chars in the upper oxidizing atmosphere of the furnace and the
           inorganic carbonate, sulfur salts, and char fall to the bottom of the
           furnace where a bed forms.  Primary air to the bed is controlled to main-
           tain reducing conditions which will convert sulfur-containing salts to
           sodium sulfide.  Secondary air admitted above the bed burns hydrogen
           sulfide to sulfur dioxide and completes the combustion of the carbona-

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           ceous material.   The sodium sulfide and  sodium carbonate  form  a molten
           smelt which flows from the furnace  and  is  dissolved  in water to form a
           solution referred to as "green liquor".

           Because of the sulfur compounds in  the  black  liquor  the flue gas from
           the furnace contains some sulfur dioxide,  and may  contain reduced  sul-
           fur compounds.  In order to achieve efficient chemical recovery, the
           sulfur dioxide must be absorbed from the combustion  gases with sodium
           carbonate or caustic solution, a process which presents special prob-
           lems because of the low sulfur dioxide  concentration.  Scrubbing can
           also help to remove hydrogen sulfide and methyl  mercaptan.

           The flue gases also contain sodium  sulfate dust with some sodium car-
           bonate.  For efficient chemical recovery,  this particulate matter  must
           be removed by electrostatic precipitators  or  high  efficiency venturi
           scrubbers.


3.3.1.4.2  Preparation of Pulping Chemical

           The green liquor, rich in sodium carbonate and sodium sulfide, is  pumped
           to the top of an absorption  tower.  There the solution is brought in
           contact with sulfur dioxide from a  sulfur burner.  The concurrent  scrub-
           bing of the S02-laden gas by the green  liquor results in  the following
           reactions:

                       2Na2C03 + S02 + H20  +    Na2S03 + 2NaHC03

                       Na2S + S02 + H20  ->  Na2S03 + H2S

           The scrubbing towers are efficient  in their absorption of the  sulfur
           dioxide.  There is, however, a large quantity of hydrogen sulfide  pro-
           duced which must be burned to sulfur dioxide  and abosrbed in sodium
           carbonate or eliminated in some other way if  atmospheric  pollution is
           to be avoided.  The sulfited green  liquor emerges  from the absorption
           tower as "cooking liquor" and is ready  for reaction  with  wood  chips in
           the digester.


    3.3.2  OTHER NSSC RECOVERY PROCESSES

           There are several variations of the NSSC recovery processes based  on
           burning the spent liquor, and three of  these  will  be briefly discussed
           under this section, and as shown in Figures 3-18 through  3-20.
                                           -77-

-------
3.3,2.1   Mead Process
         The first of the three methods to be discussed is the Mead  Process,
         developed and patented by The Mead Corporation.   Basically, the  process
         operates by separating the sulfur from the sodium complex by carbonation
         of the green liquor with waste flue gas.  The sulfur, driven off as  H2S,
         can then be oxidized by burning in air either in the furnace or  in a
         special burner, and is then recombined with sodium by washing the SC^ con-
         taining gases with the sodium carbonate solution formed in  the first
         step.    Processes similar in general approach have a considerable his-
         tory, but this process has several novel features which are what make
         it feasible.  The scrubbing of the totality of furnace flue gases with
         a Na2C03 solution gives a clean, S02 free, C02 rich, gas to use  for
         carbonation, as well as minimizes sulfur losses.  The splitting  of the
         gas stream between the precarbo'nation and carbonation towers provides
         the maximum concentration of H2S to the furnace and still  does not re-
         sult in sulfur loss.

         Following through the process, the concentrated liquor from the  multiple
         effect evaporators is evaporated further in the venturi scrubber-
         evaporator.  This liquor is burned in a kraft type furnace, which oper-
         ates with a reducing atmosphere in the "hearth" zone.  The molten
         Na2S - Na2C03 mixture flows into a dissolving tank.  The green liquor
         is. then clarified.

         The flue gases from the furance pass through the superheater, boiler
         and economizer for purposes of steam production, and then to the venturi
         scrubber where the gas velocity is increased and black liquor is in-
         jected into the gas stream.  The high gas velocity (approximately 300
         fps) atomizes the liquor.  This provides a cloud of droplets with a
         tremendous surface for heat transfer and on which the dust in the flue
         gas is collected.  The liquor is spearated from the flue gas in  the
         cyclone separator, and the clean gas containing N2, C02, 02 and  S02
         is passed to the sulfiting tower.

         The sulfiting tower makes the cooking liquor by absorption of the S02
         from the flue gas in a Na2C03 solution.  This carbonate solution is
        .obtained from the carbonating towers, where it is made by carbonation
         of green liquor with a part of the clean, substantially S02 free, flue
         gas from the sulfiting tower.  It is in these carbonation towers that
         the sulfide in the green liquor is removed as H2S.

         The gases leaving the carbonating tower contain H2S and the C02  not used
         in carbonization.  The concentration of this H2S is sufficiently low to
         present difficulty in combustion.  Therefore, the precarbonation tower
         is a device used to bring about an increase in H2S concentration.  About
         a third of the gas leaving is passed through this tower.  The high alka-
         linity of the liquor at this point removes the H2S from the gas  stream,
         forming NaHS.  The gases leaving this tower can be discarded with
                                          -78-

-------
FIGURE 3-18.   MEAD PROCESS SIMPLIFIED  FLOM SHEET
                                                      TO
                                                      COOKING
                                                      LIQUOR
                                                      STORAGE
FIGURE 3-19.   INSTITUTE PROCESS
               SIMPLIFIED FLOW SHEET
          BL.LIQ.               .	S02,C02,N2
            TO STACK
               f"TO STOCK
                OR
HgS H

bU|
SULFIT
TOWER
GREEN LIQL
NG

IOR
SULFUR
BURNER
FIGURE 3^20.   WESTERN PRECIPITATION  PROCESS SIMPLIFIED  FLOW SHEET
                                 FURNACE
                                               PRECIPITATOR
               OXIDATION
                       BLACK


                    __rrai,.

                     THICKENER



                        COCOg
                                           WATER
                                       SMELT  I
      OQ.
CRYSTAL
     J5R7
                  w
                         , TO STACK
                      SULFATING
                AlR
R_N02CO
ss.


FILTER

No
•PCX,
SOLI
n

'ION
                                      -79-

-------
         negligible loss  in sulfur,  while the  H2S  thus  absorbed will  be  released
         in the carbonation tower.   Consequently,  there is  a  very  substantial
         enrichment in H2S content of that portion of the gases returned to  the
         furnace,  insuring satisfactory combustion.


3.3.2.2  I.P.C.  Process

         The next  process to be discussed is one involving  direct  sulfitation  of
         the green liquor (Figure 3-19).   This process  has  been developed by the   .
         Institute of Paper Chemistry.   It is  a less complex  system  in that  no .
         sulfur recovery  is attempted.   The drawback to the process  lies in  the
         production of some Na2S203Which, although inert in the NSSC cook, re-
         sults in  higher  overall  chemical losses and possible difficulties with
         bleaching.  The  sulfur losses  are complete unless  the H2S formed is
         recovered.


3.3.2.3  Western Precipitation Process

         Basically, the process uses the furnace as a carbonator and, by increas-
         ing green liquor concentration, Na2CC>3 is salted out. The  sulfide  rich
         mother liquor is recycled to the multiple effect evaporators and added
         to the entering  black liquor.   The sulfide is  stabilized  by oxidation
         to prevent losses through evolution of H2S during  evaporation and sub-
         sequent venting.  A simplified flow sheet based on the published infor-
         mation is shown  in Figure 3-20   By scrubbing  the  flue gases.from the
         recovery  unit with the carbonate solution, this process could achieve
         high recovery efficiencies.  It is no simpler  than the other processes,
         with its  oxidation and crystallization replacing gas absorption and
         stripping, but it has some  advantages.  One simplification  is that  no
         H2S has to be piped from a  tower to a burner.


  3.3.3  EMISSIONS FROM NSSC PULPING

         Because of the milder pulping  conditions  employed, the emissions from
         semichemical plants are less intense  than those from conventional pulping
         processes.  The  emissions will also vary depending on the process em-
         ployed; e.g., neutral sulfite, or kraft.   In the latter case, the air
         pollution problems will  parallel those described under kraft pulping
         but will  be of a lower order of magnitude.  Particulate problems from
         recovery furnaces are much  the same throughout the industry.

         Published data on emissions from NSSC pulping  are  virtually nonexistent.
         Certainly information exists in the files of various mill engineering
         departments and  perhaps in  the files  of state  and  local control agencies.
         This data is proprietary however and  not available.   The  data in Table
         3-5  have been excerpted from various technical and  commercial  publica-
         tions.  The data for newer  technology represent improvements made in
                                         -80-

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                 TABLE 3-5



EMISSIONS FROM NSSC PULPING (IBM/TON  ADP)
Source po1 Tutant . Techno! ogy
Recovery Furnace S0?
or Smelter H?S
RSH
Total
Sulfiting Tower S0?
H2S
Total
Blow Tank S02
H?S
RSH
Other Organic
Total
Dissolving Tank H2S
S0?
Total
Evaporator H2S
Total Organic S
Total
Mashers H?S
S02
Total
FUndized Bed ' S02
Total Organic S
Total
Cope! and Process SO
Total Organic S
Total
8.20
4.20
0.30
12.70
0.80
8.55
9.35
0.30
' 4.20
1.56
3.12
9.18
0.10
0.04
.0.14
0.13
0.09
0.22
0.05
0.01
0.06
Newer
Technology
2.45 - 1.40
1.10 - 0.20
0.10 - 0.05
3.65 - 1.65
0.30
0.30
0.25
2.10
0.78
1.50
4.63
0.10
0.04
0.14
0.13
0.09
0.22
0.05
0.01
0.06
.004 ~ .008
.004 - .007
.008 - .015
0.06 - 0.20
0.18 - 0.32
0.24 - 0.52
                       -81-

-------
         the past five to six years.   Combination  of NSSC spent liquor with kraft
         black liquor prior to evaporation  and  combustion results in an increased
         sulfur dioxide and hydrogen  sulfide  emission from the kraft recovery
         system.   No quantitative data on this  increased emission rate are avail-
         able.
3.3.3.1   LITERATURE CITED

         1.   O'Donoghue, Roderick,  TAPPI  38  No.  6  162A-7A  (1955).

         2.   Haywood, Gerald,  TAPPI 37  No. 2 134A-6A  (1954).

         3.   Collins, T.T.,  Jr.,  SOUTHERN PULP AND PAPER MANUFACTURER 19 No. 1
             94-106 (1956).

         4.   Bauer, T.W., Dorland,  R.M.,  CAN. J. TECH.  32, 91-101  (1954).

         5.   Campbell, Jr.,  Jr.,  Shiek, P.E., "The Mead Recovery Process"
             presented at the  Tenth Alkaline Pulping  Conference, New
             Orleans, Louisiana,  (November 14-16,  1956).

         6.   Mai, K.L., Babb,  A.L., IND.  ENG. CHEM. 47, 1749-57  (1955).

         7.   Whitney, R.P.,  Han,  S.T.,  Davis, J.L., TAPPI  40, 487-94  (1957).

         8.   Nugent, R.A., Boyer, R.Q., PAPER TRADE J.  140, No. 18,  29-32,
             34, 36, 38, 40, 42,  (1956).

         9.   Boyer, R.Q., "Application  of Green  Liquor  Phase Separation to
             Neutral Sulfite-Kraft  Integration," presented at the  Tenth
             Annual Pulping  Conference, New  Orleans,  Louisiana,  (November
             14-16, 1956).
                                          -82-

-------
  3.3.4  THE EFFECT OF PROCESS AND CONTROL  EQUIPMENT  VARIABLES ON  PULP
         PRODUCTION AND EMISSIONS

         The following sections describe variables  in process and  emission
         control  which affect pulp production  rates and  attendant  emission
         levels for the NSSC pulping process.

3.3.4.1  Liquor Pyrolysis and Chemical  Recovery Operations

         Many of the unit operations utilized  in both the NSSC  and sulfite
         processes are similar to those used in kraft operations.   There-
         fore, the variable relationships and  their subsequent  effect on
         emissions would be similar, although  the range  magnitude  may differ
         somewhat.

         NSSC spent liquors are treated in  a number of ways,  and there  exists
         very little information regarding process  variable and  control equip-
         ment effects on the attendant  emissions.   The various  methods  for
         recovery have been previously  discussed in this chapter,  which in-
         cluded among other kraft-NSSC  cross-recovery, fluidized bed, and a
         modified "kraft type" recovery boiler.  Kraft-NSSC cross-recovery
         has been discussed under kraft recovery boiler  operations and
         therefore will not be further  discussed.

3.3.4.2  Chemical Recovery Furnace

         There is a relationship between the Na/S ratio  in  the  liquor and the
         emission of sulfur dioxide. When  TRS emissions are  reduced the Na/s
         ratio decreases and sulfidity  increases.   Consequently, less alkali
         is available for recombination with the S02  in  the secondary zone
         and thus S02 emission increases.  Figure 3-21 _gives the experimental
         data showing the relationship  between Na/S ratio and S02  emissions.

         Adequate turbulence and cooling of the gases is essential  to promote
         efficient recombination and low alkali losses.   There  is  a need of
         about a  1000°F drop in temperature for best  recombination results,
         but it should be rapid to avoid formation  of other sulfur compounds.
         Cool  tertiary air  is  also  considered  to be helpful.

3.3.4.3  Sulfitation Towers

         Sulfur dioxide from sulfur burners or other  make-up  sources are
         scrubbed with an alkaline solution of sodium base  in the  amount
         required by the Na make-up of  the  mill.   The solution  should have
         a molar  ratio bisulfite/sulfite of 4:1 at  a  pH  of  around  7.0.
                                       -83-

-------
     2500 t—
     2000
I   1500
TD
X
o
-o

S-
    1000
     500
           \
       2.0
2.1
       a By analysis
       o Estimated
2.2      2.3

    Na/S ratio
2.4
2.5
2.6
                                   FIGURE 3-21


              SULFUR DIOXIDE REDUCTION WITH INCREASE IN Na/S RATIO
                                      -84-

-------
         The formation of the bisulfite-sulfite solution  takes  place  in  the
         original  sulfitation tower.   The bisulfite-sulfite  liquor can be
         contacted with green liquor  instead of directly  with the  smelt, as
         is often  done.

3.3.4.4  D-irect Contact Evaporation

         In this type recovery operation, where direct contact  evaporators
         are involved, removal  of S02 is  an important tool  in reducing the
         total  emission of sulfur from the smelter,  since the smelter, per
         se, does  not favor the best  control  of sulfide and  sulfur oxide
         emissions.   In order to improve  emission  control  from  the smelters,
         existing  concentrated  black  liquor used in  the venturi  evaporators
         may be replaced with a weaker black  liquor,  containing  12-17 percent
         solids for  instance.

3.3.4.5  Fluidizied Bed Pyrolysis Operations

         Emissions associated with the operation of fluidized bed  units
         were previously discussed.  These systems are not nearly  so  com-
         plex as other recovery methods;  and, based on the limited data
         available, indications are that  emissions for these sources  are
         minor.

         The major variables associated with fluidized bed operations,
         which could affect emissions, are the feed solids concentration,
         combustion bed temperature,  fluid bed height, and the  feed liquor
         sodium/sulfur ratio.  The main variables  affecting  the venturi
         evaporator-scrubber performance  are pressure drop across  the
         scrubber and scrubbing liquor solids concentration.


    3.4  DESCRIPTION OF SULFITE PROCESS

         The sulfite pulping process  produces easy bleaching pulps from
         non-resinous woods.  The characteristics  of the  pulp make it
         suitable for use in many grades  of paper, but it is especially
         suitable for tissues and fine papers.

         Recovery of cooking chemicals and the heat values in the  spent
         cooking liquors was not widespread until  fairly recent years
         when the older calcium base  has  been replaced in many  mills  by
         a  soluble base such as sodium, magnesium, or ammonium.   Sodium
         and magnesium bases require  recovery for  economic reasons.  Of
         the two, magnesium is more widespread in  its use because  on  com-
         bustion the  inorganic constituents break  down directly to magne-
         sium oxide and sulfur dioxide which can readily be recycled.
                                      -85-

-------
       Spent liquors from ammonia base pulping  may be  incinerated  with
       recovery of most of the S02-   The  ammonia  burns completely  to
       nitrogen and water vapor.

3.4.1  GENERAL  DESCRIPTION OF  SULFITE  PROCESS

       Sulfite  pulping  is an acid  chemical method  of dissolving the lignin that
       bonds  the  cellulose fibers  together.  Many  of the older mills use a
       sulfurous  acid -  calcium bisulfite solution  for the cooking acid.  Ca.lcium-
       base  spent liquor, because  of problems associated with evaporation and
       chemical recovery, is discarded  and may  result  in water pollution problems.
       In  order to overcome the problem of water pollution, several other acid
       bases  have been  developed,  the  most important being sodium, magnesium, and
       ammonium.

       Because  sulfite  pulp is used in  a wide variety  of end products, operations
       will  vary  considerably  between  mills.  These products can include pulp for
       making high grade  book  and  bond  papers or tissues for combining with other
       pulps, and for making dissolving pulp for producing cellophane, rayon,
       acetate, films,  and others.

       The pulping operation involves  cooking the  wood  chips in the presence of
       an  acid  within a  digester.  The  heat required for cooking is produced by
       the direct addition of  steam to  the digester or by the steam heating of
       the recirculated  acid in an external heat exchanger.  The cooking liquor,
       or  acid, is made  up of  sulfurous acid and a bisulfite of one of the four
       above  mentioned  bases.  The sulfurous acid  is usually produced by burning
       sulfur or.  pyrites  and absorbing  the S02  in  liquor.  Normally, part of the
       sulfurous  acid is  converted to  the base  bisulfite to buffer the cooking
       action.  During  the cooking action, it is necessary to vent the digester
       occasionally as  the pressure rises within the digester.  These vent gases
       contain  large quantities of sulfur dioxide  and,  therefore,  are recovered
       for reuse  in  the cooking  acid.

       Upon  completion  of the  cooking  cycle the contents of the digester, con-
       sisting  of cooked  chips and spent  liquor, are discharged into a tank.
       During this operation some  water vapor and  fumes escape to  the atmosphere
       from  the tank vent.  The pulp then goes  through a washing stage, where
       the spent  liquor is separated from the fibers.   The washed  pulp is either
       shipped  or kept  within  the  plant for further processing.  Block diagram
       flowsheets of the  sulfite  pulping  processes are contained in Figure 3-22.

       The spent  liquor that was washed out of  the pulp can be discarded or, as
       an  alternative,  can be  concentrated by evaporation and run  through a re-
       covery cycle.  The concentrated  liquor is sprayed into a furnace where
       the organic compounds are  burned.  The residual  inorganic compounds may
       be  collected and reused in  the  manufacture  of cooking acid.
                                      -86-

-------
A-Tower  System
                   B-Milk-of-Lime System
COMBUSTION
CHAMBER OR
SCRUBBER
1
t
                          REUEF(b)
SULFUR..
OR
PYRITES


SULFUR.. BURNER!
0 R
PYRITES FURNACj
                                       WATER
                      F=l
                                                    SLAKINS TOWER
                                      | L'ME  j	1   | ABSORPTION TANK3_»j EXHAUSTER
                                                                           ATM.
                   WASTE LIQUOR
                   TO SEWER
                   OR RECOVERY
                                         WASTE LIQUOR
                                         TO SEWER
                                         OR RECOVERY
            FIGURE  3-22.
SULFITE  PULPING FLOW  SHEETS
DIRECT OR  INDIRECT COOKING
WITH OR  WITHOUT FORCED  LIQUOR CIRCULATION
                              -87-

-------
  3.4.2  SULFITE PROCESS VARIATIONS

        There are a wide variety of processes in use for recovery and disposal
        of  spent sulfite pulping liquors.  Because for a number of years there
        was little attempt to recover chemicals at all, and during the en-
        suing years a variety of systems were applied as process modifica-
        tions,  there is very little available comparing operating variables.
        Only recently have several systems been designed for complete recovery
        applications in sulfite operations.  This section, will be devoted to
        briefly discussing some of the operating variables associated with
        certain systems.

3.4.2.1  Ammonia-Base  Liquor  Burning and  Sulfur  Dioxide Recovery

         The use of  ammonia-base  for sulfite  pulping  requires  consideration
         of waste liquor burning  and recovery,of sulfur dioxide -  the  com-
         bustion product.   Depending on  the pulp products desired, an  ammonia-
         base  mill  can  use  any  one of  three basic  pulping techniques:  acid
         sulfite,  bisulfite,  and  neutral  sulfite semichemical.

         Coupled with  the liquor  burning  process,  one of the  combustion
         products,  sulfur dioxide reacts  in an absorption system with  anhydrous
         or aqueous  ammonia makeup chemical to produce ammonium bisulfite
         acid.   Several  mills in  North America are burning  ammonia—base
         liquor  without  sulfur  dioxide recovery.

         Limited data from  the  test on ammonia-base liquor  burning indicates
         solid  loading  in  the stack gases was 1  Ib per 1000 Ib of  flue gas un-i
         der stable  operating conditions.   Limited flue gas analyses showed
         1 % sulfur  dioxide by  volume on  a  dry basis  and 100  to 300 ppm of sul-
         fur trioxide.   It  has  been determined small  variations in firing
         liquor  solids  content  can have  a major  influence on  the heat  load and
         burning intensity.   The  higher  flame temperature should reduce un-
         burned  carbon  carry  over.

         Burning intensity  is also adversely  affected by large particle size,
         hence  the  necessity  to obtain good atomization.  Good atomization is
         affected  by liquid viscosity.   Table 3-6 and Figures  3-23 and 3-24
         relate  some of  the operating variables  associated  with ammonia-base
         liquor  burning.

         In absorption  system design,  interdependent  factors  affecting absorp-
         tion  effectiveness must  be  balanced. Acid  concentration, concentra-
         tion  of sulfur dioxide in  the  gas, and  operating  temperature  determine
         the arrangement and  amount  of  absorption surface.
                                     -88-

-------
Table 3-6.  Ammonia-Base Liquor Burning Tests.

Liquor rate, Ibs/hr
Solids concentration, %
Natural gas rate, Ibs/hr
Heat release rate,
million BTU/hr
Total air at stack, %
Air temperature, °F
Liquor temperature, °F
Furnace exit gas tempera-
ture, °F
Stack dust loading,
lbs/1000 Ibs gas
Average S02 at stack
volume, %
Average $03 at stack
volume, ppm
Test 1
773
48.4
180
6.9
105
500
206
2240
—
0.42
70
Test 2
909
44.6
157
6.7
108
750
165
1800
0.70
0.9
84
Test 3
1100
53.7
0
5.1
110
750
165
1820
1.4
1.13
350
Test 4
815
54.6
0
3.75
114
550
165
1750
0.70
1.01
10
                                -89-

-------
    3600
    3?00
o:
LU
D.
LU
    2300
    2400
         100
80            60

 Solids, weight °t
40
Figure 3-23.  Effect of ammonia-base  liquor solids content on  flame
              temperature.
                              -90-

-------
                . 160
  180      200
TEMPERATURE, °F
220
240
Figure 3-24.   Viscosity of ammonia  and magnesium liquors  (54.5%
              solids  content.)
                              -91-

-------
         Available technology limits absorption system design to a temperature
         level  of about 100°F, requiring that the combustion gases leaving  the
         boiler be cooled by dehumidification before entering the absorption
         equipment.   In one operation, combustion gases were cooled to 104° in
         a packed cooling tower, and 99% recovery of sulfur was achieved  from
         gases  containing 0.5-0.7 vol. % sulfur dioxide in the production of
         a 6.25 pH solution of ammonium bisulfite and sulfite.

3.4.2.2  Magnesium Oxide Recovery System

         The recovery of magnesium in a sample recovery system is made pos-
         sible  by the chemical and physical  properties of the base chemical.
         Spent  liquor burned at elevated temperature in a controlled oxidizing
         atmosphere  yields the base in the reusable form of an active magne-
         sium oxide.   The oxide is readily recombined in a simple secondary
         system with sulfur dioxide produced in the combustion to yield cooking
         acid for pulping.

         The concentration of sulfur dioxide in the stack gas from a recovery
         system can  be maintained at less than 250 ppm by dry volume.  For  a
         magnefite mill, this is about 3 Ibs sulfur per ton of unbleached
         pulp,  which is a small amount compared to the total  mill  sulfur
         loss of 70-80 Ibs/ton.  The 250 ppm is equivalent to 2-3% of the
         sulfur in the liquor feed to the recovery furnace.

         The sulfur dioxide recovery efficiency of the three absorption
         Venturis has been measured at 97.5% when producing an acid with  an
         average concentration of 5.7% total sulfur and 3.2% combined sul-
         fur dioxide.  Concentrations of sulfur dioxide in the gases
         entering and leaving each absorption venturi are plotted in Figure
         3-25.   There is considerable difference in the capacity and per-
         formance, of recovery systems designed for the various processes.
         This diversity is presented by Tables 3-7  and 3-8, using as a
         basis  of comparison typical conditions for a kraft recovery unit.

3.4.2.3  Other Magnesium Oxide Sources

         Test data from a magnefite pulp recovery system presented by Figure
         3-26 illustrates factors to be considered in an evaluation of sec-
         ondary system performance.  The system consists of a packed tower
         for cooling combustion gases to 104°F prior to their entering a
         series of three absorption Venturis.

         Sulfur dioxide gas from the burning of makeup sulfur enters the  re-
         covery system at the induced draft fan inlet after passing through
         the fortification system and this quantity is included in the gas
         analysis at the cooling tower inlet.  Digester relief gases enter
         the recovery system at the base of the cooking tower.
                                       -92-

-------
  oo
  i—i
  00
o
sg
1.2


1.0



0.8



0.6



0.4
d£   0.2
00 O
     INTL
VENTURI
   f
2ndiVEN
                       EN^UIR
IN1,ET } AVG.  =
£,
                                             1.05%
                                            .   ,

        IN^ET f AVG.  = 0.765%
              T
      Figure 3-25.
              Secondary recovery system performance for a
              product acid composed of 5.75% total  SO^
              and 3.25% combined S02.
                                 -93-

-------
Table 3-7.  Recovery Unit Performance - Relative Comparison for 1-lb
            Solids.

Liquor heating value,
BTU/lbs solids
Thermal efficiency,
% total input
Steam generation,
Ib/lb solids
Flue gas leaving
evaporator, Ib/lb solids
Table 3-8. Recovery Unit
Unbleached Pul

Lb solids/a. d. ton
unbleached pulp
Yield, % (approximate)
Solids flow, Ib solids/hr
Total heat input, million
BTU/hr
Steam flow, Ibs/hr
Lb steam, ton pulp
Board
Linerboard
6600
59.7
3.7
7.0
Performance at
P
Linerboard
3000
45
37,500
213
139,000
11,120
Magnesium
and
Magnefite Bisulfite
News Dissolving
Furnish Grade
6800
64.1
4.1
7.0
300 Tons/Day
Magnefite
News
Furnish
1850
60
23,120
169.5
95,000
7,600
8000
68.9
5.2
8.5
Air-dried
Magnesium
and
Bisulfite
Dissolving
Grade
3200
37
40,000
343.0
208,000
16,649
Flue gas leaving cyclone
  evaporator, Ibs/hr
262,500
162,000
340,000
                                 -94-

-------
00
i—i

c/l

-------
         Overall  performance data indicates that the  concentration  of  sulfur
         dioxide in the gas discharged to the atmosphere gives  a  more  defi-
         nite measure of system performance than an efficiency  value based
         on inlet and outlet concentrations of sulfur dioxide.

3.4.2.4  Jenssen Exhaust Scrubber

         Sulfite cooking acid is often produced in a  Jenssen-type,  two
         tower limestone system.  Data show that weak tower exhaust
         contains an average of 0.5% S02 with trace amounts of  sulfur  tri-
         oxide.   These data are summarized in Table 3-9.   Typical  mass
         transfer type scrubbers have resulted in S02 recovery  efficiencies
         of over 98%, with about 50 ppm S02 in the scrubber exit  gases.
         Data on the liquid composition of the NaOH-SO?-H20 system  as  a
         function of pH are plotted in Figure 3-27, and a schematic of the
         scrubbing system indicating controlled variables is shown  in
         Figure 3-28.

3.4.2.5  Scrubbing Blowpit Gases

         Sulfur dioxide loss from digester blowpit vents is a major emission
         source for most sulfite pulp mills.  Such losses may be  virtually
         eliminated by the application of a chemical  scrubber on  the resid-
         ual  gas from an existing water absorption S02 recovery system.   The
         gas collection system for the .scrubber is designed such  that  a
         portion of the high volume, low S02 content  gas released during  the
         initial  45 seconds of the digester blow bypasses the tower and  is
         vented to the atmosphere.  During the remaining 13 to  14 minutes
         of the blow, outside air is drawn in, allowing the scrubber to
         process a constant volume.

         Scrubbing liquor is a mixture of makeup NaOH and a 4.5%  solution of
         Na2 C03/NaHC03 from the recovery process at  a pH of 9-10.  Operating
         the tower at a rate of 10,500 lbs/ft2 liquor and 2,000 lbs/ft2  gas
         (90°F)  has resulted in S02 absorption efficiencies of  99 to 99.5%.

         Because nearly all of the sulfite mills built in the past  20  years
         have used the magnesium-base system, this report will  give greater
         emphasis to a description of that process.   The magnesium-base  sys-
         tem provides maximum recovery of process chemicals and minimizes
         air and water pollution problems connected with the pulping system.
         Aside from the liquor recovery system, however, the sulfite process
         is independent of the base chemical used. Figure 3-29 illustrates
         a typical system.
                                    -96-

-------
Table 3-9.  Jenssen Tower Gas Analysis.
Gas
Sulfur Dioxide
Oxygen
Nitrogen
Carbon Dioxide
Sulfur Trioxide
Concentration
Inlet
(%)
20.5
5.1
74.3
0.1
0.03
Concentration
Exhaust
(%)
0.5
5.3
85.3
8.9
0.03
                                  -97-

-------
Q.
90



80




70


60



50



40
         06
               07     08     09     10

                 WEIGHT RATIO,1 NaOH SO,
12
 Figure 3-27.
             Liquid composition of the NaOH S02-HpO system as a
             function of pH.   By defining two variables, the
             third is fixed.
                              -98-

-------
JEHSSEN
EXHAUST
                                       J	
                                        ,	jsUv	..-^S-L--'1
                                        1	i>NY^A>\J
                                                             15% S00
->
                                                                                            ABSORPTION
                                                                                            COLUMN
                                                                                             TO  NSCM
                                                                                             PROCESS
   Figure 3-28.   Jenssen exhaust scrubber process flow.  (FIC,  flow control; DIG, density
                 control; pHIC, pH control.)

-------
                          Mg(HS03)2 + H2S03
                           Cooking Liquor
     Chips
                           To Atmosphere

                              _L
                          MgO     To  Stack
                    Blow Gas
    Digester
o
o
           Blow
                              Scrubber
Blow
Tank
                     Pulp
                    Fi1ter
                  Pulp
       Spent (Red)
       Liquor
                        Slurry
                         OJ
                        -Q
                        -Q
                         3
                         i~.
                         O
                        CO
                                Abs.
                                Tower
                                                       (HS03)2
Abs.
Tower
                                             •iy (HSOo)-
Abs.
Tower
                       Cooled  Gases
                       (1% S02)
                              Scrubber
                                                                                                          ID Fan
                                                                                                         O
                                                    To Atmosphere
                                                            Mult.
                                                           Effect
                                                         Evaporators
                                              Concentrated
Red Liquon
Sulfur
Makp-yp . 	 	



MgO Slurry
Magnesia
Make-up _»,
Water -•.
V
!
/
SI urry
Tank


                 Recovery
                  Furnace
                                                                            Gases
                                                                          MgO + S02
                                              Gases
                                             '(1%  S02)
                                                                                                           Cyclone
                                          FIGURE 3-29.   SULFITE  PULPING PROCESS
                                                        MAGNESIUM  BASE RECOVERY

-------
The cyclone collection system, coupled with the wet scrubbers and absorbers
used to remove S02 from the recovery furnace gases, control particulate
losses from this operation.  In addition, many mills generate their own
steam and power, and those using fossil fuel and bark are subject to the
normal emissions from this type of equipment.

A summary of emission data relative to various sulfite pulping processes
is contained in Table 3-10.
                              -101-

-------
                                                     TABLE  3-10

                                    SUMMARY OF EMISSION DATA - SULFITE PROCESS
                                              (Emissions in Ibs/ADT)
          Digester Blow Pit                                             40-100
               or Dump Tank                                             10-25

          Water Scrubbers Following Blow Pit                           0.8-20

          Chemical Scrubbers Following Water Scrubbers               0.015-0.4
i
o         Oenssen Tower Exhaust                                         10-15
ro
i
          Scrubbers Following Jenssen Tower Exhaust                   0.22-0.5

          Multiple- Effect Evaporators                                   5-10

          Recovery Furnaces,(Magnesium Sulfite Process)                  50-75
               Following Scrubbers                                       3-15

          Incinerators, Ammonium Base                                  250-500
                                                                                         Particulate

-------
3.4.3  PULPING PROCESS
       The pulping operation  (or cook) is carried out in a pressure vessel called
       a digester.  Up to the present time, batch digesters have been used ex-
       clusively for sulfite  pulping.  Recently, the first continuous sulfite
       digesters have been put into operation.  Batch digesters may be as large
       as 10,000 cubic feet capacity and hold up to 100 tons of wood chips.  The
       cooking liquor, containing a mixture of magnesium bisulfite and sulfurous
       acid, is pumped into the digester cold and then heated by steam in an ex-
       ternal heat exchanger  or by direct addition of steam to the digester.
       Normal maximum cooking temperatures will range from 250°F. to 300°F. at
       pressures up to 110 psi depending on the pulp grade being made.  Cooking
       times will vary from as low as six hours to as high as 20  hours.  Low
       temperatures and longer cooking times are associated with a special type
       of sulfite pulp known  as Mitscherlich pulp for glassine paper.  Where
       dissolving pulps are being made, careful control at the digesters is ex-
       tremely important to final pulp quality.

       During the cooking cycle, it is necessary to vent the digester occasionally
       as the temperature rises.  These "relief" gases are rich in sulfur dioxide
       and are collected in accumulators for direct reuse.  When the accumulators
       are operating properly, little or no air pollution is associated with the
       cooking cycle.

       Upon completion of the cooking cycle, the digester pressure is reduced to
       atmospheric pressure and the pulp is washed into a tank.  In some cases,
       the dump tank has a perforated, false bottom to allow the pulp to be washed
       in the same tank or blow pit.  Newer systems dilute the pulp and pump it
       to countercurrent drum washers.   During the blow,  sulfur dioxide and volatile
       materials are released.  The blow gases are normally passed through an
       absorption tower to remove sulfur dioxide.  Although the noncondensable
       gases from a sulfite mill have a characteristic odor, in general, they have
       not been considered offensive and in comparison with the much more serious
       problems associated with kraft pulping, little attention has been paid to
       the air pollution .aspects of sulfite pulping.

       After being discharged from the digester, the pulp goes through a washing
       stage.  Spent liquor from this stage is sent to evaporators, if chemical
       recovery is practiced, and the washed pulp is either sent to the bleach
       plant or is used directly in products requiring unbleached pulp.

       Up to this point in the system, the process is independent of the base
       used.
                                        -103-

-------
3.4.4  SPENT CHEMICAL RECOVERY CYCLE (MAGNESIUM-BASE SYSTEM)

       The spent liquor (red liquor) separated from magnesium-base pulp is
       concentrated in multiple-effect evaporators to the desired concentra-
       tion for firing the recovery furnace.  As the strong red liquor is
       showered into the furnace, the organics dissolved from the wood burn
       away, leaving a magnesium sulfite ash.  At the temperature of the
       furnace (about 1600°F.), the ash dissociates into magnesium oxide (MgO)
       and sulfur dioxide (SC^)-  The magnesium oxide is removed from the
       flue gas by a cyclonic collection system and is slurried in water.
       This slurry is later caused to react with sulfur dioxide to form the
       magnesium bisulfite for the cooking acid.  The sulfur dioxide is
       scrubbed from the flue gases with water to form the sulfurous-acid
       solution for cooking acid.

       Chemical recovery is efficient for both magnesium oxide and sulfur
       dioxide.  The wet scrubbers used to recover  sulfur dioxide from the
       flue gases also remove particulate matter getting past the cyclonic
       separators.  The major components of a magnesium bisulfite recovery
       system are illustrated in Figure 3-30.


3.4.5  PREPARATION.OF PULPING CHEMICALS

       The magnesium-oxide slurry from the recovery furnace is fed into an
       absorption tower with sulfur dioxide scrubbed from the flue gases or
       produced in a sulfur burner.  Magnesium bisulfite is formed as follows:

                          MgO + 2S02 + H20 -*• Mg(HS03)2

       In the preparation of calcium-base sulfite liquor, S02 from a sulfur
       burner is passed through a limestone-packed tower countercurrent with
       water to form Ca(HS03)2.  An excess of S02 is added to form sulfurous
       acid according to the need for the grade of pulp being made.  Pulp
       characteristics and pulping conditions can be affected drastically by
       varying the ratio of "combined" and "free" S02.  Some minor SO? losses
       may occur around the absorption system, but no data  are  available with
       regard to the extent of such losses.


  3.5  SULFITE RECOVERY SYSTEMS, PRESENT AND FUTURE PROSPECTS

       The choice of a recovery process for sulfite pulping is not a simple
       one.  This is in part because sulfite recovery technology is still in
       a state of active development, as evidenced by the variety of processes
       now in use or proposed for use.  This is also in part because of the
       widely differing requirements with regard to both cooking liquor com-
       position.and load on the recovery over the whole range of sulfite pulp-
       .ing processes from high yield semi-chemical pulps to low yield dissolving
       pulps.  And, this is in part because of the varying interrelationship
                                       -104-

-------
                                                                    STEAM FOR PROCESS
                                                                    AND POWER
  CHIPS
DIGESTER
                                                         RECOVERY
                                                         BOILER
                                   S02IN FLUE OAS
                                 STRONG
                                 RED
                                 LIQUOR
                                 STORAGE
            FORTIFICATION
              TOWER
                                                         MECHANICAL
                                                         DUST COLLECTOR
                                                                  MAKEUP
                                                                  Mg(OH)_
                                                                      LIQUOR HEATER
                                          MAKEUP
                                          SULFUR
                COOKING
                  ACID
                STORAGE
                                                         SULFITE
                                                         LIQUOR
                                                         EVAPORATORS
                                      SULFUR
                                      BURNER
                3 STAGE
                 WASHERS  I	»•
                     WEAK
                     RED
                     LIQUOR
                      FIGURE 3-30.   MAGNESIUM  BISULFITE PROCESS  FLOM
                                            -105-

-------
      - of technical,  ecological,  and  economic  factors  for  each  installation, as
       a function of  size and  location  as  well  as  of special  situations,  such
       as integration with other  pulping processes or  the  manufacture  of  by-
       products.   It  is,  nevertheless,  possible to draw  some  general conclusions
       regarding  the  present or probable trends in sulfite recovery, based on
       the information available  today.  It is believed  that  these  choices
       represent  the  most direct  solutions to  the  problem  of  .eliminating  air
       and stream pollution from  spent  sulfite liquors.


3.5.1   SULFUR RECOVERY ONLY

       For small, independent, low combined acid sulfite mills  with either
       calcium or ammonia base, the lowest' cost solution would  appear  to  be
       based upon recovery of heat values  and  the  possible recovery of sulfur
       dioxide, but with no attempt at  recovering  the  base for  reuse. _ After
       concentration, both liquors may  be  burned in a  conventional  boiler
       equipped with  a Loddby furnace or  in a  fluidized  bed;  and the sulfur
       dioxide may be recovered from digester  blow gases and  from the  spent
       liquor prior to evaporation.  When  burning  in  a conventional furnace,
       adequate dust collection should  be  provided and for the  ammonia base
       liquors, nitrogen oxides may present a  problem  at higher furnace tern-.
       peratures.  Both boiler and evaporator  investments  may be minimized  by
       use of most of the recovered heat  for direct contact liquor evaporation.
       For most paper-grade pulps, higher  yields may be obtained with  soluble
       bases, which should justify the  use of  ammonia  base for  small installa-
       tions.

       It might also be noted that Spring  Chemicals,  Ltd.  has recently announced
       recoveries for calcium, magnesium or ammonia base acid sulfite or bi-
       sulfite liquors, with recovery of both  the base and sulfur dioxide.   The
       first step is precipitation of calcium as calcium sulfite, which reduces
       or eliminates scaling and also serves as the base recovery in calcium
       base pulping.


3.5.2  MAGNESIUM-BASE ONLY

       For larger installations, use of magnesium or sodium with recovery of the
       base can  be justified.  The recovery of  the magnesium base  can be carried
       out by  conventional  (Babcock & Wilcox  and  Lenzing) or fluid bed (Copeland)
       combustion to give magnesium oxide  in  a  form which may be reused  in the
       process.  These available recoveries are now well  established; however,
       magnesium base systems  are  limited  to  pulping on the  acid side and,there-
       fore, are not  suitable  for  the newer high  strength alkaline sulfite
       pulping processes.

       Sodium  base may be  used over the entire  pulping  pH range.   In  part, for
        this  reason,  there  are  a  greater variety of sodium base  recoveries with
        none  so well  established  as those  for  magnesium  base.
                                         -106-

-------
3.5.3  CROSS AND SALTCAKE RECOVERIES

       Where location and capacities are suitable, the simplest sodium base
       "recovery" is combustion of the spent sulfite liquor as make-up with
       kraft liquor in the kraft recovery furnace (cross recovery).   For small
       isolated mills, sodium base liquors may be burned in a fluid  bed to
       produce by-product sodium carbonate and sodium sulfate, suitable for
       kraft make-up or as alkali in the manufacture of glass (Copeland and
       Dorr-Oliver).


3.5.4  CONVENTIONAL SODIUM RECOVERIES

       The larger, independent sodium base' pulp mills must have their own re-
       coveries.  The majority of present sodium base recoveries are based on
       the displacement of hydrogen sulfide from kraft-type green liquor with
       carbon dioxide, the combustion of the hydrogen sulfide to sulfur dioxide,
       and the recombination to form a pulping liquor (Sivola-Lurgi, Stora
       Kopparberg, and Tampella).  One is based on so-called "shock  pyrolysis"
       to separate sulfur as hydrogen sulfide from the sodium base,  which is
       recovered as sodium carbonate (SCA-Billerud).  Ion exchange is also
       practiced for partial recovery of sodium base (Ontario Paper  Co.).
       Direct sulfitation of green liquor with recovery only of the  base has
       also been used (IPC).


3.5.5  NEWER' SODIUM-BASE- RECOVERIES

       In their more recent forms, sodium base sulfite recoveries are reported
       to be economically competitive with comparable magnesium base recoveries.
       They are also of the same order of cost as kraft recovery, in particular,
       where the higher yield of the sulfite pulp places a lower organic load
       on the recovery system.  With further development of sulfite  recovery
       systems, these costs should be further reduced.  Several such systems
       are depicted in Figures 3-31 through 3-35.

       Among such possible developments are bisulfite sulfitation (IPC), solid
       state carbonation (Mitsubishi), a new and simplified green liquor car-
       bonation recovery (Owens-Illinois-Vulcan Cincinnati), direct  oxidation
       of smelt or green liquor  (Bratislava-Lurgi and Owens-Illinois), and fluid
       bed pyrolysis (Owens-Illinois).


  3.6  SUMMARY OF AIR POLLUTION PROBLEMS

       The terpene-like odors from the digesters and leaks of SOp in the various
       accumulators, storage tanks, washers, dump tanks, absorption  towers, etc.,
       are the normal sources of air pollution connected with sulfite pulp mills.
       Sulfur dioxide can readily be removed from gas streams with water scrubbers,
       Most sulfite mills in operation today find it economically sound to re-
       cover all the S02 possible.


                                     -107-

-------
CONCENTRATED
SPENT
LIQUOR
\


p RASES*. ,. 	 ^__
SMELT
1 '
GRANULATION
No2CO a Nq2S


STFAM Z U*IUAIIU™
^~~~^^ '
NcgCOj i 6L Na2S03
H«0 	 	 *> SOriJTION


N^co^a^so,
COOKING LIQUOR Pf

10 ABSORPTION 	 — 	 .... n.0

1
;o3a
Na2S03
1 1
EPARATION
FIGURE 3-31. DIRECT OXIDATION RECOVERY
CONCENTRATED CONaCpi!T5ATED
SPENT LIQUOR
LIQUOR I
i



, ^MELT **£mo*
H2o 	 •*• SOLUTION » H2s BURNER! — i No2so3

Na2coja Na23 H s' S02
1 2I . f
BISULFITE 	 1 1 S02 •*
TTPAM < ^. ^A Mullen 1 ^m
STtAM »- R|]| F|TAT|ON -«-NaHSOvl ABSORPTION "* ,TACK

NapSO, NaHSO
i t
COOKING LIQUOR PREPARATION
-— - «^ SFOONDARY
r-n»«iF«-^ PYROLY3IS - GASES-^ — I
GASES'^ 6ASES-*- COMBUSTION ^
No2C03aC FLUEOA3
	 sri- ^1
-AIR — ». OXIDATION . 	 ». . . 	 »>
- HsO^* ABSORPTION STACK GAS
Na2C03
— H20 ••• SOLUTION Na,C03
1 1
N,, C03 MP2S03aNoH303
COOKING LIQUOR PREPARATION
FIGURE 3-32.  BISULFITE SULFITATION RECOVERY     FIGURE 3-33.  FLUID BED PYROLYSIS RECOVERY
                                          -108-

-------
       CONCENTRATED
         SPENT
         LIQUOR
CONCENTRATED

LIQUOR
                                   STACK SA3
FIGURE 3-34.   SOLID CARBONATION RECOVERY     FIGURE  3-35.  GREEN LIQUOR CARBONATION  RECOVERY
                                           -109-

-------
                            CHAPTER   4

            MONITORING PROCESS AND CONTROL EQUIPMENT VARIABLES
     This chapter presents those major process and control  equipment
     variables that may be monitored with in-line instrumentation
     associated with modern wood pulping operations.   The importance
     of the measurement of these variables as they relate to pro-
     duction and emission levels has been described in Chapter 3.
     In addition to standard on-line process instrumentation, applied
     to both process and control equipment, emission  monitors for
     particulate and gaseous components that have proven application
     are discussed.  Major emphasis has been placed on the kraft
     pulping process because of its dominance in the  chemical wood
     pulping industry.
4.1  KRAFT PROCESS INSTRUMENTATION

     Tables 4-1  and 4-2 in concert with Figures 4-1  through 4-13
     depict instrumentation symbols and codes and standard kraft
     process flow sheets with superimposed in-line instrumentation.

     The descriptions and depictions presented herein are for a kraft
     pulp mill  and includes a typical  bleaching operation.  Although
     the kraft process was utilized for this illustration, the same
     approach would apply to both the sulfite and NSSC processes.
                                   -110-

-------
Table 4-1.  Kraft Mill Instrument Applications.
DIGESTER ROOM
Liquor drawdown and refill
Total steam flow
Heater condensate level
Heater condensate conductivity
Steaming
Temperature-pressure
Gas-off
Blow tank level
Turpentine condenser temperature
Liquor circulation flow

BROWN STOCK HASHER
Blow tank level
Blow tank motor load dilution
Stock to washer flow
Knotter dilution
Shower
Filtrate tank level
Repulper dilution
Strong liquor baume
Strong liquor filter
Liquor to evaporator - flow
Strong liquor storage level
Washed stock storage level
H. D. chest dilution
SCREEN ROOM
Washed stock storage level
Consistency
Stock flow
Dilution
Screened stock storage level

BLEACH PLANT
Screened stock storage level
Consistency
Chemical flow
Tower levels
Tower temperatures
Dilution
Mixer temperatures
Shower flows
Total steam flow
Total water flow
Fresh water make-up flow
Filtrate overflow to sewer
Bleach stock storage level
H.  D. storage dilution
Chemical storage level
Effluent to sewer - flow
Hot water temperature
                               -111-

-------
Table 4-1.  Kraft Mill Instrument Applications.
(Cont'd)
BLOW STEAM HEAT RECOVERY
Condenser temperature
Condenser water make-up temperature
Heat exchanger temperature
Clean hot water tank level
Clean hot water tank temperature

BLACK LIQUOR EVAPORATOR
Strong liquor storage level
Strong liquor baume
Flow ratio - liquor to 5 and 6 effects
Temperatures
Pressure and vacuum
Soap tank level
Steam flow and pressure
Boiling point rise
Condensate level
Thick liquor flash tank level
Condensate diversion
Thick liquor storage level

RECOVERY

Thick liquor storage level
Thick liquor flow
Cascade evaporator level
                               -112-
Precipitator wet bottom level
Multiple indicating draft gauge
Temperature in & out - cascade
Liquor-salt cake ratio
Primary heater temperature
Secondary heater temperature
Liquor to nozzles-pressure
Feed water control  system
Oxygen
Steam temperature and pressure
Air flow
Dissolving tank density
Dissolving tank level

CAUSTICIZING
Liquor storage level
Raw green liquor flow
Green liquor temperature
Hot water temperature
Clarifier rake-torque
Water to lime mud filter
Lime mud density
Lime mud filter shower flow
Filter cake thickness
Lime mud filter vat - level

-------
Table 4-1.  Kraft Mill Instrument Applications.
(Cont'd)
CAUSTICIZING (continued)
White liquor flow

KILN
Oil temperature
Oil pressure
Oil storage level
Hot end temperature
Exit gas temperature
Draft control  and gauge
Atomizing steam pressure
Kiln speed
Drive motor load
Scrubber level

CHEMICAL MAKE-UP AND HANDLING
Storage levels
Chlorine gas pressure
Chlorine vaporizer temperature
Caustic strength of solution
Strong caustic  temperature
Hypo mixing
Chemical flows
Lime feeder
CHLORINE DIOXIDE PLANT
Chemical storage levels
Chemical mixing
Temperature
Cold water make-up
Spent liquor pH
Chlorine dioxide flow
High-low alarms
                               -113-

-------
                                      Table 4-2   TYPICAL LETTER INSTRUMENTATION  SYMBOLS


Process
variable

Analysis3
Burner Flame
Consistency
Density
Electric6
Flow0
Hand
Level
Moisture
Pressure0
Speed
Temperature0
Viscosity
Weight
t letter
CO
t.
Ll_

A-
B-
C-
D-
E-
F-
H-
L-
M-
P-
S-
T-
V-
W-
cn
c
o

TD
t— i
-I
AI
BI
CI
DI
El
FI
HI
LI
MI
PI
S-
TI
VI
WI
ricaDL
en
c
-a
i.
o
o
01
CtL
-R
AR

CR
DR
ER
FR
HR
LR
MR
PR
SR
TR
VR
WR
u i ny i
0 HI
en o c
en c -i- o
C T- > -r-
•i— +-> aj -t->
N n3 T3 rtj
•r- t- >
i — en to t-
ea oj t/i tii
O C r- _Q
1— -r- C3 O
-Q -G
AQ



EQ
FQ FG

LG


SQ

VG
WQ
pin
c

ca
-T
AT
BT
CT
DT
ET
FT

LT
MT
PT
ST
TT
VT
WT
cUlbllll til
en
c
n3
O

-b
tr

-IT
AIT
BIT
CIT
DIT
EIT
FIT

LIT
MIT
PIT
SIT
TIT
VIT
wn
"9-1
en
c
i.
0
o
01
a:
-RT
ART

CRT
DRT
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                                                                NOTES

  Readily recognized self-defining  symbols  such  as  C0?, 0?, pH, and ORP may be used in place of A.
i                                                    £   £
  Letter subscripts  c (current),  v  (voltage),  or w  (power) may be used after E to designate type of measurement.
0 Lower case letters r,  d,  and t  may  be  inserted to distinguish ratio, difference, and time respectively.

  Q may also be used with letters I,  R,  and C  where indicating, recording, or control functions also exist.
e Lower case letter  subscripts 1  and  h may  be  used  to denote  low or high alarm functions.

/ If required note (a)  could be expanded to cover any first letter, not in conflict with those listed, as  long as a description for such a
  designation is part of the flow diagram.

-------
 LOCALLY
 MOJMTEO
 o
JNSTIiUM E NT     -
 SERVICE AND  FUNCTION
                              TRANSMITTER
                              •Hi'—
                             .PRIMARY FLOW
                              DEVICE
                                             JWCUM ATI C.TRANSMISSION..
                                             JM3I!M'!ML (ELECTRIC
                                              TRANSMISSION THE SAME
                                              EXCEPT FOR TYPE OF
                                              CONNECTION.)
 LOCALLY
 MOUNTED
 BOARD
MOUNTED
 COMBINATION  INSTRUMENT
 OR DEVICE WITH TWO SERVICES
 OR  FUNCTIONS
                             DIAPHRAGM
                             MOTOR VALVE
                            ELECTRICALLY   PISTON
                            OPERATED
                            VALVE
                            (SOLENOID OR
                            MOTOR)
                                         OPERATED
                                         'VALVE
                  3-WAY BODY
                  FOR ANY VALVE
      (HYDRAULIC
      OR PNEUMATIC)
                SAFETY
               (RELIEF)
                VALVE
              PNEUMATIC TRANS-
              •MlSSjON FROM	
             _[NSTRU^E_NJ JTO	
              DIAPHRAGM 'MOTOR
              VALVE
                                   SELF ACTUATED
(INTERGHAL)
REGULATING VALVE
                INSTRUMENT  AIR  LINES

                INSTRUMENT  PROCESS  PIPING

                INSTRUMENT  CAPILLARY TUBING
	    INSTRUMENT ELECTRICAL  LEADS
  FIGURE 4-1  TYPICAL  PICTORIAL INSTRUMENTATION SYMBOLS
                                          -115-

-------
 A-
 LOCALLY
 MOUNTED FLOW
 RECORDER
FLOW TRANSMITTER
WITH PNEUMATIC
TRANSMISSION TO
BOARD-MOUNTED
FLOW RECORDING
CONTROLLER
LEVEL TRANSMITTER  WITH
PNEUMATIC TRANSMISSION  TO
BOARD-MOUNTED LEVEL
RECORDER CONTROLLER
TEMPERATURE  TRANSMITTER  WITH
PNEUMATIC TRANSMISSION TO
BOARD-MOUNTED TEMPERATURE
RECORDER CONTROLLER
                   CASCADE CONTROL LOOP PRESSURE RECORDER
                   CONTROLLER  SETS FLOW RECORDER CONTROLLER
  FIGURE  4-2  TYPICAL  BASIC  INSTRUMENT  DIAGRAMS
                                        -11.6-

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STEAM
                                                         RELIEF
   Flftl iPF
("U'^F
\J v> i ^ (-...
      i^3TKUiViEMTAT!OM  FOR  KRAFT BATCH  DIGESTER
  FT-I
  STEAM
F..OV/ TRANSMITTER
 FHC-I  STKAM FLOW RECORDING
       CONTROLLER
 LSR-I  LOW  SELECTOR RELAY
  RR-I  Ri£VEf?SING RFLAY
  FY-I  STI-:AM FLOW CONTROL VALVE
  PT-2  DIGESTER  PHtySUHE TrtAiJGMlT
CPC-2  CAM PRESSURE CCNTROLLER
TPR-2  D!(.-cGT;IR TEf/IP. PRESS. RECORDER
 FT-3  RELIEF FLOW TRANSMITTER
PIC-3  RELIEF FLOW INDICATING
                                 380-4 SLOW BACK CONTROLLER
                                 SBV-4 BLOW SACK CONTROL VALVE
                              -117-

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               L.P. STEAM
                CONDENSER
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          WHITE     fi\

          LIQUOR    VLi
           BLACK

           LIQUOR
                                                                                                                                               STEAM
                                                                                                                                                  TO

                                                                                                                                               EVAPORATOR
                                                                                                                                      »TO BLOW TANK
                               COLO BLOW LIQUOR
                                                 FIGURE  4-4 INSTRUMENTATION  FOR A CONTINUOUS  DIGESTER

-------
FIGURE 4-5   HOT STOCK SCREENING  INSTRUMENTATION
                                                                                                      PRIMARY
                                                                                                      BROWN STOCK
                                                                                                      WAShER

-------
                                                                                                                             HOT

                                                                                                                             WATER
ro
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                                             y_ ELACK LIQUOR
                                             T TO EVAPORATORS
                                        FIGURE  4-6 PULP WASHER INSTRUMENTATION

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                                                            i  LJ^O^   ,<=^-?^
                                                            . \—:—j ,—>	-^    f . ' V  •  S
FIGURE 4-7  FOUR-STAGE BLEACH PLANT INSTRUMENTATION

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                               LOW PRESSURE
                               ALARM
UNLOADING LINE
FIGURE 4-8  SODIUM HYPOCHLORITE BLEACH LIQUOR  PREPARATION INSTRUMENTATION.

-------
                                 H.P. AIR

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                  TANK CAR

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                                                                                                                         SYSTEM
                                                                                                                  * EMERGENCY SHUTDOWN SYSTEM
                                                                                                                    FROM HI-TEUP AT TR-15 NOT
                                                                                                                    SHOWN
                        FIGURE .4-9  CHLORINE  DIOXIDE  BLEACH  LIQUOR  PREPARATION  INSTRUMENTATION

-------
                                                                                                        CCNOEH3ATE
                        COMPENSATE
                        TO BOILER
FIGURE 4-10   INSTRUMENTATION FOR MULTI RLE-EFFECT EVAPORATOR SYSTEM

-------
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       F.ECY:I.E
       TO L!a£
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                                                   REBURNEO LIME TO
                                                   SLAKER
                 FIGURE 4-11   INSTRUMENTATION  TO CONTROL  COMBUSTION IN THE LIME RECOVERY PROCESS.

-------
            "
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                                                                                          ,-L   I   - BOILER
                                                                                          J.TA  A / ORUM
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                                                                                                                                        (3—<-FEED WATES
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                                          S^O COU^LIMO
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                       STOniGE
                 r
                                                                                                                                              CSEEN LIOUOR TO
                                                                                                                                              RECAUSTICiZiNG PLANT
                                                                                                                                         LV 19
          FIGURE 4-12  SOME OF THE  MORE IMPORTANT  INSTRUMENTATION USED ON  A HIGH CAPACITY RECOVERY FURNACE.

-------
                                                                                    i—""V—i
                                                                                    NEW '
I
ro
          TO i£WES *•
                          FIGURE 4-13  TYPICAL INSTRUMENTATION FOR LIQUOR CAUSTICIZING IN ALKALINE COOKING.

-------
4.2   INSTRUMENTATION  FOR  EMISSION  MONITORING

      There  are  three  basic  approaches  to  instrumented source monitoring.
      In  the first,  which  may  be  called  extractive, a continuous sample
      stream is  drawn  from the stack and transported to the analyzer, which
      can be mounted in  any  convenient  location.  This requires a probe
      mounted in the stack or  duct, and some  form of interface system to
      provide the analyzer with a sample that is  in an appropriate  state
      of cleanliness,  temperature,  pressure,  and  moisture  content.  This
      approach is the  oldest and  has provided the most experience to date.

      The second approach  may  be  called in-situ monitoring.  The instrument
      is  mounted either  inside the  plenum  or  just outside  the stack.  In
      the case of optical  instruments,  the source may be mounted on one
      side and the detector  on the  other,  so  that the instrument scans the
      full width of the  stack.  This method is most commonly used for
      visible particulates or  "smoke."   A  combination of the first  and
      second methods is  to mount  the analyzer directly on  the stack and
      draw the sample  through  it  with little  or no preconditioning.
      Obviously, this  requires an instrument  that can accept the sample
      in  its natural state.

      The third  approach is  to monitor  the plume  above the stack with a
      remote optical instrument.  So far,  this approach is in the research
      stage, whereas the other two  methods have been reduced to a more
      practical  state.

      The in-situ across-the-stack  approach and the remote method offer
      an  advantage over  the  extractive  approach in that they provide an
      average reading  rather than a point  reading.   However, it is theo-
      retically  feasible to  use multiple extractive probes and obtain an
      integrated sample  that is representative of the complete cross
      section.

      The potential  pollutants which may be measured continuously in a
      kraft'pulp mill  include  sulfur dioxide,  TRS, and particulate matter.

 4.3  CONTINUOUS SULFUR DIOXIDE MONITORS

      As previously stated,  sulfur dioxide (S02)  emissions arise from the
      oxidation of sulfur  bearing compounds normally  found in all three
      of the chemical  wood pulping processes.  Generally  speaking,  S0£
      emissions from the kraft process  are limited  to  the  recovery  furnace
      and the ancillary power  generating facilities.   S02  emissions from
      the sulfite and  NSSC processes can be significant  from a  standpoint
      of air pollution and reusable chemical  losses.   The  following des-
      criptions of continuous  S02 monitoring  systems can  be adapted to
      any of the aforedescribed pulping processes.
                                    -128-

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Three methods have been used to monitor sulfur dioxide from the
sulfite process.  These methods include infrared and ultraviolet
spectroscopy and conductivity.

A non-dispersive infrared analyzer has been used in a magnesium base
acid bisulfite mill with success.  The~ reference cell contained all
of the flue gas components less the sulfur dioxide.  The flue gas
is passed through the sample cell at 3.5 CFH and the differential
output is related to the S02 in the flue gas.  The IR cell windows
must be protected from water.  In one instance, a large filter is
followed by a refrigerated dryer reducing the flue gas to -10°F.
Particulates in the flue gas caused frequent plugging of the sample
line and the instrument environment was unduly corrosive for the
electronic circuitry.  It is estimated that one installation cost
in excess of $10,500 and has been continually plagued with ap-
proximately 50 percent instrument downtime.

Thoen's ultraviolet system by contrast is quite simple in design,
relatively inexpensive (less than $2,000), and extremely reliable.
The ultraviolet source and detector are mounted externally to the
flue gas duct and protected from the flue gas by quartz windows.
A 2 1/2 inch diameter tube is located at 90° to the flue gas flow
and connects the externally mounted source and detector.  One-half
inch holes are placed 2 1/2 inches apart at 90° to the gas flow.
These physical arrangements minimize particulate and water ac-
cumulation in the light path tube.  Maintenance is limited pri-
marily to a cleaning of the quartz windows every three weeks.
The instrument has been calibrated externally to the flue gas
duct by passing nitrogen-sulfur dioxide mixtures through the
light path tube.  (Possibly a more reliable calibration pro-
cedure would involve the addition of known quantities of sulfur
dioxide to a flue gas matrix rather than the nitrogen gas base
which has been used.)

A variety of conductivity instruments from home-builts to modified
commercial units have been successfully used by several sulfite
mills.  Conductivity units require close control of reagent and
sample gas flow to maintain calibration.  These instruments are
relatively inexpensive.

Correlation spectrometry and multiple-scan interferometry have
been proposed for use as remote sensing devices to determine the
S02 concentration from industrial and power plant stacks.  In
theory the instrument could be used by the emitter at the source
to monitor S02 emissions or by regulatory officials located in
a mobile unit at some distance from the source.  Significantly,
this can also be done at night.  This instrumentation is con-
siderably more complex than Thoen's ultraviolet system.  Thus
initial expense and subsequent maintenance could be significantly
greater.

                              -129-

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  4.4  GAS/LIQUID CHROMATOGRAPHIC  ANALYSIS  OF  REDUCED  SULFUR  COMPOUNDS

       Pulp mill  emissions  often contain  an appreciable  amount of water
       vapor,  water droplets  and particulate matter  such as fiber, organic
       and inorganic chemicals  and mists.   Proper  sample preparation and
       handling must precede  injection  of the  sample into a chromatographic
       system.   Sample conditioning requirements are dictated by the impuri-
       ties which must be removed  to protect the analytical equipment, or
       by necessity to maintain the physical properties  of the gas so as
       to prevent a material  alteration of  the components of  the gas stream.
       Consideration must,  therefore, be  given to  (a)  appropriate particu-
       late and gas separation  schemes, (b) sample collection and convey-
       ance systems that do not react with  the sample, and (c) sample col-
       lection and conveyance systems that  maintain  the  sample above its
       dew-point temperature.

4.4.1  OPERATING PRINCIPLES

       The function of a gas  chromatographic system  is twofold:  (1) separa-
       tion of the sample into  its individual  components, and (2) determination
       of desired isolated  components with  a suitable  detector.

       Separation of the sample into its  components  is effected by a chroma-
       tographic column.  During analysis,  a uniform flow of  inert gas
       (commonly called carrier gas) is maintained in  the system.  A small
       volatile liquid or gas sample is injected into  the inert gas stream
       prior to its entry into  the column.   As the sample components are
       carried through the  column  by the  carrier gas stream,  absorption and
       desorption from the  liquid  support proceeds in  accordance with the
       individual component's coefficient of distribution.  As the components
       are eluted from the  column, quantitative analysis is performed by a
       detector which monitors  a common property of  the  compounds.  Reten-
       tion time of the component  in the  column is used  to qualitatively
       identify the compound  and measured detector response is used to
       quantitatively identify  the compound.

       For proper operation of  a gas-liquid chromatographic system, the
       sample  handling system,  injection  technique,  column and detector
       must be carefully selected  for the specific application.  Temperature
       and carrier gas flow control  are also important items.  Figure 4-14.
       a  block diagram of a typical gas liquid chromatographic system.

4.4.2  SAMPLING SYSTEMS

       The sample handling  equipment must be constructed of materials which
       will not react with  individual components of  the  gas stream to be
       analyzed.   Those suitable for use  in pulp mill  situations dealing
                                     -130-

-------
,....,  Op)
        FLOW  REGULATOR
INERT
GAS
CYLINDER
         SAMPLE
         INJECTION

         VALVE
         INJECTOR
         HEATING
         ZONE
                              COLUMN
                              HEATING
                              ZONE
L C

LUMN







DETECTOR

PETECTOR
HEATING
ZONE
FIGURE 4-14 GASCP.ROMATOGRAPHY SYSTEM
                       -131-

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       with sulfur gases,  terpenes,  and alcohols,  in  the  one  ppm volume
       basis (v/v) range,  are listed below.

       Teflon and glass are the least reactive  of  the materials  listed
       and are preferred materials of construction for gas  handling  sys-
       tems where batch samples are  handled  and where any absorbance or
       reaction may significantly alter the  sample composition.   Type 316
       stainless steel  is  satisfactory for continuous flow  systems,  and
       after several  exposures, because of saturation characteristics, is
       generally suitable  for batch  sample handling systems.

       The other two  materials, polyethylene and polypropylene must  be used
       with care.   They are sufficiently reactive  to  limit  their use almost
       exclusively to continuous flow systems where any reaction between
       the construction material  and a gas component  alters the  gas  composi-
       tion insignificantly.

                       CONSTRUCTION  MATERIALS FOR  GAS
                       	HANDLING SYSTEMS	

               Least  Reactive                     Teflon
                                                  Glass

               Satisfactory for Continuous        316 - Stainless Steel
               Flow Systems

               Must be  used with care             Polyethylene*
                                                  Polypropylene

               *Limited to temperatures of 250°F or less.

4.4.3  PREPARATION AND  CONDITIONING

       Many emission  sources  at the  point of sampling contain liquid mists
       (a)  which are  not properly a  portion  of  the sample since  they are
       removed prior  to discharge, or (b)  for which no suitable  system can
       be  devised  for their incorporation in the sample.

       Even when judgement dictates  these droplets should be a portion of
       the sample,  their entry into  a heated sampling system and subsequent
       evaporation may  cause  random,  unpredictable and nonrepresentative
       gas  concentrations  in  the sample stream.  As a matter of  course it
       is  therefore a common  practice to remove large liquid droplets from
       the gas stream before  sampling.

       These droplets can  be  removed  by a properly designed entrainment
       separator on the end of the sample probe as illustrated in Figure 4-15.
                                      -132-

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                                     2-TO SAMPLE LINE
                    -ENLARGED'PROBE END
                     .SPLASH PLATE
!£?'" <:'*  !*"  PCJ
 i {.',,. iC»-!'..»  i ii
                         -133-

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With this device, water droplets are diverted by the splash plate
and the small amount that circumvents the plate will fall by gravity
from the enlarged low gas flow velocity area incorporated in the
probe design.  Nothing precludes the use of a properly designed
cyclone for droplet removal providing it is located in the duct so
that evaporation on heated surfaces of a transfer system can be
avoided.

Coarse particulate removal is a requirement in all continuous sam-
pling systems.  Stainless steel tubes of 1 to 2 inches diameter
and 6 to 12 inches long packed with glass wool have been used.
Ceramic or sintered stainless steel- diffuser tubes have also been
used (1 ).  Commercial probes are also available (1 ).  Either
manual or automatic blowback systems for cleaning are required
if frequent removal from the stack for cleaning is to be avoided.
The blowback cleaning system should isolate the probe from the
remainder of the sampling system to avoid major surges in flow
that may cause damage.  Fine particulate filtration following
coarse filtration is a common requirement on continuous flow gas
handling systems.  Walther and Amberg report the use of a com-
mercially available system (2 ).  One filter which removes
particles down to one micron in size found extensive use for
this purpose.  A stainless steel body and sintered stainless
steel filter cartridge make it well suited for use in systems
heated above the gas dew pointf!'   •	

Water vapor is present in most emission sources at concentrations
generally ranging from 20 to 95% (v/v).  When cooled to ambient
temperatures either (a) condensation occurs which entraps unknown
and variable amounts of the components of primary interest, or (b)
some of the components may be cooled below their boiling point
resulting in their condensation.  To prevent these occurrences  the
sample must be maintained above its dewpoint temperature.  This can
be done either by (a) using heat traced sampling equipment, or (b)
dilution of the source gas to the point at which its dewpoint is
below ambient temperature.

Even when dilution is used as a means to avoid condensation, seldom
if ever can the use of a heated sampling line be completely avoided.
Care must be taken to assure that the gas sample temperature remains
above its dew point prior to dilution which normally involves some
heat traced sampling line.  The sample conditioning equipment for
chromatographic analysis is listed below.
                              -134-

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                        SAMPLE  CONDITIONING  EQUIPMENT

              Sample Components        Sample  Preparation Device

              Liquid Droplets           Entrainment  separators

              Participate              Coarse  filtration and fine
                                       filtration

              Water Vapor              Heated  equipment - Dilution
                                       with  an inert gas

4.4.4  COLLECTION  AND TRANSPORTING

       Batch  Systems - One  commonly  used method of  batch sampling involves
       drawing a known vacuum on  a heated  container and subsequently draw-
       ing  a  sample from the source  into the heated container until a
       pressure equilibrium is  established.  This technique has major dis-
       advantages.   Care must be  taken  to  assure that collection lines are
       well purged to assure collection of a representative sample.  Main-
       taining the gas temperature above the dew point when subsequently
       transferring to a multiport sampling  valve is difficult.  If the
       gas  temperature is permitted  to  drop, dilution of the sample may
       occur  as pressure is equalized.  Displacement with an inert gas
       line leading to the  bottom of the container  is the common means of
       forcing the sample to a  multiport sampling valve.  This may result
       in some dilution.  A simple procedure minimizes these problems by
       drawing a sample through an adequate  probe,  a heated sample line, and
       heated sample container.   This permits  purging of the sample con-
       tainer, line and probe,  as well  as  allowing  the walls of the
       sample container to  reach  equilibrium with the gas components
       present.  Such a system  is diagrammed in Figure 4-16.

       The  sample  collection container  is  normally  a glass burette fitted
       with Teflon stopcocks (stopcock  grease  reacts witH most sulfur
       compounds)  although  any  glass container can  be used.  Either must
       be equipped with a heating mantle.  It  is necessary to heat the
       container prior to its use and heating  while collecting the sample
       to avoid any condensation  is  also required.

       The  temperature of the heated sample  is maintained above the dew
       point  prior to injection into the chromatograph.  Transfer of the
       sample is by drawing or  forcing  a portion of the sample in the
       container into a multiport sample injection  valve with care taken
       to insure the sample is  maintained  above its dew point at all times.
       Enough sample should be  drawn through the valve to replace all gas
       in the sample loop and transfer  line  and yet not allow the signifi-
       cant dilution by the incoming inert gas or ambient air in the heated
                                     -135-

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FIGURE
                   BATCH  SAMPLING  SYSTEM
oo
CTi
I
                  HEATED LINE
          A
                                   VACUUM

                                    P U M P


                               HEATED CONTAINER

                                    (GLASS)
                A. ENTRAPMENT SEPARATOR

         SOURCE   AND  PRIMARY FILTER

-------
container.  The multiport sampling valve can be heated in an enlarged
injector oven of the gas  chromatograph  or in a separate oven.   It
is not recommended that this valve be placed in the column oven as
temperature can be varied at this location and can affect the perfor-
mance of most commercially available valves.

Transfer of the sample from the sample container to the chromatograph
injection port can be accomplished by syringe.  A septum is placed
on one port of the container, both stopcocks opened and at least one
syringe of gas (more if required to evacuate any dead spaces) is
removed and wasted to condition the syringe.  The procedure is  sub-
ject to some error due to the condensation that occurs in the syringe
and remains in the needle, as well as the dilution that occurs  as
either ambient air or an inert gas replaces the sample taken from
the sample container.  This dilution is minimal and probably neg-
ligible if displacement gas is introduced opposite the point of with-
drawal and care is used in rapidly transferring a minimum of sample
volume.

Continuous Sampling Systems - Continuous sampling with the gas
chromatograph may be performed by continuously drawing a conditioned
sample from the desired source through a heated inert line attached
to a multiport sampling valve.  Injection of a sample into the  col-
umn then consists of operating the sample valve on a routine basis.
Electrically or steam heated Teflon sample lines are available  com-
mercially ( 1, 2, 3  ).  The system used must include provisions
for removal of particulate matter and entrained liquid as previously
discussed.

Movement of the sample through the continuous flow line and the
sampling valve must be accomplished with an air or water aspirator,
or a vacuum pump since no known suitable inert and leak-proof pump
is known to be available at this time.

Multiport sampling valves are available in six, seven, or eight-
port models constructed of Teflon or 316-stainless steel or other
suitable inert material ( 1, 2, 3  ).  The use of Viton and other
rubber or synthetic materials should be avoided since reduced
sulfur gases can become adsorbed on the material, alter the gas
composition, as well as cause mechanical malfunctions of the valve.
Provisions for leak detection in systems operated under a vacuum
must be made.  Leaks are checked by isolating the complete system
or sections thereof and placing them under negative head.  The
vacuum can be monitored with a manometer or gauge.  A leak would
be indicated by loss of vacuum.

The high sensitivity of the flame photometric detector (FPD) which
results in non-linear detector response above a sulfur concentration
                             -137-

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of about 5 ppm (v/v) either required dilution of the sample or
equipment modifications which permit analysis of samples containing
well above 5 ppm concentrations.  Stevens et_ a_l_ ( 3) describe a
dilution system used in conjunction with the FPD for continuous
analyses of source gases.  While the system is complex it has func-
tioned well in special study application.  A drawback of the system
is the use of at least three pumps whose short term performance
casts some doubt on long term performance capability in routine
monitoring situations.  NCASI has constructed and used a dilution
apparatus in continuous flow special studies of source emissions.
In this system a previously filtered source gas is maintained at a
temperature above the dew point.  -After fine filtration for further
particulate reduction, a known volume of source gas is mixed with
a known volume of inert gas such as nitrogen.   Flows of gas are
measured with rota'neters calibrated under the pressure and tempera-
ture conditions of use (e.g. 190 to 200°F,  negative and positive
head) and flow rate controlled with micrometering valves.  A com-
mercial dilution device to be used in continuous monitoring appli-
cations in conjunction with thair FPD is currently marketed by
Meloy Laboratories, Inc., Springfield, Virginia.
                              -138-

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4.5  ELECTROLYTIC TITRATION OF SULFUR COMPOUNDS

     An electrolytic titrator which is commercially available has found
     fairly widespread use in the kraft wood pulping industry, particu-
     larly in the more modern installations.  This analytical  system is
     most commonly referred to as a Barton titrator and is commercially
     available from the Barton Instrument Company, a division of Inter-
     national Telephone and Telegraph Corporation.  The system, as
     currently marketed, has direct application to the continuous moni-
     toring of recovery furnace gases  However, with some modifications,
     described herein, the titrator is adaptable to most major gaseous
     sulfur emissions in the kraft pulp mill.

     The concentration of the reactive compounds may be expressed in
     terms of the amount of known reagent added.   In the Electrolytic
     Titrator, the gas sample continuously passes through the  titration
     cell at a constant flow rate.   The reagent for sulfur compounds is
     bromine, which is generated by an electrical  current passing through
     the cell solution.   The amount of current supplied to the cell  is
     automatically adjusted by the  solid-state circuit in the  control
     module.   The current provided  by the control  module produces just
     enough bromine to satisfy the  demand of the reactive compounds  in
     the sample and thus continuously maintain the end-point  condition.
     The amount of current required to maintain the end-point  condition
     is proportional  to the concentration of reactive compounds in the
     sample ( 2).

     The main functional components of the titration cell consist of a
     set of three electrodes arranged to form two functional  pairs.   One
     pair acts as the bromine-generating electrodes and the other pair
     serves as the sensing and control electrodes.  The anode is common
     to both pairs of electrodes.  Changes in the bromine level of the
     cell electrolyte cause the sensing electrodes to vary the current
     supplied to the input of the electronic circuit in the control  mod-
     ule.  As a result of the action of the sensing electrodes and the
     electronic circuit, current is allowed to pass through the gene-
     rating pair of electrodes only when the bromine level in the cell
     falls below the preset operating bromine level ("blank"  level).
     The current is proportional to the TRS present in the sample.

     All compounds oxidizable by bromine will contribute to the bromine
     demand  as the sample  passes through the cell.  The various organic
     and inorganic sulfur  compounds react according to  their chemical
     nature.
                                   -139-

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Sulfur combined in the form of mercaptans or organic sulfide does
not require the same smount of bromine for reaction as sulfur com-
bined as hydrogen sulfide.   Furthermore, one compound can react
according to two or more patterns.   In a very low concentration
range, the reproducibility of the bromine oxidation reactions is
reliable to about + 10% over reasonable periods of operation on a
given sample source.  For a specifically accurate sulfur measure-
ment, it is necessary to titrate compounds each as h^S, RSH, and
RSR separately and apply an appropriate factor to the titration
current required for each.   The total  then would equal the total
sulfur concentration.  This can be  done by manual or automatic
filtration using a scrubber solution selective to the compound
in the sample stream.  Usually, the total of TRS is expressed as
equivalent
The decrease in titration current that occurs when the compound
is removed in the scrubber solution is a measure of its concentra-
tion.   In most applications, however, the selective filter system
is not .required, since it is necessary to know only the variation
in the total  bromine generated for all compounds present.   The in-
strument may be used as a continuous monitor on wet gas streams
providing the moisture in the gas stream is reduced to the dew
point at ambient conditions and the bulk of the particulate material
is removed before the gas enters the cell.   The system is  normally
operated to determine the total reduced sulfur concentration (minus
SC>2) with the manual selecte scrubber-filter system to establish
the concentration of individual components.,

Figure 4-17 depicts a system which has  functioned well at sources such
as the kraft recovery boiler,  kraft recovery stack, and smelt tank
vents.  The system consists of  (a) a  probe which is packed with glass
wool for use where particulate  concentration is high,  (b) a reservoir
for storing 5 percent potassium biphtal.ate,  (c) an orifice which re-
stricts flow of biphthalate solution  to 0.5 to 1 ml minute, (d) a
scrubber which removes particulate and S02 and cools the gas stream
to ambient temperatures.,  (e) the necessary tubing to conduct  the
scrubbed gas sample to the cell, and  (f) the pump, filter rack and
other equipment used in batch  sampling.

Figure 4-18 presents a modified  sampling system which may be utilized
as a continuous monitor on the  recovery complex as well as other
reduced sulfur sources in pulp mills.  The substantial difference  in
the two transmittal and sensing systems shown is the thermal oxida-
tion furnace preceding the titration  cell.  The function of the
furnace is to oxidize the remaining sulfur gases, subsequent to the
S02 scrubber to sulfur dioxide.  This accomplishes two major objec-
tives.  The reduced sulfur compounds  are all oxidized  to S02 and
sensed as S02 thus minimizing  the calibrations which would be
necessary for the individual compounds and also eliminates the pos-
sibility of "interference" from other non-sulfur bearing organic
conponents .

                            -140-

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             !;•;• j' i) ;•,/'•. r,;

             i 1.1 •••."]• T I •.-
             I I -.' i I L.I...
             I
       Ov'Ls
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  4.6  PARTICULATE  MONITORS

       Continuous particulate  sampling  and  detection  systems are currently
       receiving more  attention  and  utilization  in  the wood pulping  industry.
       To  date,  although  not in  widespread  use,  extractive and  in-situ
       methods  have been  employed with  varying degrees of success on wood
       pulping  process units.  The following  sections describe  those sys-
       tems  which have been used to  continuously monitor particulates from
       such  operations as kraft  recovery  furnaces,  smelt dissolving  tank
       vents, and lime kiln scrubber exhaust  gases.   As previously mentioned,
       the particulate material  from these  sources  mainly consists of sodium
       sulfate,  sodium oxide,  calcium carbonate, and  calcium oxide.

4.6.1  BOLOMETER-IN-SITU  MONITOR

       A light absorption device, the bolometer, used for many  years in
       measuring smoke density has been found applicable for measurement of
       particulate  loadings in kraft mill recovery  furnace stack emissions.
       Calibration  techniques  involving wet test methods have shown  that the
       instrument output  signal  has  a semi-logarithmic relationship  to par-
       ticulate  concentrations (6 ).

       The bolometer utilizes  a  light absorption principle in continuously
       measuring the concentration of particulate matter passing a_g.iyen
       point in  the kraft mill recovery furnace  flue  gas system.  The bolo-
      meter instrument consists  of a light source and a detector head  mounted
      on  the opposite ends of a  gas  sample pipe or tube.   The gas sample
      tube  is commonly a length  of standard 4-inch pipe with a 5-foot  by
      3 1/4-inch longitudinal  slot cut on both sides of the pipe.   This
      slot  is normally centered  in a horizontal  or a vertical  section  of
      the ductwork or the stack  being monitored.  The light source is  pro-
      jected through  the  dist laden  gases passing through the slot.  The
      filament  of  the detector  head  is connected to a Wheatstone bridge
      measuring circuit.  Changes in the dust loading or the dust density
      result in changes  in the  electrical resistance of the filament.  A
      servo motor  and measuring  slide wire resistor maintain the Wheat-
      stone bridge circuit balance and provide the instrument readout  on
      the recorder.   Normal  instrument readout supplied by the vendor  is
      from  0 to 100 percent of  full   scale  (6).

      As  supplied  from the vendor, the bolometer can be used for the
      measurement  of  dust density or smoke density.  If the first measure-
      ment  is desired, the instrument can be calibrated in either of the
      two commonly used  units of dust loading measurement—grains per
      standard  cubic  foot of dry gas or grains per actual  cubic foot of
      gas.  If  smoke  density  is  the  desired measurement,  as is sometimes
      the case  on  power  and/or  combustion boilers, the problem of accurate
      Ringelmann Number  determination is not encountered  (5 ).
                                     -142-

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       Figure 4-19 depicts the bolometer with a dial  readout in  a  typical
       installation.   Most of these instruments are installed with a  recorded
       output on the control panel  of the unit process in order  that  a  con-
       tinuous and permanent record of the operation  may be accomplished.
       The continuous measuring aspects of this instrument enable  optimiza-
       tion of operating variables  which normally result in minimizing  par-
       ticulate  .mission levels.  Malfunction of control devices (i.e.,
       electrostatic precipitators) are rapidly detected which results  in
       an economic saving of reusable chemicals.

4.6.2  CONDUCTIVITY (EXTRACTIVE) MONITOR

       This monitor, Figure 4-20 uses a twin tubed sample probe  to provide
       a non plugging sample line through which a flue gas sample  is  drawn.
       Water is continuously metered down one line of the sample probe  to
       a point just back of the sample probe tip where it joins  the second
       line which is carrying the gas away from the probe inlet.  The water
       is sheared off by the gas flow and mixed with it until it reaches a
       separation-mixing tank.  By the time the gas leaves this  chamber it
       has left most of its heat and almost all of its dust load in the
       water.  The water runs down an overflow tube to a water cooler and
       then to a conductivity cell  connected to a continuous recorder.   The
       conductivity is measured and is related to the sodium content of the
       water solution.  A gas meter measures the gas drawn off the separa-
       tion tank by a vacuum system.
       With the water flow, gas flow and conductivity,  i.e.  sodium concentra-
       tion, all known the sodium concentration in  the  flue  gas  is found  by:

                                sodium flue gas =
                water flow X sodium concentration
                         sample gas flow

       To determine the total  losses with the flue  gas  it is also  necessary
       to know the volume of flue gas flow.   The sodium losses are simply
       the flue gas flow times its concentration.

       Although just out of the experimental  stage,  the monitor  provides
       a continuous record of sodium losses  with recovery flue gases.   The
       principle of using a twin tube wet tip probe  may be applicable  to
       several  other tests.  By passing a solution  of cadmium chloride
       through the tip and measuring the resulting  turbidity of  the final
       solution the amount of H2$ in the flue gas may be determined.   If
       a fuschin solution were used in place of water and the color
       monitored,  the amount of SO? in the stack gas might be determined.
                                      -143-

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        S.V.Ct-D  FLAI-iCJiiS FOR
        AIR
•LIGHT SOURCE
                                                     BOLOMETER
                                      SMOKE OR DUST
                                      PASSAGE
                      SPACED FLANGES  FOR
                      AIR INLET
      FIGURE  4-19 -
Bolometer for Measurement of Particulate
Emissions
                          -144-

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FIGURE    4 -
20  - Titrimetric  Instrument  for
      Measuring  Particulate Emissions
                      -145-

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4.6.3  SPECIFIC ION (EXTRACTIVE)  MONITORS

       At least one kraft mill  has experimented with a  specific  ion
       electrode method to continuously monitor particulate  emissions  from
       the recovery furnace complex.

       Briefly the system employs a transmittal  system  which extracts
       particulate material from  the  exhaust gases  at or near a  previously
       determined, by conventional methods,  isokinetic  rate.   The  sample
       stream then enters a sensing cell  equipped with  a sodium  ion  elec-
       trode.   The sodium ion concentration  thus sensed is then  translated
       and read out as sodium sulfate concentration.  As stated, this
       method, although appearing to  have application to wood pulping
       unit processes, has not found  wide acceptance and, therefore, must
       be considered as still in  the  applied research and development
       stage.
                                      -146-

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4.7  LITERATURE  CITED

 1.   Chapman,  Robert L.,  POLLUTION ENGINEERING,  pp.  38-39,  September
     1972.

 2.   Section 11A -  Gaseous  Emissions  -  Automatic Techniques -  Electrolytic
     Titration,  Technical Bulletin No.  38,  NCASI, New York, N.Y.,  December
     1968.

 3.   A Guide to  the Use  of  Gas  Chromatography in Emission Analysis,
     Technical Bulletin  No.  59, NCASI,  New  York, N.Y.,  February 1972.

 4.   Marks,  Lionel  S.,  "Inadequacy of the Ringelmann Chart," MECHANICAL
     ENGINEERING, September,  1937.

 5.   Cooper, S.  R.,  and  Haskell,  C.  F.,  "Cutting Chemical Ash  Losses  in
     a Kraft Recovery System,"  PAPER  TRADE  JOURNAL,  March 27,  1967.

 6.   MacDonald,  Wayne G.  L.,  "BCFP Monitor  Cuts  Recovery Boiler Stack
 .-   Losses  50%,"  PULP  AND  PAPER, April, 1966.

 7.   "Determination  of  Collecting Efficiency  at  Electrostatic  Precipita-
     tor  Plants  for Soda  Recovery Units," Method of  AB  Svenska Flakt
     fabriken.
                                   -147-

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                             CHAPTER   5

                        AIR POLLUTION CONTROL SYSTEMS
5.1   INTRODUCTION

     Control  methods presently in use in the wood pulping industry consist
     of add-on hardware or process modifications.  The methods considered
     in this section are those which have been in reasonably successful
     operation for at least one year at one or more locations.  Control
     methods are briefly described in general terms and are evaluated under
     conditions of specific applications.  The evaluations include an
     effectiveness study as well as a discussion of engineering factors
     which are unique to the application.

     A variety of methods is found to be useful  in controlling particulate
     emissions from pulp mill  sources.  Efficiencies of 99+% are possible.
     The listing which follows identifies those methods most commonly used.
     It should be noted that the direct contact evaporator following the
     kraft recovery furnace is an important particulate control device.
     It should also be noted that where primary or secondary wet scrubbers
     are used as particulate collectors on combustion sources, the emis-
     sion of gaseous sulfur compounds may be increased or decreased de-
     pending on the nature of the scrubber medium.
            Kraft Recovery Furnace
            Kraft Lime Kiln
            Kraft Smelt Dissolving
              Tank
            Kraft Lime Slaker
            Power Boilers
Electrostatic Precipitators
Venturi Evaporator/Scrubbers
Electrostatic Precipitators
  plus Secondary Scrubber

Venturi Scrubber
Cyclonic Scrubber
Impingement Baffle Scrubber
Electrostatic Precipitators
  (recently)

Mesh Pads
Packed Tower Scrubbers •
Orifice Scrubbers

Mesh Pads
Cyclonic Scrubbers

Mechanical Collectors
Electrostatic Precipitators
                                    -148-

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             Combination Boilers
  -  Mechanical  Collectors
     Cyclonic Scrubbers
       Fewer  numbers of methods are in use for the control of gaseous emis-
       sions,  particularly  the odorous reduced sulfur compounds.  The majority
       of  odorous  emissions can be grouped into three categories: (a) recovery
       furnace offgases;  (b)  low volume high concentration sources such as
       the noncondensible gases from the multiple effect evaporators, and di-
       gester  relief and  blow gases; (c) high volume low concentration sources
       such as brown stock  washers and smelt dissolving tanks.  Wet scrubbers
       have received limited  application on combustion sources  in the.kraft
       process because of the difficulty-of absorbing effectively all of the
       odorous compounds  with a single scrubbing medium.  Also  as indicated
       previously,  the emission of gaseous sulfur compounds may be increased
       or  decreased depending on the nature of the scrubbing medium.  The
       following list identifies those methods most commonly used and which
       are described in the chapter:
              Kraft  Recovery  Furnace
-  Weak Black Liquor Oxidation
-  Strong Black Liquor Oxidation
-  Proper Operation
-  Venturi Evaporator/Scrubber
-  Cyclone Evaporator/Scrubber
-  New Recovery System Design
              Kraft  Smelt  Dissolving   -   Packed Tower Scrubber
                Tank                  -   Orifice Scrubber
              Kraft  Digester  Relief
                and  Blow plus M.E.
                Evaporator
              Sulfite  Acid  Tower

              Sulfite  Blow  Pit  .
   Chlorination
   Incineration
   Packed Tower Scrubbers
   Weak Black Liquor Oxidation
     (M.E.  Evaporators)
   Steam Stripping of Condensates
   Air Stripping of Condensates

   Additional Absorption Tower

   Packed Tower
  5.2  GENERAL DESCRIPTION OF CONTROL EQUIPMENT

5.2.1  ELECTROSTATIC PRECIPITATQRS                                      :

       An electrostatic precipitator consists  in principle of a  number of
       discharge (emitting)  electrodes,  collecting electrode plates  and a
       high-voltage power unit.   This power unit comprises high-voltage
                                    -149-

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transformers and rectifiers to convert the available AC power to high-
voltage DC power.  Lately, silicon diode rectifiers have almost
exclusively replaced other types of rectifiers.

The dust laden gas enters the electrostatic precipitator and flows in
the passages created by the collecting electrodes.  When high-voltage
power is applied to the discharge electrodes located in the passages,
ionization or corona discharge occurs near the surface of the dis-
charge electrodes.  The negative ions attach themselves to dust
particles near the electrodes giving the particles a negative electric
charge.  The charged dust particles are repelled by the discharge and
attracted to the collecting surfaces connected to ground.   Here the
dust particles lose their electrical charge and are deposited on the
collecting electrodes.

The collecting electrodes are provided with a rapping mechanism for
dislodging the dust precipitated on the electrodes.  This  rapid system
must be designed very carefully to avoid creation of a dust cloud in
the space between the electrodes.  Incorrect rapping operation or pro-
gramming may cause the dust to re-entrain which, in turn,  would greatly
decrease the dust collecting efficiency of the precipitator.  Incor-
rect rapping is the most common cause for so-called "snow-outs."  The
rapping mechanism, which is generally operated on an automatic time
cycle basis, is either of vibrator or motor driven fall-hammer type.
Vibrators are preferred for pulp mill applications rather  than the ham-
mer rappers which are used more frequently, for example, on fly ash
precipitators.

The high voltage power level  is controlled by an automatic control unit.
The discharge electrodes are connected to the negative rather than to
the positive side of the power supply.   A higher voltage can thereby
be maintained without excessive arc-overs which, in turn,  would cause
waste of electric power and eventually lead to operating difficulties.
The automatic voltage rate of sparking provides a feedback to the con-
trol unit making it possible automatically to operate the  electric
system of the precipitator at optimum conditions.  Little  or no spark-
ing will increase the voltage and too much sparking will reduce the
voltage, thereby preventing arc-overs detrimental to the precipitator.

Gas conditions are never uniform throughout the precipitator.  Aside
from unintended irregularities in gas distribution and other conditions,
the dust loading varies from inlet to outlet of the precipitator.   To
reach optimum dust collecting efficiencies, the electrical  control units
must accomodate these variations.  A high dust loading will increase the
sparking and reduce the voltage.   If the precipitator would have only
one electric system with one automatic voltage control, the voltage
throughout the precipitator would be limited to the lowest voltage
permissible at any point in the precipitator.  The modern  precipitator
is, therefore, divided into independent electrical units,  each controlled
for maximum voltage depending on the gas conditions in that particular
                              -150-

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       section of the precipitator.  The discharge system close to the outlet
       of the precipitator will consequently operate at a higher voltage level
       than the inlet.  This need for sectionalizing has led to increased use
       of the horizontal flow, plate-type precipitator.  This type has super-
       seded the tube-type, vertical  flow precipitator, once very common in
       the pulp and paper industry.  The tube-type precipitator does  not
       easily lend itself to sectionalizing.

       The electric power consumption of a precipitator depends on several
       factors.  The input of current is necessary to sustain the voltage level.
       There is a constant power drain due to ionization in the corona, due
       to the controlled sparking and other voltage leakages because  of poor
       maintenance, dust build-up, et cetera.  The collection efficiency de-
       pends on the voltage level; but, on the other hand, the higher the
       voltage level, the greater the power drain.  At 90 percent collection
       efficiency, the power consumption is approximately 0.2 kw/1000 CFM of
       gas and at 99.9 percent efficiency, the power consumption has  risen  to
       approximately 0.8 kw/1000 CFM.

       Most precipitators used in the wood pulping industry on recovery boilers
       are designed for collection efficiencies  of 90 - 99.9 percent.  The  pres-
       sure drop of the gas passing through the  precipitator is usually below
       0.5 inch W.G.   A typical wet-bottom precipitator with tile shell is
       shown in Figure 5-1.

5.2.2  VENTURI SCRUBBERS

       The Venturi scrubber consists  in principle of a convergent section (throat)
       and a divergent section.  Dust laden gas  enters the convergent section
       and is accelerated to high velocity as it approaches the throat.  Gas
       velocities in the throat section vary from 100 to 500 FPS.

       Water or other scrubbing liquid is injected either directly into the
       throat section or the top of the Venturi.  In the latter case, the scrub-
       bing liquid cascades down the  walls of the convergent section.  The high
       velocity gas stream atomized the liquod into a fine mist--the  greater the
       velocity, the finer the droplets.  Collison between the dust particles
       and the water droplets takes place and causes the dust to be entrapped
       in the water.   Further collison between the water droplets occurs.  This
       will create aggregate droplets of relatively large size.  These droplets
       are easily separated from the  gas stream  in a subsequent separator.   The
       collision or impaction phenomenon is rather complex, but is mainly due
       to mass forces created by the  great velocity differential  between the
       dust particles and the water droplets.  For submicron particles, the
       Brownian molecular movement, diffusion, and electrostatic forces also
       play an important role.

       In the divergent section, the  gas and the dust particles are decelerated
       thereby creating a new velocity differential with additional agglomeration.
       Finally, in the elbow connecting the Venturi and the separator, as well
                                     -151-

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                GAS
               OUTLET
                     •yi  -- ••-,-\'  ,n
                     ;!'•/;•'•:  >J;H
                         BLACK  LICHJOUR FTE'
                FIGURES.-!

    PRECIPITATOR  FOR RECOVERY BOILER
1I1LET
-152-

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as  in the inlet to the separator (if radial), changes of direction of
the gas  flow cause additional impaction and agglomeration.

The gas  and liquid enter the separator, usually of the cyclonic type,
where the liquid is thrown to the walls by centrifugal forces and
drains to the bottom by gravity.  The clean gas exists through the .up-
per portion of the separator.

The elbow connecting the Venturi with the separator is either of the
regular  type or of so-called flooded types. The flooded elbow is
developed to prevent erosion.  Here the liquid surface absorbs the
brunt of the water and dust stream.  For pulp mill applications, such
as  lime  kiln scrubbers, the flooded elbow is recommended.

Normally the separator is of the cyclonic type with conical  bottom and
either top outlet or side outlet.  The type of outlet depends on whether
the fan  is located before or after the scrubber.  The top outlet lends
itself to a direct mounted stack.  In order to facilitate the installation,
the separator is sometimes provided with a flat bottom.   This may some-
times create drainage problems.   For special purposes a so-called false
bottom is also installed.   The false bottom creates an intermediate re-
serve for the scrubbing liquid where de-aeration can take place making
the scrubbing liquid (e.g., black liquor) more suitable to pump.  Scrub-
bers for recovery boilers are almost always provided with facilities for
wall wash of the separator.  This prevents build-up of black liquor solids
which can be a fire hazard, in addition to being a maintenance problem.

The Venturi scrubber is capable of high efficiency collection of dust
and fumes even in the submicron range.   The efficiency of collection is
a function of the pressure drop across  the scrubber which in turn is a
function of the gas velocity in the throat and the liquid flow rate
(liquid to gas ratio).   The higher the  gas velocity or the liquid flow
rate, the greater will  be the pressure  drop and consequently the
greater the efficiency.  There is, however, a cut-off point  where in-
creased liquid flow rate will have an adverse effect on the  collecting
efficiency.   The throat becomes  "flooded."  This occurs  at about 20
gallons per 1000 CFM.   In order to attain high collecting efficiency,
the water droplet size  distribution has to be in a certain relation to
the dust particle size  distribution.   Too large droplets would reduce
the probability of collection drastically, and even if collection would
take place the chance for the dust particles to be entrapped in water
would also be reduced.

Increased gas velocity  (pressure drop)  increases the atomization.   A
fine dust will, therefore, require a higher pressure drop than a
coarse dust for the same collecting efficiency.

Scrubbing liquid is injected into the Venturi at low pressure through
relatively large jets  or open weirs.   In order to be able to recirculate
                             -153-

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       the scrubbing liquid, in other words maintain a high concentration of
       solids, the manufacturers try to completely do away with narrow
       constrictions and weirs.  The liquid rate is normally 3 - 15 gallons
       per 1000 CFM of gas.  A typical Venturi scrubber is shown in Figure
       5-2.

5.2.3  CYCLONIC SCRUBBERS

       The cyclonic scrubber is an efficient device for removing dust particles
       two microns and larger and is also a relatively good gas absorber.  In
       this unit, the dust laden gas enters tangentially at the bottom of a
       cylindrical tower and spirals upward through the scrubber in a con-
       tinuously rotating path.  A spray manifold is located axially in the
       center of the scrubber with banks of spray nozzles directed radially
       toward the walls.  The spray sweeps across the path of the gas stream
       intercepting and entrapping the dust particles.  The centrifugal motion
       of the spray impacted by the rotating gas causes the droplets to im-
       pinge against the walls of the scrubber and drain to the bottom due to
       gravitational forces.

       In another type of cyclonic scrubber, the spray nozzles are mounted on
       the wall  rather than in a central spray manifold.  The advantage with
       this type is that the nozzles may easily be serviced or replaced while
       the scrubber is in operation. .

       The mechanism of collecting particles in the cyclonic scrubber is in es-
       sence the same as in a Venturi  scrubber; namely, impaction and agglomera-
       tion of liquid droplets and dust particles with subsequent centrifugal
       and gravitational separation.

       The liquid pressure ranges  from 50 to 400 PSIG.  The flow rate is norm-
       ally 3-8 gallons per 1000 CFM.

       The cyclonic scrubber is most efficient on relatively coarse dust and
       the efficiency drops off markedly for particles under two microns.  The
       pressure  drop is considerably less than for a Venturi scrubber and
       ranges normally from 0.5 to 3 inches WG.  A typical  cyclonic scrubber
       is shown  in Figure 5-3.

5.2.4  IMPINGEMENT BAFFLE SCRUBBERS

       The impingement baffle scrubber is a vertical  tower equipped with one
       or more impingement baffle  stages.  The impingement  baffle consists of
       a perforated plate having a multitude of small  holes so arranged that
       a baffle  is located directly above each perforation.  A weir on each
       plate maintains a level  of  scrubbing liquid.

       The contaminated gas enters  radially at .the bottom of the scrubber
       and is subjected to a  water spray that will  precipitate out the coarser
       dust particles.   The gas then passes through  the perforations and impinges
                                    -154-

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                                       SEPARATOR OUTLET
                          GAS
                        •INLET
LIQUID INLETS
           THROAT-
  SEPARATOR  INLET NOZZLE-
                             FIGURE 5-2


                   VEMTURI  SCRUBP.ER WITH CYCLONIC
                                         SEPARATOR
                                 -155-

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                 SCRUBBER OUTLET
IET
                                          .-^LIQUID  INLET
                                          WALL MOUNTED SPRAYS-
                                           MAY BE CENTER PIPE,
                       FIGURE  5-3

                    CYCLONIC  SCRUBBER
                          -156-

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       on the baffles.  The gas velocity through the perforations, ranging
       from 75 to 100 FPS, atomizes the scrubbing liquid and the velocity
       differential between gas and liquid results in the impaction and
       agglomeration of liquid and particulate matter.  The scrubbing liquid
       is introduced into the scrubber through low pressure spray nozzles
       located below the plates and spraying upward.  These sprays not only
       deliver liquid to the plates, but also serve to cool and humidify the
       gasses; remove coarse particles; and keep the bottom of the plates
       clean.  For scrubbers with more than one stage, the scrubbing liquid
       is drained off the plates downward from stage to stage in the scrubber.
       In addition to the multiple impaction, the change of solids concen-
       tration in the liquid also contributes to increasing the collecting
       efficiency.

       The pressure drop for impingement'baffle scrubbers ranges from 2 inches
       WG to 8 inches WG depending on the number of stages, size, and numbers
       of perforations and baffles.   As would be expected, increased number
       of stages and smaller perforations result in higher pressure drop and
       subsequent higher efficiency.  An impingement baffle scrubber is shown
       in Figure 5-4.

       The impingement baffle scrubbers are normally used in lime kiln appli-
       cations.   The efficiency is,  however,  not high enough to comply with
       today's air quality requirements.   For upgrading of existing impinge-
       ment baffle scrubbers, it is  possible  to install  a Venturi  and an elbow
       ahead of the scrubber and to  use the scrubber shell  as  a cyclonic
       separator.  The inlet to the  scrubber  must,  in such  a case,  be changed
       to enter the shell  tangentially, and all the internal  parts  have to be
       removed.

5.2.5  PACKED TOWER SCRUBBERS

       The packed tower scrubber is  used  primarily  as a gas absorber.   Its use
       for collection of solid particulates is  limited because  it is  rather
       inefficient for particles under five microns and is  subject  to becoming
       plugged because of dust build-up.   It  is, however, an excellent device
       for absorption of such gases  as HC1, S02, Cl2> H2S,  and  NH3.   Other
       advantages of the scrubber are simple  design and low manufacturing cost.

       The scrubber consists of a vertical  cylindrical  shell with  the gas in-
       let at the bottom and the outlet at  the  top.   Above  the  gas  entrance is
       a  packed section  consisting of four  or more  feet of packing  material.
       This  packing may  consist of Raschig  rings,  Pall  rings, saddles,  et
       cetera, made from stoneware,  ceramic,  or polypropylene.   Water is  dis-
       tributed uniformly over the packing  by means of low  pressure  spray noz-
       zles  or weirs located above the packing.   Normally,  there is  a mist
       eliminator above  the  spray nozzles to  prevent entrainment of liquid in
       the clean gas leaving the tower.   Normally  a reservoir is located at
       the bottom of the scrubber for direct  recirculation.  A  typical  packed
       tower scrubber and packing are shown in  Figure 5-5.
                                   -157-

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                                                            TARGET PLATE
      CLEAN GAS OUTLET
ENTRAPMENT
ELIMINATOR
   IMPINGEMENT
   BAFFLE PLATE
   (SECOND STAGE)
  WATER SEAL-

   IMPINGEMENT	
   BAFFLE PLATE
   (FIRST STAGE)
                                                WATER LEVEL
                                                            ORIFICE PLATED
                                     ,DRAIN

                        FIGURE 5-4


                   IMPINGEMENT SCRUBBER
IMPINGEMENT SCRUBBER
     MECHANISM
                                                    LIQUID INLET
                                                 WATER SEAL

                                                >s*\
                                                      CONTAMINATED

                                                      GAS INLET

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                                   CLEAN  GAS  OUTLET
      DEfllSTER PAD
      CONTACT BED
      CONTAMINATED
      GAS INLET
                                            LIQUID  INLETS
                                RECYCLE SECTION
RASCHIG
  R I NG
SPIRAL
 RING
          COUNTER-FLOW PACKED TOWER  SCRUBBER
LESSING  CROSS-PARTITION
  RING        RING
 ^F>
 BERL
SADDLE
           INTALOX
           SADDLE
        CERAMIC PACKINGS
                          FIGURE 5-5
                                        ^S-
                            ^^)

                           PALL RING
                                      TELLERETTES*
MASPAC'
                                             If.'TALOX
                                             SADDLE
                                         PLASTIC PACKINGS
                               -159-

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       The contaminated gas enters at the bottom of the tower and moves up-
       ward through the packing counter-current to the scrubbing liquid.
       The packing forces the gas to follow a tortuous path over the contact
       surfaces and interstices creating intimate contact with the descending
       liquid.

       The pressure drop over the tower depends on the height of packing  but
       is normally in the order of 1 - 2 inches WG.

       As mentioned before, the packed tower is an excellent gas absorber,
       but less suitable for dust removal due to dust build-up.   When dust
       is present in the gas, special attention has to be given  to the selection
       of packing material.  A larger size packing; i.e., 4-inch Pall rings in-
       stead of 2-inch should be chosen in order to prevent plugging.  The
       contact surface will thereby be reduced and the gas absorption efficiency
       will  drop.   This can be compensated for by increasing the height of  the
       packing but the plugging tendencies will increase simultaneously.

5;2."6  MECHANICAL COLLECTORS

       There are a great number of different mechanical  collectors in use '
       throughout in.dustry.  The most common ones within the wood pulping in-
       dustry are the large diameter cyclones and the multi-tube collectors.
       This  description will be limited to these two types.

       Cyclone dust collectors are of cylindrical or conical type,  utilizing
       centrifugal and gravitational forces for separation of dust particles
       from a gas  stream.   The dust laden gas enters the collector tangentially
       either directly or via an expanded involute section where the dust
       particles are subjected to the separating forces.   The centrifugal force
       drives the dust particles to the collector wall;  the gravitation drives
       the concentrated dust dov/nward to the cone outlet; and the dust is dis-
       charged into a collection hopper while the cleaned gas flows upward  in
       an inner vortex to the gas outlet tube.

       Two basic types of cyclone collectors are available—the  tangential  in-
       let type shown in Figure 5-6 and 5-7 and the axial vane type.   The former
       is sometimes referred to as large diameter cyclone, or cyclone collector,
       and the latter one as a tubular collector.   In the tangential  inlet  type,
       the gas enters the cyclone through a straight tangential,  helical, or
       involute inlet section.  Axial vane units employ  inlet vanes to provide
       the spiraling motion to the dust laden gas stream.

       Many  sizes  and designs of cyclone collectors can  be provided to meet
       specific dust collection problems.  The  units may  be  installed in  single
       or multiple arrangements, in parallel  or in series.  Cyclone collectors
       are generally suitable for separating solid particles in  size ranging
       from  about  3 microns to 200 microns.   They can, of course  be used  for
       larger particle sizes also.
                                     -160-

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 GAS
INLET
                                                               GAS
                                                              OUTLET
                                     DUST OUTLET
                           FIGURE 5-6

               LARGE DIAMETER CYCLONE COLLECTOR
                     STANDARD ARRANGEMENT
                               -161-

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                 GAS
                INLET
                OUTLET  TUBE
                       SPIN  VANES
                     INLET  TUBE
            -TUBE  COLLECTOR
                                                                   GAS
                                                                  OUTLET
                                              FIGURE  5-7
COLLECTOR ELEMENT
-162-

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       For a given cyclone collector, the overall collecting efficiency can
       be determined  if certain parameters are known.  These parameters in-
       clude dust particle size distribution, density, concentration, and
       other properties of the dust.  Gas temperature, pressure, moisture con-
       tent and gas composition, as well as pressure drop limitations and
       local conditions, are also factors of consideration.   The efficiency
       increases with increased dust particle size, density, and concentrations.
       Collection efficiency increases with increased pressure drop across the
       cyclone.  The collector can be designed for pressure  drops of less than
       2 inches WG for large diameter cyclones and for 2-7 inches WG for
       the smaller diameter (high efficiency) units.

       Increasing temperature will decrease the efficiency of the cyclone.
       However, up to 700°F, the influence of the gas temperature is not great.
       For the same pressure drop, increased gas viscosity or density will low-
       er the collecting efficiency.

       As particle size, dust density, and inlet gas velocity decreases  the
       efficiency tapers off.   Overall efficiency of the collection system can
       be increased by arranging the cyclones in series.  By reducing the
       diameter of the cyclone the centrifugal  forces increase, thus increasing
       the efficiency.  The gas volume capacity will, however, simultaneously
       be reduced and the number of cyclones has to be increased.   This  principle
       is utilized in the multi-tube collectors where the tube diameter is from
       12 inches or less up to 24 inches.  Batteries of tubes are mounted in
       the same casing and high efficiencies are attainable.

       Since high efficiencies require high radial  gas velocities, abrasion
       is often a problem for cyclone collectors.  Proper selection of material
       of construction is imperative.  Materials in use include carbon steel,
       low alloy steels, aluminum and special  materials. Abrasion resistant
       linings  in castable form or brick linings can also be used.

5.2.7  BLACK LIQUOR OXIDATION

       Black liquor oxidation  is practiced for the  purpose of oxidizing  the
       sodium sulfide in the liquor.  This is  accomplished by reacting the
       sodium sulfide with oxygen in the air to form sodium  thiosulfate.
       This  compound is  relatively stable and will  not break down in passing
       through  the direct contact evaporator.   Sodium sulfide reacting with the
       carbon dioxide and sulfur dioxide in the flue gases is the cause  of
       hydrogen sulfide  emissions.   The chemical  reactions of sodium sulfide
       (unoxidized liquor) and C02 and S02 in  the flue gases are as follows:
                   Na2S + C02 + H20 -> Na2 .003 + H2S


                   Na2S.+ S02 + H20 + Na2 S03 + H2S




                                  -163-

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Black  liquor oxidation can be applied either to weak black liquor or
to  concentrated black liquor.  The choice is dependent to a considerable
extent on the characteristics of the liquor.  Usually weak liquor  '
oxidation is used on non-foaming liquor and concentrated liquor oxida-
tion on foaming type liquor.  Regardless of the type of oxidation, it
is  essential that complete oxidation of the sodium sulfide takes place,
if  hydrogen sulfide emissions from the direct contact evaporator are
to  be  prevented.

Lately, investigations have been conducted into sodium sulfide reversion
taking place after weak liquor oxidation.  Instances are known to exist
where, although there is 99 plus percent oxidation during weak liquor
oxidation, the concentrated liquor shows the presence of sodium sulfide.
One solution is to add a second system of concentrated liquor oxidation.
Among those who have installed weak liquor oxidation and who are having
sodium sulfide reversion, there are suggestions that concentrated liquor
oxidation might be the correct installation (14).

There are three types of oxidation systems:

     1.  Packed Towers
     2.  Bubble Tray Towers
     3.  Air Sparged Reactors

Packed Towers

Packed towers have been applied primarily to weak  black liquor oxida-
tion.  The principal advantage of a packed tower lies in reduced power
costs.  The pressure drop through a packed unit is usually about 1  to
2 inches WG, and a tower for a 500 ton-per-day  mill  will  require about
20 hp to operate the required air blowers.  In  regions of high power
costs, this is an important factor in selecting an oxidation unit.   The
disadvantage of this unit is that it has plugging  tendencies and has
lower oxidation efficiency.

Bubble Tray Towers

The bubble tray oxidation tower is used for weak black liquor oxidation
only.  The liquor is pumped out on a perforated steel  plate, under which
air is blown from a fan.   The air passes through the perforations and
bubbles through the liquor.  The liquor height  on  the plate is normally
four to six inches and the liquor makes several  passes over the plate.
In order to accomodate larger flows of liquor,  a number of these aeration
chambers (bubble trays)  are connected in parallel  and stacked on top
of each other.

The liquor,  air, and foam are discharged into a foam tank,  where mechan-
ical foam breakers convert the foam to liquor.   Certain liquors with
low foam characteristics  may not require foam breakers if the tank  is
large enough.   The air leaving the system through  foam breakers carries
some entrained liquor.   This liquor is  separated from the air in a  cy-
clone and returned to the foam tank,  while the  air is exhausted to  the
                             -164-

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atmosphere.  This air stream, although relatively small, contains some
hydrogen sulfide, methyl mercaptan, dimethyl sulfide, and dimethyl
disulfide.

The system operates at 25 - 35 inches WG pressure drop.  The foam
breakers draw approximately 10 BMP each.  Including necessary pump
capacity, the total power consumption runs about 0.25 BHP/GPM.
The air to liquor ratio is 15 - 20 CFM/GPM and a retention of 4 - 6
minutes is required on the perforated plates.

Air Sparger Reactors

The air sparged reacters are of two types--air sparging with agitation
and without agitation.

Air Sparger With Agitation.  Air sparging with agitation is used for
both weak and concentrated liquor.  This system requires more electric
power, it is more complicated, and the equipment cost is higher than
for the non-agitation system.  The liquor is pumped into a tank where
an air header comes in centrally at the top.  The header conveys the
air into the sparger located approximately six feet from the bottom of
the tank.   The sparger has a number of arms  extending radially from the
header and each arm has a number of branches with aeration nozzles. . The
sparger is submerged ten to fifteen feet in  the liquor depending on the
desired retention time.  The incoming liquor is distributed above the
surface in a system of pipes and nozzles.  In addition to being evenly
distributed", the liquor helps to beat down the foam floating on the sur-
face.

Air Sparger Without Agitation.  Air sparging without agitation is used
exclusively for concentrated black liquor oxidation.  This system
operates at about 10 psig air pressure and draws approximately 1.5  -
2.0 BHP/GPM of liquor.  The air to liquor ratio is  20 - 30 CFM/GPM
and the retention time 2-3 hours.  Systems with agitation use more
horsepower, but should otherwise be comparable.

Effect of Batch and Continuous Digesters

Mills  with continuous digesters usually experience  higher sodium sul-
fide loadings than mills with batch digesters.   This is attributed
to the fact that batch digester systems expose  the  liquor to more con-
tact with  air (primarily during washing) than continuous digester sys-
tems,  thus resulting in more oxidation of the liquor.   For batch
digester systems the sodium sulfide content  in  the  weak black liquor
storage tanks may be 50 percent of that in the  white liquor storage
tanks.  This condition must be considered when  selecting oxidation  sys-
tems.
                             -165-

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        Summary

        As stated previously, foaming is a major consideration in the selection
        of an oxidation system.  Foaming depends on the wood species, which
        will contain varying amounts of resin and fatty acid salts.  These
        compounds will create a foam, that in some cases will preclude the
        oxidation of weak liquor.   The foaming is less pronounced in strong
        liquor.  Especially severe is the foaming of liquors from southern
        pine.  The addition of fuel oil  or kerosene to the liquor to reduce the
        foam helps in some cases.   Foaming characteristics of the liquor in-
        fluences the geographical  locations of the various oxidation systems.
        In general, the air sparger type is located in the South  due to the
        resinous content of the southern liquors.  Weak liquor oxidation has
        found extensive application in western United States.   The mid-west and
        northeastern United States have installed primarily weak  liquor oxidation
        systems; however, (]_) only one installation is reportedly operating at
        a high oxidation efficiency.  Currently, the general trend in oxidation
        systems appears to be directed towards more acceptance of the air sparger
        type for concentrated liquor oxidation.

 5.2.8  ORIFICE SCRUBBER

        The orifice scrubber is a collection device consisting of a restricted
        air passage partially filled with water.   The resulting dispersion of
        the water causes wetting of the  particles and their collection.  Pres-
        sure drop is comparable to cyclonic scrubbers.

 5.2.9  MESH PADS

        Mesh pads are collection devices composed of material such as knitted
        wire mesh.   Dust and liquid droplets are collected on the pads.

        A spray washing system is  provided for back washing the mesh pads to re-
        move accumulated solid particulate.   In normal  operation, a maximum pres-
        sure drop of approximately 0.2 inches WG is maintained by periodic opera-
        tion of the spray system.

5.2.10  STRIPPING CONDENSATES

        Many condensate streams, especially from the "foul" streams of the MEE,
        contain TRS compounds.  Countercurrent stripping by either air or
        steam has successfully removed more than 95 percent of these compounds.
        Thus, the stripped condensate can be used as process water where its use
        prior to stripping would have resulted in TRS emissions to the atmosphere.
        It can be used as scrubber water in the smelt dissolving  tank, and lime
        slaking.  The stripped compounds are usually incinerated  in the recovery
        furnace, limekiln, or power boiler.

   5.3  POWER AND COMBINATION BOILERS, GENERAL

        The emission control  equipment used in the steam power plants has been
        almost exclusively limited to removal  of particulate matter.   Lately
                                    -166-

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efforts have been made to find ways and means to remove sulfur from
the  fuels  and alternatively sulfur dioxide from the flue gases.  As
yet  no commercially economic and feasible method is in operation, but
a number of promising pilot studies have been made.  The recognition
of nitrogen oxides as undesirable compounds in the flue gases is re-
latively new and efforts in that direction have only begun.

Power and  combination boilers in the pulp and paper industry incorporate
a wide variety of firing equipment.  Some of these types are:

      Oil  and Gas Burners

      Pulverized Coal

      Spreader Stokers with Traveling Grates

      Spreader Stokers with Vibrating Grates

      Spreader Stokers with Water Cooled Grates

      Spreader Stokers with Stationary Grates

      Spreader Stokers with Dump Grates

      Dutch Ovens

Aside from coal the main fuels are oil, gas, and bark.   Today the burn-
ing of bark for steam generation is confined to locations where bark is
available as a waste or by-product.  In producing lumber half of the
wood in the log is often discarded as saw-dust, bark, shavings, slabs
and ends, all  of which can be used as fuel.  New methods in barking and
pulping, however, are continuously reducing the quantity of waste wood
available.

The devices commonly used for removal of particulate matter in flue gases
of steam boilers are centrifugal collectors and electrostatic pre-
cipitators.  The following list indicates the type of dust collectors
normally used for various types of fuel.

                           Mechanical      Electrostatic Precipitators

Coal  (pulverized)               X                       X

#6 Oil                          X          Has  been used but is not common

Gas

Bark                            X

Bark + Coal                     X

Bark + Oil                       X

Bark + Gas                       X


                             -167-

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 Fly  ash may be  approximately classified according to type of firing as
 shown  in Table  5-1.   Fly ash from pulverized coal fired boilers is
 generally quite fine—about 70 percent (or more) smaller than 325 mesh.
 It is  usually light gray in color as it contains only a small amount
 of unburned carbon.   The small particles, having a large surface
 area,  will impart a definite color to the stack gases.  This may,
 under  certain light conditions, indicate that a sizeable amount of fly
 ash  is being discharged into the atmosphere.  Fly ash from stoker fired
 boilers on the  other  hand is much coarser and has, since it contains
 larger quantities of  unburnt carbon, a dark gray to black color.  This
 fly  ash does not discolor the flue gas in the same manner as described
 above.  A clean appea/ing stack discharge from a stoker fired boiler
 does not necessarily  indicate that there is no emission problem.  The
 coarse particles will fall out relatively close to the stack and on an
 equal weight basis will cause a greater local nuisance than fly ash
 from pulverized coal.  Thus fine particles make a small plume appear
 much denser than coarse particles.  It is for this reason that removal
 of particles larger than 20 microns has little effect on the appearance
 of the plume.

 Electrostatic Precipitators

 The performance of an electrostatic precipitator is directly related.to
 the level of power input maintained.   The amount of electric charge that
 the dust particles will acquire depends upon the conductivity or re-
 sistivity of the dust.  When the resistivity exceeds approximately
 2 x 10^0 Ohm centimeters excessive sparking is to be expected with sub-
 sequent drop in collecting efficiency.   Research has shown that the re-
 sistivity of the fly  ash is closely related to the presence of water,
 soluble sulfates, and free sulphuric acid formed on the surfaces of the
 dust particles by absorption of 803 from the flue gas.  If the sulfur
 content is greater than 1  percent in the coal there is likely to be
 sufficient 863  in the flue gas to create favorable conditions for an
 acceptable resistivity.  However, $03 is formed by oxidation of SO?
which occurs between  750°  and 1500°F.   The amount of SO? formed will de-
 pend on the design of the  boiler and the rate of combustion.  The lower
 limit of soluble sulfur compounds in the coal ash, necessary to create
 an acceptable resistivity  has been found to be between 0.5 and 1.0 per-
 cent.  The resistivity also varies with the flue gas temperature and
 reaches a peak at approximately 300°F for average fly ash.   The peak
 resistivity of some fly ash is high enough to adversely effect the pre-
 cipitator performance^  Yet 300°F is a favorable temperature level for
 boiler and evaporator operation.   Thus, requirements for the boiler
 and for the precipitators  are contradictory.   The amount of magnesium
 and aluminum in the coal ash is also believed to be a factor contributing
 to high resistivity.  Fly  ash from strip mined coal  usually has higher
 resistivity than fly ash from deep mined coal.

 Fly ash containing more than 15 percent carbon will  effect precipitator
 performance adversely.  The reason for this is that carbon is a relatively
                             -168-

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.cr>
UD
       TOTAL
                                                    TABLE  5-1

                   TYPICAL PARTICLE SIZE DISTRIBUTION OF FLY  ASH  FROM BOILER GASES  OF VARIOUS  BOILERS
(Percent by Weight)
Particle
Size
Microns
0-10
10-20
20-30
30-40
40-74
74-149
+ 149
COAL FIRED BOILER
Pulverized
Coal
25%
24
16
14
13
6
2
Cyclone
Furnace
72%
15
6
2

5

Spreader Traveling
Stoker Grate
11%
12
9 11
10
12 12
17 30
29 47
Underfed
Stoker
7%
8
6
9
8
19
43
100 Percent Bark Fired
Boiler
12%
10
7
6
14
16
35
100
100
100
100
100
100
            Data frpm Bituminous Coal Research Association, Pittsburgh, Penn. and the Industrial
            Gas Cleaning Institute, "Criteria for the Application of Dust Collectors to Coal
            Fired Boilers."

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good conductor and will acquire, but also loose, an electrical charge
very easily.  When a particle with high carbon content precipitates
on the collector plate it loses its charge immediately.  Owing to
a phenomenon referred to as  "charge by induction," the particle as-
sumes a weak positive charge.  It is repelled from the collector
plate and reentrains into a  gas stream.  This phenomenon is repeated
over and over again until the particle is carried out by the gas stream
and escapes from the precipitator.  In order to overcome this problem,
the collector plates are given a special form and the so-called pocket
or screen grid collecting electrodes have proven to be very effective.
There is also a certain correlation between the carbon content and the
coarseness of the fly ash.  A coarse fly ash has normally a high carbon
content.

Recent improvements in the design of electrostatic precipitators have
reduced many of the advantages of combinations of electrostatic pre-
cipitators and mechanical collection systems, so common some years ago.
The plate electrode precipitators did not have sufficient collecting
efficiency on high carbon fly ash with problems of "snow outs" from the
stack during soot blowing and collector plate rapping periods.  Pocket
electrodes and continuous rapping have, to a large extent, circumvented
these problems.   Another advantage of a combined system installation
was that the mechanical collector wou.ld still remove a major portion
of the fly ash should the precipitator be out of order for some reason.
Sectionalized design and more reliable rectifiers have shortened the
shut-down time considerably on modern precipitators.

Mechanical Collectors

Bark char is a difficult material  to collect.  While  the particle size
is relatively large, the specific gravity is very low and the sliver
shape of the particles makes collection difficult.   Bark char has a
specific gravity in the 0.2 range; pulverized coal  ash for  example,  is
10 - 15 times heavier.   In addition to the unique particle shape, the
low specific gravity and the very fragile particles,  the bark boiler
collector must also be able to handle abrasive sand accompanying the
bark.   There are  consequently a number of considerations to make when
selecting a collector for a bark boiler.

Electrostatic precipitators are not generally suitable for use on bark
boilers due to (1)  the poor electrical  characteristics of bark char
and (2) the possibility of fires.

Some studies report that the bark char disintegrates  into fine
particles in a multi-tube collector due to the high centrifugal  forces
imposed.   These  fine particles coupled with  their low specific gravity
have a tendency  to float through the outlet  tube of the collector and
out the stack.   This phenomenon is also attributed  to the short dis-
tance from the wall  of the collecting tube to the outlet tube.  A sur-
vey shows that there are more large diameter cyclone  installations
                             -UO-

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 than multi-tube  units operating on bark boilers in the wood pulping
 industry.   It should be noted, however, that both collection devices
 can give sufficient efficiency providing they are selected properly.

 Many bark char collectors in the southern part of the United States
 are operating with reinjection systems that are not equipped with
 provisions  for separation of sand from the char before reinjection.
 Sand separation  is essential for reducing excessive erosion of the
 collector and the boiler tubes.  It is not unusual for a system
 operating on bark from southern pine to accumulate a number of truck
 loads of sand in an operating ,day.  Some mills are now selling the
 collected bark for manufacturing of charcoal briquettes.

 In many multi-tube collectors recovery vanes are installed to reduce
 pressure drop and collector size.-  The experience shows that collectors
 operating on boilers firing oil in combination with bark must be de-
 signed without recovery vanes.  Some oil fractions having high dew-
 points combine with the bark char particles and plug the recovery
 vanes..  One single plugged outlet tube can by-pass some 10 times its
 normal share of  flue gas uncleaned into the stack.  It is consequently
 imperative  to prevent plugging of the tubes.

Studies show that substantial improvement of the collecting efficiency
of bark char collectors can be attained by changing the normally coni-
cal bottom  outlet of the cyclone (tube).  By using straight cylindrical
tubes with  a peripheral discharge rather than conventional conical dis-
charge, the ash is removed from the tube before the gas reverses into
the inner vortex and in sufficient distances from the turning point.
This prevents re-entrainment of already collected particles.

The volume  handled by a given diameter collector tube depends on the
shape of the inlet guide vane.  Shallow pitched vanes give more spin
and handle  less volume.  Steep pitched vanes reduce the spin and can
handle more volume.   The shape of the inlet guide vane can make a
difference  in volume capacity of the tube at a ratio of 1 to 2.    The
vanes are of obvious importance for collector size as well as operating
efficiency.

Bark char collectors should be easily accessible for inspection, main-
tenance and repair because of the difficult operating condition under
which they work.   One always has to bear in mind the abrasiveness of
the dust and possibility of clogging.  Large diameter cyclone collectors
are easily  accessible for maintenance.  Some modern multi-tube col-
lectors also offer design with accent on maintenance.  The place sub-
ject to wear in a well  designed collector is limited to the collection
tube or cyclone cone.  Hard cast iron is often used in tubes.   Hardness
of 420 Brinell  has proven to be a maximum, because hard tubes are sub-
ject to thermal shock damage.  Cyclone cones, as well as the  entire
cyclone, are sometimes  furnished with abrasion resistant linings.
This lining is  usually  installed over a hexagonal  steel liner.
                             -171-

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 Both  mechanical  collectors  and electrostatic precipitators are
 sensitive  to  uneven  gas  and dust  distribution.  The entrance to the
 collector  is  normally  provided with devices for correction of uneven
 gas distribution.  The space  for  proper distribution ahead of the col-
 lector  is  almost always  very  limited.  Sharp bends and short transitions
 tend  to produce  uneven distribution across the entrance.  Various de-
 vices such  as spreaders,  turning  vanes and perforated baskets in the
 collector  entrance are used in efforts to overcome these problems.

 Hopper  fires  occur in bark  char collectors.  Unlike ash from coal
 fire  boilers, bark char must  be continuously and completely removed.
 A  small  air leakage  is enough for accumulated char to catch fire.  Gas
 tight construction is essential in bark char collectors.

 Design  must consider the  possibility and effect of fires.  This removal
 from  the hopper  must be accomplished without a back flow of air.  This
 can be  done most successfully with rotary steel valves.

 Bark  boiler dust collectors should be carefully sized for correct
 pressure drop inlet  velocity.  While efficiency generally increases with
 increased pressure drop (and  velocity) there are limits beyond which
 fragile material  like bark  char will be broken into smaller particles
 which has a detrimental effect on the collecting efficiency.

 The low specific gravity  of bark char, when the boiler is operated on
 100 percent bark without  reinjection, or the finer particle size dis-
 tribution when the ash is reinjected, create operating conditions which
 limit the application of  large diameter cyclones on these installations.

 Only when other  conditions  are superimposed over these conditions can
 the large diameter cyclone  approach 92 percent efficiency in  a single
 stage unit.  One of  the conditions which will  increase the efficiency
 is the amount of sand in  the bark char.

When operating on 100 percent bark, the efficiency will vary  greatly de-
 pending upon the amount of sand imbedded in the bark.   Without rein-
jection, much of the imbedded sand remains in  the bark char.   This
 greatly increases the average specific gravity of the  bark char, making
 the centrifugal   separation easier with higher  efficiencies.

      Example:   80% Bark  Specific Gravity (as char)  0.3

                 20% Sand Specific Gravity            2.8

      S. G. = (0.8)  (0.3) + (0.2)  (2.8) = 0.24 + 0.56  = 0.80

 For a large diameter cyclone where the specific gravity is assumed at
o.3, the most practical unit would give efficiencies  in the  70 to 75
percent range.   If, as in the example above,  the char  contained 20
sand,  the efficiency would increase to 85 to 89 percent.
                              -172-

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         The performance of mechanical collectors, with 40 percent bark and 60
         percent oil feed to the boiler, is greatly improved due to the higher
         specific gravity of the fly ash.  The nature of this dust, however, in
         multi-tube collectors creates a plugging problem.  The higher specific
         gravity and tendency not to plug make the large diameter cyclone
         practical for combination fired boilers.  It is possible to achieve
         the 92 percent design efficiency in both multi-tube and large dia-
         meter cyclones with single-stage units.  The 96 percent design ef-
         ficiency is possible with two-stage large diameter or multi-tube units.

    5.4  SULFITE SOURCES

         The evaluation of control methods for sulfite sources is limited to
         those which are distinct from the kraft sources.   The reader is refer-
         red to the previous discussions o-f kraft sources  for the following
         sulfite sources:  Washer vents, evaporators, power boilers, and com-
         bination boilers.  It should also be noted that control  methods have
         not been considered for the following sulfite sources:  Dump tank
         vent, Venturi absorbers, absorption towers, and ammonia incineration.
         These sources are either of minor importance from an emission stand-
         point, or there are no control methods presently  in use.

  5.4.1  ACID TOHER

5.4.1.1  Application

         The pressure accumulator is vented into the acid  storage tank because
         the two tanks are nearby.  The acid storage tank  is then vented to the
         absorption tower.   This system effectively prevents emissions from
         these items of equipment, thereby leaving the acid absorption tower
         as the only significant source of emission in the acid system.

         The construction of most absorption towers incorporates  a mesh  pad
         distribution system for absorption liquid.  Therefore, additional
         mesh pads are deemed necessary.

         The efficiency of absorption of most sulfiting towers exceeds 90 per-
         cent.   Some mills have placed a second absorption tower in series with
         the sulfiting unit for scrubbing exhaust gases.   This method has been
         tried only where an existing second tower was available  and could be
         used economically.   An example would be the conversion of calcium
         base,  requiring two towers, to ammonium base which requires one tower.

  5.4.2  BLOW PIT

5.4.2.1  Application

         Two systems were considered to replace the existing multiple wooden
         blow stacks and showers with a high efficiency S02 recovery system as
         follows:
                                      -173-

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           1.  Condenser with Cyclone and Absorption Tower

           2.  Packed Tower

     Flash steam, sulfur dioxide, and inert gases  are released in  the  blow
     pit during a digester blow.   These gases  then exit from the blow  pit
     and after the steam is condensed, the noncondensible  gases, mainly
     sulfur dioxide, are absorbed in a packed  tower.   The  recovered  sulfur
     dioxide is reused in the process and the  condensate creates a source
     of hot water.

5.5  NSSC SOURCES

     Evaluations of control.methods  applied to NSSC sources  are not  in-
     cluded due to the lack of emission data and application experi-
     ence.  The reader is referred to the previous kraft discussions for
     the following NSSC sources:   washer vents, evaporators, combination
     boiler,  and power boiler.
                                  -174-

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5.6  REFERENCES

     1.    Shah, I.  S.  and  Stephenson, W.  D.,  "Weak Black Liquor Oxidation
          System:   Its Operation  and Performance,"  TAPPI 51 (a), 87 -,
          1968.

     2.    "Steam,  Its  Generation  and Use,"  37th Edition, The Babcock and
          Wilcox Company,  New  York.

     3.    Fryling,  G.  R.,  "Combustion Engineering," Revised Edition First
          Impression,  Combustion  Engineering,  Inc., New York.

     4.    MacDonald, R.  G.,  Editor, "Pulp and  Paper Manufacture - Volume
          I,  The Pulping of  Wood," Second Edition, McGraw-Hill, New York
          1969.

     5.    Whitney,  R.  P.,  Editor,  "Chemical Recovery in Alkaline Pulping
          Processes,"  TAPPI  Monograph Series No. 32, TAPPI, New York, 1968.

     6.    Theon, G. N.,  DeHaas, G. G., Tallent, R. G., and Davis, A. S.,
          "The  Effect  of Combustion Variables  on Release of Orodous Com-
          pounds from  Kraft  Recovery Furnaces,"  TAPPI 51 (8), 329-,
          1968.

     7.    Harding,  C.  I. and Galeano, S. F., "Using Weak Black Liquor for
          Sulfur Dioxide Removal  and Recovery," TAPPI 50 (10), 48A-,
          1967.

     8.    Tomlinson, G.  H.,  Chapter 5, page 419, "Pulp and Paper Manu-
          facture - Volume I,  Preparation and  Treatment of Wood Pulp,"
          First Edition, McGraw-Hill, New York, 1950.

     9.    Thomas, E.,  Broadus, S., and Ramsdell, E.W., "Air Pollution
          Abatement at S.  D. Warren's Kraft Mill in Westbrook Maine,"
          TAPPI  50  (8),  81a-,  1967.

    10.    Hough, G. W. and Gross, L. J., "Air  Emission Control  in a Modern
          Pulp  and  Paper Mill," American Paper Industry, 36-, February
          1969.

    11.    Mullen, J. F., "A  Method for Determining Combustible Loss, Dust
          Emission, and  Recirculated Refuse for a Solid Fuel  Burning System,"
          Paper presented  at ASME Winter Annual Meeting, New York,  November
          29  -  December  4, 1964.

    12.    Wrist, Peter,  Mead Corporation, Verbal Communication, Liaison
          Meeting, New York, November 6, 1969.
                                -175-

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13.   Carlton-Jones, Dennis and Schneider,  H.B., "Tall  Chimneys,"
      Chemical Engineering, 75. October 14, Iy68.

14.   Martin, F.,  "Secondary Oxidation Overcomes Odor from Kraft
      Recovery," Pulp and Paper, 43,  June 1969.

15.   Industrial Gas Cleaning Institute,  "Test Procedure  for  Gas
      Scrubbers,"  Publication No.  1,  IGCI,  Box 448,  Rye,  New  York.
      1964.

16.   Industrial Gas Cleaning Institute,  "Criteria  for Performance
      Guarantee Determinations,"  Publication  E-P3,  IGCI,  Box 448,
      Rye, New York, 1965.

17.   NAPCA, "Tall  Stacks - Various Atmospheric  Phenomena  and Related
      Aspects,"  Publication No. APTD 69-12.

18.   Wrist, Peter, Mead Corporation, Personal  Communication, Sept.
      2, 1969.

19.   Blosser,  R.  0.,  and  Cooper, H.B.H.,  "Current  Practices in
      Thermal  Oxidation of  Noncondensible Gases  in  the  Kraft  Industry,"
      Atmospheric  Pollution Technical Bulletin No.  34,  National
      Council  for  Air and Stream Improvement,  Inc.,  New York.
                              -176-

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                              C  H  A .P  T  E  R    6

                        .   FIELD ENFORCEMENT  EQUIPMENT

       When  the FEO visits  a.pulp  mill  in  order  to  perform a  routine or special
       inspection,  it  is  not  anticipated that he will perform any  substantial
       amount of source  sampling.  He  should, however, carry  certain basic equip-
       ment  and records  pertaining to  the  facility.

  6.1   BASIC EQUIPMENT REQUIRED

       Normally the FEO  will  have  an official  vehicle equipped with a two-way
       radio to provide  adequate transportation  and  communications equipment.
       The car should  always  contain the basic equipment which will make  it
       possible for the  FEO to perform his inspection properly, and comply with
       all applicable  safety  rules and regulations.  The plant manager is
       responsible  for. insuring  that the OSHA regulations are complied with  by
       his own employees  and  visitors.  Thus the FEO should  be prepared  to  comply
       with  these regulations  also.   In  certain  areas it is required that all
       personnel  wear  safety  shoes, hard-hats, and  safety glasses.

       The following list indicates the  minimum  basic equipment which the FEO
       should carry with  him  and use:   hard-hat, safety glasses, safety shoes,
       asbestos gloves,  coveralls, Ringlemann chart or opacity guide, Polaroid
       camera, compass,  wind  speed indicator, flashlight, thermometers covering
       the range 50-800°F,  stop  watch, 50-foot tape  measure,  6-foot rule, manometer,
       or pressure/vacuum gauge  (0-30  inches  Hg  and  0-10 H?0), sample containers,
       thermocouple with portable  millivolt meter.

  6.2   RECORDS AND  FORMS REQUIRED

       Prior to the time of his  visit, the FEO should review  carefully  any  pre-
       vious field  inspection  forms concerning the  installation and the permit
       application  form.   He  should also carry with him on each inspection a copy
       of the previous field  inspection  form, a  copy of the air pollution code, and
       a copy of the emergency episode procedures.   He also should carry  with him.
       on a  clipboard  a  form  for recording his observations as well as data  obtained.
       from  the mil 1.

  6.3   PROCEDURES AND  EQUIPMENT  FOR SOURCE SAMPLING

       In the event that the  results of a  mill inspection and survey suggest, that
       source .sampling is required to  evaluate a particular unit,  the FEO may have
       his own personnel  conduct the  sampling or may require  mill  personnel  to con-
       duct  the sampling with an agency employee observing.   Regardless of who does
       the sampling, it  is  important  for the  FEO to assure himself that the  equipment
       to be used has  been  properly calibrated.  Generally the agency will be inter-
       ested in sampling for  particulate matter  and gaseous sulfur compounds.

6.3.1   PARTICULATE  SAMPLING PROCEDURES (AND  EQUIPMENT SPECIFICATIONS)

       Particulate  sampling procedures and the equipment utilized, should essentially
       conform to that outlined  in the Federal Register  (EPA). Vol. 36, No. 274, Part
       II (Dec. 23, 1971),  "Standards  of Performance for New  Stationary Sources."

                                    -177-

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  6.3.2  GASEOUS (SULFUR) SAMPLING PROCEDURES (AMD EQUIPMENT  SPECIFICATIONS)

         This section will  outline procedures and  equipment descriptions  which  have
         been utilized for sampling the major gaseous  constituents  emanating  from
         wood pulping processes.   Currently two  basic  methods have  been developed,
         sanctioned by the EPA and various states  for  sampling gaseous emissions,
         the Barton Titrator and  Gas Liquid Chroma-tograph  (GLC).

6.3.2.1  Gas/Liquid Chromatograph (GLC)

         Figure 6-1 illustrates the system which may be employed  in conveying
        .the gases from the source to the GLC sensing  equipment.  The  stainless
         steel  probe and Teflon sampling line are  maintained  at temperatures  ex-
         ceeding the dew point of the source gases.  The sampling line consists of
         an insulated, electrically heated 1/4-inch  Teflon tube.  The  sample  gases
         are transmitted to the heated dilution  box  where  they are  split  into two
         separate streams.   One stream is conveyed to  the  vacuum  source and wasted
         to minimize lag time in  the sampling line.  The remainder  of  the flow  is
         diluted with nitrogen by an amount sufficient to  lower the dew point of
         the gases below ambient  temperature. A portion of this  diluted  sample is
         injected into the Chromatograph through the Gas/Liquid Chromatograph (GLC)
         sampling valve.  The remainder of the diluted gas is wasted through  the
         vacuum source.

         Gaseous sulfur concentrations may be determined with a Gas/Liquid Chromat-
         ograph.  This unit is equipped with a flame photometric  detector which
         is specific for sulfur compounds.  Two  analytical columns  are utilized
         in the separation and analysis of the gaseous sulfur compounds.   One
         is a 36-foot by 1/8-inch OD Teflon column packed with polyphenyl  ether
         (liquid phase) on a solid support of granular Teflon. The second column,
         constructed of identical materials, is  8  feet long.   Both  columns are
         operated at 50°C.

         The 36-foot column is utilized for analyzing  hydrogen sulfide, sulfur
         dioxide, and methyl mercaptan while the 8-foot column facilitates the
         analysis of dimethyl sulfide and dimethyl disulfide.

         Several sampling loops of different volumes may be employed on the GLC
         sampling valve to accommodate a wide range  of gaseous sulfur  concentrations.

         The Chromatograph is calibrated for hydrogen  sulfide, sulfur  dioxide,
         methyl mercaptan, dimethyl sulfide and  dimethyl disulfide, using the
         "spinning syringe" technique or permeation  tubes.

6.3.2.2  Barton Titrator

         Figues 6-2 illustrates the system which is  employed  in conveying the gases
         from the source to the Barton Titrator.  The  stainless steel  probe and
         Teflon sampling line are maintained at  temperatures  exceeding the dew  point
         of the stack gases. -The sampling line  is identical  to the sampling  line
         used with GLC.  The sample gases are transmitted  to  the  Barton Titrator by
         a vacuum source.

                                        -178-

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Total reduced sulfur (TRS) concentrations are analyzed using a Barton
Titrator, Model  400..  Furnace gases are scrubbed through a 3% solution
of potassium acid phthalate (KHP) which removes sulfur dioxide and a
large fraction of water vapor from the sample gases.   The scrubbed gases
are then passed  through a combustion tube maintained  above 1500°F where
all the remaining reduced sulfur compounds are oxidized to sulfur dioxide.
The sample gas is then introduced to a coulometric titration cell which
utilizes hydrobromic acid (HBr) as an electrolyte.  The electrolytic cell
generates bromine from the HBr electrolyte which reacts with the sulfur
compounds entering the titration cell.  The quantity  of current required
to generate the excess bromine, to consume the sulfur compound, is pro-
portional to the gaseous sulfur concentrations introduced.  The current
required to operate the titration cell is sensed and  transmitted to a
recorder where a continuous readout is accomplished.   The recorded output
is converted to TRS concentrations, as S02» from calibration data generated
with the "spinning syringe" technique.
                                -179-

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               Glass  Wool
Source
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                         oo
                                  r
                                 u
                                        Dilution System

                                              O)
                                                       n
                                                        O)
"	_ _	',	I
                                                                 i i
                              n
                              u
                                                                                        Chart


                                                                                      Recorder
                                         In
Out
                                                  Gas/Liquid

                                                Chromatograph
                                                                                   Carrier Gas
                                                                .J
                                                                                          Vacuum Pump^
                                                             Dilution Nitrogen
                                             GAS  SAMPLING  SYSTEM

                                                  Figure  6-1

-------
I

oo
I
      Source
                     Glass  Wool
                    Heated
                    Probe





QJ
c'
	 1
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c
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Combustion

  Furnace
                                                                          Data

                                                                        Recorder
                       Barton
                     Titration


                        Cell
                                                                                                          -1-
                                                         O)
                                                         •*->
                                                         o>
                                                                                            Drying
                                                                                                                            Meter
                                                                                                                            Valve
                                                                                                                  Vacuum Pump
                                                   BARTON SAMPLING SYSTEM

                                                         Figure 6-2

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                                CHAPTER?

                        UTILIZATION OF FIELD DATA AND RECORDS

  7.1   GENERAL INFORMATION

       Most states have air implementation  plans  approved by the Administrator of
       EPA which contain provisions for a permit  system.  Normally, a permit is
       required for both construction  and operation of an air pollution source.
       The plans also require a  limitation  on  emissions of certain compounds .to the
       atmosphere as well  as pre-planned strategy for meeting an air pollution
       emergency.

       The application for permit  usually requires complete information on the
       site, a description of the  process and  process design, and information on
       the air pollution abatement strategy which is  intended to be used.  The
       application states  the level  of emissions  from all parts of the process
       without any abatement strategy.  In  an  application for a permit to construct,
       the applicant is required to make an estimate  of the level of emission to
       be expected with the proposed control  equipment whereas a permit to operate
       may not be granted  until  performance tests are conducted on the source and
       it can be shown that the  source will meet  applicable regulations.  Usually
       the regulations require that any modification  to the process or any modifi-
       cation to the control devices be reported  to the agency.  Usually the
       regulations also require  immediate notification of the agency in the case
       of an upset or emergency  condition.

       These requirements  implicitly call for  a continuing program of reports by
       the holder of the operating permit plus a  continuing program of inspection
       and observation of each source.  A visit by the FEO may be triggered by
       complaints, by reports from the mill, or a routine periodic inspection.  Ad-
       ditional information such as complete plans and specifications, operating
       conditions and similar data may be required by the director of the state
       agency.  All of the information previously cited will form the basis for a
       file on a specific  source.

  7.2  FILE OF FIELD DATA

       A file on each company (source) should  be  opened as soon as an inquiry from
       an official of the company is received  at  the  state agency.  The file should
       contain the completed application for a permit to construct and/or operate
       with any supporting data  submitted by the  mill  (such as flow diagrams).
       This file should also contain emissions data collected by the state pollution
       control staff or the mill staff, copies of permit, copies of complaints,
       and/or observed violations, and reports on inspections by the FEO.  In some
       instances, the complaint  file may be a  separate file, depending on the num-
       ber received, but copies  should be placed  in the general file for that source.


7.2.1   INDUSTRY DIRECTORIES                 " "	

       Information of a general  nature relative to a  particular plant may be
       obtained from one of several  pulp and paper industry directories, such
       as those of Post and Lockwood.   An example of  pertinent information which


                                        -182-

               environmental science  and engineering, inc.

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       may be found in these directories is as follows:   (1)  Company name and  or
       specific division, location, executive office location,  and phone  numbers.
       (2)  Production capacity, types of wood pulping processes and raw material
       consumption.  (3)  Management personnel and their area of responsibility.
       (4)  Summary of process equipment such as the number of  individual units,
       capacities, manufacturer, and miscellaneous information.

       A review of information contained in these sources  should be invaluable
       in assessing the extent and type of survey which  should  be performed  as
       well  as an indication of the technical  review required prior to  outlining
       the site inspection.


  7.3  ADDITIONAL SOURCES OF INFORMATION

       In building up the technical information file on  a  specific company,  and in
       preparation for an on-site inspection, the following additional  sources of
       information are suggested.  A suggested procedure for the on-site  inspection
       is described in the next chapter.

       Most pulp mills maintain excellent operating records.   The daily operating
       statistical report and the operating log sheets from the major process
       areas are somewhat similar from mill to mill.  These reports can be utilized
       to provide the FEO with a profile of operating levels  for various  mills.

       Many pulp mills routinely conduct source sampling tests  to determine  the
       performance level of air control equipment.-  This test may be conducted
       periodically or continously as indicated in previous chapters.  The reports
       are usually kept on file in the technical department.   In some states the
       results of emission monitoring are required to be submitted to the state
       agency on a periodic basis.

7.3.1  PROCESS EQUIPMENT SPECIFICATIONS

       Quite often, pulp mill equipment capacities are specified by the number of
       pulp production "tons" which they will support, and this does not  relate to
       the true engineering design criteria.  For instance, identical capacity
       equipment will support a variable pulp production rate,  depending  on  the pulp
       yield range which is being attained.

       Almost all pulp mill production equipment is specified and designed based
       on pounds of dry solids per unit time  processed.   These design capacities
       may be expressed as Ibs/hr, tons/day,  etc., with further qualifications
       regarding operating temperatures, inlet and outlet concentrations, etc.
       With proper conversion factors and pertinent knowledge,  it is possible
       to express specified design capacities in more convenient units  for com-
       parisons  or other reasons.  The Appendix of this report contains  information
       which will assist in converting process material  units.

       Pulp mill technical personnel  may quote "nominal" equipment capacities  and
       specifications when questioned in this regard, which may or may not reflect


                                        -183-

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       design and/or actual  operating rates.   Therefore,  the only sure way to
       determine the actual  design specifications  is to request a review of the
       quoted equipment specifications contained in the engineering file, as well
       as any designed modifications which may have altered the original.

       Examples of the type information which may be outlined and summarized in
       engineering design specifications is illustrated in Tables 7-1  and 7-2,  and
       Figures 7-1 and 7-2 for an evaporator  set and recovery boiler.

7.3.2  EMISSION CONTROL EQUIPMENT SPECIFICATIONS

       For the major pulping processes, emission control  equipment specifications
       will be tied closely to the process equipment specifications, particularly
       where the control  equipment is an integral  part of a "system."   In'a recently
       constructed mill,  these specifications would be included in a file with  the
       major process equipment.  In the case  of an older mill, in all  probability
       the control equipment has been updated by. modification or replacement,  and
       engineering data and specifications would be contained in a separate file.
       Control equipment  on the miscellaneous sources, because of the  various  avail-
       able-alternative methods, are usually  specified separately as additions  to
       the process.  An exception to this may be the case with mills which were
       built very recently.   (See Table 7-3 and Figures 7-3 and 7-4.)

       Control equipment  design specifications normally stipulate a performance
       guarantee based on inlet gas volume, grain loading, moisture content, and
       temperatures.  In  the case of sub-micron particulate "fume" and gaseous
       constituents,further stipulation may include quantitative limits' on compon-
       ents contained in  the process input feed or streams.  Design criteria also
       state static pressure and pressure drop relationships as well as liquid  rates
       and pH in the case of scrubber applications.

       Tables 7-4, 7-5, 7-6, and 7-7, contain results of performance tests on
       several different  types of control  devices. The data and nomenclature contained
       in these tables is similar to that which would be itemized in design
       specifications for similar control  devices.  More recently the trend has
       been to specify control systems as a "system" as opposed to individual
       components.  Where a system has been engineered as individual components,
       it is often difficult to determine the precise performance guarantee point,
       and where the responsibility and liability lies.

  7.4  AGENCY RECORD KEEPING REQUIREMENTS

       The FEO must be cognizant of agency record keeping requirements and/or
       plans.  The next chapter of this manual will contain recommended data
       format sheets, sequential inspection outline, and other pertinent informa-
       tion.  The final reporting of data for files, however, may require some
       individual judgement.

       If the agencies involved have not provided specific guidelines in these
       regards, the inspector may want to make recommendations or suggestions  to
       make files more functional for future reference and site inspection compar-
       isons.  These factors will become much more obvious after several pulp  mill
       inspections have been performed.   Inasmuch  as agency requirements are


                                         -184-

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constantly changing, it would not be appropriate to make concrete reconrr
mendations relative to these in this manual.
                                   -185-

-------
                  Table 7-1.   Operating  Conditions in a Sextuple-Effect Evaporator
                                     Flash
    Conditions                       Tank        IA        IB       II         III        IV         V        VI

Steam pressure                                              .
   psi                                         31.5       31.5      9.4       1.2
   vacuum, in. Hg                                                .                       8.3      16.2      22.0
Steam temperature, °F                           276        276      238       216        196       175        152
Working Temp,  drop, °F               -            24         26       13        13        15        17        24
Liquor Temp.,  °F                       232       252        250      225       203        181       158        128
Boilino pt. rise, °F                    14        13         11        7         5          4         3-3
Saturated vapor temp., °F              218       239        239      218       198        177    .   155        125
Vapor pressure
   psi                                          9.8        9.8      1.8
   Vacuum, in. Hg                                                             7.4       15.6      21.4      26.0
Latent heat of vapor, Btu/lb                     953        953      967       979        992      1005      1023
Pressure drop
   psi                                          0.4        0.4      0.6
   vacuum, in. Hg                                                             0,9        0.6       0.6
Vapor pressure                                                                                 '
   Next effect, psi                             9.4        9.4      1.2
   Vacuum, in. Hg
Feed, Ib/hr
Discharge, Ib/hr
Solids in, %
Solids out, %
Heating surface, ft2
Heating transfer coefficient,
   Btu/(hr)/(ft)2/(°F)     .                      174        242      392       386        316       240        190

90,605
89,200
51.1
52.0


109,775
90,605
42.2
51.1
4,400

135,825
109,755
34.2
42.2
4,400

178,815
135,825
26.0
34.6
8,800
8.3
219,585
178,875
21.2
26.0
8,800
16.2
251,995
219,585
18.4
21.2
8,800
22.0
166,520
130,475
13.9
17.8
8,800

166,520
121,520
13.9
19.1
8,800

-------
                                                                                                                   Water
 STEAM
CO

I
   THICK
   LIQUOR
-£
  fcOMBINED
  i  CONDENSATE
                      STEAM
                     CONDENSATE
                                               Figure 7-1.  A sextuple-effect evaporator.

-------
                               TABLE 7-2

                       COMBUSTION OF BLACK LIQUOR

                     Typical Operating Performance
Capacity* black liquor at 50%
  solids                          .      lb/24hr        3,000,000
Black liquor solids                     lb/24hr        1,500,000
Steam temperature                          °F               .825
Steam pressure S.H.. outlet               psig                850
Feedwater temperature                      °F                275
Air temperature at F
-------
                             TABLE 7-2  (cont.)

 Distribution
   Water  vapor loss all sources         1593.2             22.51
   Dry  gas  loss                          319.6              4.52
   Heat of  reaction correction           392.8              5.55
   Reduction of salt cake                119.8              1.69
   Heat of  fusion and sensible
      heat  in smelt                      233.7              3.30
   Radiation                              29.7              0.42
   Unaccounted for                       273.6              3.86

   Total  unavailable                 .   2962.4             41.85
   Heat available for steam             4116.4             58.15

   Total  distribution                   7078.8            100.0
   Enthalpy in steam, Btu/lb                                1410
   Enthalpy in feedwater, Btu/lb                             244
   Steam, Ib/hr                                          220,600

Quantity
   Steam  to liquor heaters, Ib/hr                          2,790
   Flue gas leaving evaporator, Ib/hr                    429,400
   Air  to air heater, Ib/hr                             . 318,400

Temperature
   Flue gas leaving economizer, °F                           648
   Smelt  temperature, °F                          .       .   1530
   Liquor to furnace, °F                                     240

Liquor  solids
   To evaporator, %                                           50
   From evaporator, %                                         68
   Reduction, %                                               95
   Sulfidity, %                           •                    25
* Before the addition of raw and precipitated salt cake.
                                   -189-

-------
o
I
                                     COMBUSTION GASES
                                   At exit gas temperature
                                   Dry gas, Moisture &  Fume
                                       (Na Compounds)
                                                           FEEDWATER
                                                                       RADIATION
                                                                                                  AIR FOR
                                                                                                 COMBUSTION
STRONG BLACK LIQUOR
 TO DIRECT CONTACT
    EVAPORATOR
     50% Solids
      200 °F
  Elemental analysis
weight percent dry solids
Carbon
Hydrogen
Sulfur
Sodium
Inert oxides
Oxygen
    SALT CAKE MAKEUP TO MIX TANK
          125 Ib / ton pulp
           Equivalent to
        0.0417 Ib / Ib solids
      at 3000 Ib solids / ton pulp
       reduce to Na$ in furnace
                                                                                                         STEAM
                                                                                                    INFILTRATION
                                                                                                        AIR
                                                              STEAM TO DIRECT  CONTACT
                                                                 LIQUOR HEATER
                                                                                              SMELT TO GREEN LIQUOR
                                                                                               DISSOLVING TANK
                                                                                              99% of Total
                                                                                              Na Compounds
                                                                                               and Inerts
                                                                                            Na2S        24.7%
                                                                                            Na2S04       1.3% y as Nc
                                                                                            Na2C03      70.0%_
                                  Figure  7-2,
                                      Typical conditions
                                      and heat balance.
for recovery unit material

-------
                                  TABLE 7-3

                                 BARK BOILER

                       DUST COLLECTOR EFFICIENCY TEST


Date of Test:


                                             BOILER      PRIMARY         SECONDARY
                                             OUTLET    COLL.  OUTLET     COLL.  OUTLET

Draft Loss                                                 2.0"               2.0"
Gas Temperature (Dry Bulb) °F                   640        640               470
Gas Temperature (Wet Bulb) °F                   165        170               175
Static Pressure Inches H20                     -2.5       -4.5              +0.1
Density @ Conditions #/Cu. Ft.               0.0326     0.0315            0.0363
Density @ 70° F. #/Cu. Ft.      '             0.0681     0.0662            0.0637
Gas Velocity in Duct Ft./Min.                  1609       1714              4233
Gas Flow in Duct @ Conditions CFM           279,000    245,960           211,650
Gas Flow in Duct @ 70°F.  SCFM               133,613    117,200           120,619
Volume Gas Sampled Cu. Ft.                   260.19     213.81            270.48
Sampling Time Min.                               35         27                30
Dust Sample Taken Grams               .      22.7924     1.5658            1.0956
Grain Loading @ Conditions Grains/Cu.  Ft.     1.3517     0.1130            0.0625
Grain Loading @ 70° F. Grains/Cu.  Ft,         2.8055     0.2345            0.1097
Collector Efficiency %                       	      91.64             53.22
Total System Efficiency %                    ——^     -	             96.09
Stack Dust Emission #/Min.                   	     	              1.89
Total Stack Emission per 24 Mrs. #/Day       —	—              2722
                                     -191-

-------
                                     Figure  7-3.
     TOO
      90
C
QJ
O
O
O
d)
80
70
      60
      50
                        9  In.;Tubes
        .0.5
             1.0      1.5      2.0       2.5       .3.0

                          Pressure Drop-In. Water

                     Cyclone Efficiency Vs. Tube Size
3.5
4.0
        Collection  Tubes

             To capably evaluate  dust  collectors,  the engineer must be aware that
        there are a wide  range of collecting  tube  designs available, affecting
        volume of gas  handled, draft loss,  efficiency,  operation, and price.
        The tube itself is  usually of  cast  iron  in  a size range between 6 and
        24 inches in diameter, nominally  9  inches  in diameter for bark boiler
        service.   The  smaller 6-inch diameter tube  is more efficient, but this
        is offset by the  higher tendency  to plug and the higher wear rate of
        smaller tubes.
                                        -192-

-------

-------
                             TABLE 7-4

                     Power Boiler Emission Data

                  FUEL:  NO. 6 OIL (NO ADDITIVES)

                    LBS. STEAM:  100,000 #/HR.



Gas Temperature (Wet) (F°)

Gas Temperature (Dry) (F°)

Gas .Volume @ Standard Conditions (S.C.F.M.)

Gas Density @ Standard Conditions (Lbs/Cu. Ft.)

Grain Loading @ Standard Conditions (Grains/S.C.F.)

Gas Volume @ Conditions (A.C.F.M.)

Gas Density @ Conditions (Ibs./Cu.Ft.)

Grain Loading @ Conditions (Grains'/A.C.F.)

Gas Volume Sampled (Cu. Ft.)

Gas Velocity (Ft./Min.)

Time Sampled (Minutes)

Dust Loading (Lbs./lOOO Lbs. Gas)

Dust Emission (Lbs./Min.)

Dust Emission (Lbs./Hr.)
INLET
125
330
29,509
0.0722
0.111
43,695
0.0494
0.07502
10,508
2819 .
840
0.2167
0.4683
28
OUTLET
125
325
30,492
0.0732
0.0137
45,429
0.0491
0.0092
10,855
2912
840
0.0268
0.06
3.6
Collector Efficiency:  87%
0=3%
CO  = 13.8%
15.4% Excess Air
                                 -194-

-------
                          TABLE 7-4A

                  Power Boiler Emission Data

                    PARTICLE SIZE-ANALYSIS

                  (INLET SAMPLE TO COLLECTOR)
The equivalent micron size is determined from the  Bahco  analyzer
having been standardized with a dust of 2.7 specific gravity  but
corrected to the actual  specific gravity of 1.22.
                    MICRON SIZE             % BY  HEIGHT


                     1.64 and Below             .66%

                     1.65 -  2.53              1.79%

                     2.54 -  5.50              8.78%

                     5.51 - 10.41              7.80%

                    10.42 - 15.62             11.26%

                    15.63 - 24.54           .  10.94%

                    24.55 - 31,24              2.16%

                    31.25 - 35.70               .72%

                    35.71 - .44.00               .53%

                    45.00 - 74.00             28.56%

                    75.00 -105.00             13.34%

                   106.00 -250.00             11.36%

                   251.00 -420.00              1.82%

                   421  and Above                .28%


                                             100.00%
                              -195-

-------
                 TABLE 7-5



SUMMARY OF TESTS ON BARK BOILER COLLECTORS
Type Collector - Mechanical,
Number Tubes
Type Vane
Design CFM
Design Temperature
Design Draft Loss
Type Fuel
Rated Steam Load
Bark
Bark & Aux. Fuel
Aux- Fuel
Steam Load, #/Hr.
Actual Oper. Temp.
Actual Oper. D. L.
MM BTU/Hr. Fired
Max. Rated #/Hr. of Bark
Volume:
ACFM, inlet
•SCFM, inlet
Dust Loading:
Inlet, #/Day
Outlet, #/Day
Inlet, #/M # Gas
Outlet, #/M # Gas
Inlet, #/MM BTU's
Outlet #/MM BTU's
Grain Loading, .gr/SCF:
Inlet
Outlet
Efficiency of Collection
Allowable Emissions, #MM BTU:
Georgia and NYC Code
Screen Mesh Size
Notes :
Multiple Tube
204
NR/A
152,530
500
2.73
bark & gas
150,000
150,000
165,000
200,000
150,000
460
228
54,700
150,190
85,323
60,120
4,096
6.797
.497
10.98
0.75
3.426
0.242
93.19
.35
24

285
NR/A
215,000
725
2.5
bark, gas ,oil
300 ,000
340 ,000
270,000
738
408
60,000
267,181
119,911
93.432
7,464
7.566
0.606
9.54
.76
3.788
0.3027
92.12
.45
30

384
NR/A
230,000
450
2.5
bark & oil
300,000
300,000
420
3.0
457
222,713
134,000
13,940
1,056
1.029
.0707
1.29
.0965
.5056
.0343
93.36
.44
14
35% bark
hardwood
65% oil
384
NR/A
230,000
450
2.5
bark & oil
300,000
268,000
410
2.5
407
188,510
114,800'
20,799
1,455
1,804
.1052
2.13
.149
.8805
.05286
94.12
.45
14
79% bark
pine
21% oil
344
NR/XD
293,000
679
3.0
bark & oil
300,000
300,000
455-425
3.5
457
241,618
1 39 ,500.
47,902
3,509
3.376
.2658
4.36
.317
1.6688
.13018
. 92.25
.44
—

340
NR/A
297,542
725
3.0
bark & gas
300,000
300 ,000
640
2.0
457
279,000
133,613
77,592
5,718
5.92
0.513
7.07
0.52
2.8055
0.2345
91.64
.44
20


-------
                              TABLE 7-6
                            SPECIFICATIONS
                           Venturi Scrubber
DESIGN INLET CONDITIONS

     Volume
     Temperature
     Humidity
     Dust Loading
     Density

DESIGN EXIT CONDITIONS

     Volume
     Temperature
     Humidity
     Dust Loading
     Density

PRESSURE DROP ALLOWANCES

     Waste. Heat Evaporator
     Kiln
     Duct Work
     Venturi Throat
     Separator
         TOTAL

HATER REQUIREMENTS
     Scrubbing Water
     Water Evaporated
     Bleed-Off at
% Solids
     Make-Up Water
     Water Recirculation

MATERIALS OF CONSTRUCTION

     Venturi Throat
     Flooded Elbow
     Separator
     Duct Work
     Stack
                                    CFM
                                    °F
                                    #W.V./#D.G.
                                    Grs/SCFD
                                    #/Ft.3
                                    .CFM
                                    °F
                                    #W.V./#D.G.
                                    Grs/SCFD
                                    #/Ft.3
                                    11 W.G.
                                    " W.G.
                                    " W.-G.
                                    " W.G.
                                    11 W.G.
                                    11 W.G.
GPM
GPM
GPM
GPM
GPM
                                  -197-

-------
           TABLE 7-6A
Venturi  Scrubber Efficiency Test
       °F
       °F
Draft Loss (inches H20)
Gas Temperature (Dry Bulb)
Gas Temperature (Wet Bulb)
Static Pressure (inches H20)
Density @ Conditions (#/cu.ft.)  .
Density @ Standard Conditions (70°F.) 3/cu.ft.
Gas Velocity in Duct (ft/min.)
Gas Flow in Duct @ Conditions A.C.F.M.
Gas Flow in Duct @ Standard Conditions (70°F.) S.C.F.M.
Volume Gas Sampled Cu.  Ft.
Sampling Time Minutes
Dust Sample Taken Grams .
Grain Loading @ Conditions (grains/A.C.F.)
Grain Loading @ Standard Conditions (70°F.) grains/S.C.F.
Collector Efficiency %                               .
Stack Emission (#/min.)
Stack Emission (#/hr.)
Stack Emission (#/day)
Dust Loading (#/1000 # Gas)
Georgia Code in #/hr. emissions based on process input.
   6000 #/hr.
                                           Inlet
400
152
 23
 Outlet

   22.6
  152
  152
                                              .0454
                                              .0695
     .275
     .0583
     .0673
                                          2011
                                         23207
                                         15159
                                           102.
                                         .   24
                                            28,
                                             4,
    72

    4204
    2692
                                             6.5319

                                            14.1524
                                           849.144
                                         20379
                                            13.4146
 1528
19208
16640
  195
   60
    0,
    0,
    0,
   99,
    0,
    4,
  114.
    0,
3633
0287
0331
49
0788
728

0704
                                                         8.56
              -198-

-------
                                                                 Table 7-7

                                            Information  Required For Complete Precipitator Survey
     COMPANY 	

     MILL	

     ADDRESS 	

     PERSON TO CONTACT FOR ANY  CLARIFICATION

                                PHONE NUMBER
Please fill-in or check appropriate blanks:

A.   Recovery information:

     1.  Boiler Manufacturer.	
     2.  Is this a conventional  unit with  a  direct contact  evapora-
         tor?  Yes 	  No 	

B.   Precipitator Design Data:
     1
     2.
     3.                       	
     4.  Inlet loading to precipitator, grains/AWCF
     5.~ Outlet loading from precipitator, grainf/AWCF
     6.  Guaranteed efficiency @ A.2.  gas volume
    Manufacturer.	
    Gas volume, actual  wet cubic feet per  min.
    Gas temperature, °F.
(AWCFM)
     7.  Gas velocity in precipitator, feet per second (FPS)

     Precipitator Construction:
         Number of chambers.
         Number of fields.
1.
2.   .. ..             	
3.  Dry bottom or wet bottom?  Wet 	  Dry 	
4.  If dry bottom, is it a hopper bottom or drag bottom?
    Hopper 	    Drag
     5.  Does precipitator have a weatherproof enclosure for trans-
         former rectifiers?    Yes 	  No 	
     6.  Is the precipitator a steel  or tile shell?  Steel  	
         Tile 	
     7.  If steel shell, do you have  a shell heating system?
         Yes 	  No 	
     8.  Is the I.  D. fan upstream or downstream from precipitator?
         Up 	  Down 	

D.   Collection System:

     .1.  Total collecting surface area, square feet 	.
     2.  Height of collecting platers, feet 	.
     3.  Number of collecting rappers	.
                                                                       E.   High Voltage Discharge System:

                                                                            1.  Number of transformer rectifiers.
                                                                            2.  Total output capacity of all  transformer rectifiers
                                                                                milliamps.
                                                                            3.  Number of discharge rappers.  	
                                                                                                                    Mechanical  Hammer
                        F.   Rappers:

                            1.  Manufacturer 	
                            2.  Type:  Electric 	Pneumatic

                        G.   Inlet and Outlet Boxes:
                                                                            1.  Do you have gas distribution devices, at precipitator in-
                                                                                let?  Yes 	No 	  At precipitator outlet?  Yes  	
                                                                                No
2.  Type of distribution devices:
        Perforated Plate    	 (Inlet, outlet or both) 	
        Adjustable Channesl 	    "       "        "   	
        Other               	    "       "        "
        None                	    "       "        "   	
-3.  Do you experience pluggage of these"devices at precipitator
    Inlet?  Yes 	  Ho 	
4.  Do you have rappers on these devices, if any?  Yes
    No 	

Shut-Off Gates:

1.  Manufacturer.
                             2.  Type of gate (slide, multivane damper or other)
                             3.  Do your gates perform satisfactorily?  Yes 	  No 	

                             Precipitator Operating Performance:  (Please complete the
                             following  if possible.)

                             1.  Date of precipitator start-up. 	
                             2.  Initial performance:
                                    Efficiency                          %
                                    Gas  Flow
                                    Inlet Grain Loading
                                    Outlet Grain Loading
                                    Gas Temperature
                                                                                                                       _AWCFM
                                                                                                                       _Grains/AMCFM
                                                                                                                       _Grains/AWCFM
                                                                            3.  Performance approximately one (1) year after start-up.
                                                                                    Efficiency            	%
                                                                                    Gas Flow              	AWCFM
                                                                                    Inlet Grain Loading   	Grains/AWCFM
                                                                                    Outlet Grain Loading  	Grains/AWCFM
                                                                                    Gas Temperature       __^	°F.
                                                                            4.  Performance approximately two (2) years after start-up.
                                                                                    Efficiency            	%
                                                                                    Gas Flow              	AWCFM
                                                                                    Inlet Grain Loading   	Grains/AWCFM
                                                                                    Outlet Grain Loading  	Grains/AWCFM
                                                                                    Gas Temperature       	°F

-------
                                                                   Table 7-7
                                                                     (cont.)
     5.  Performance approximately three  (3) years  after  start-up.
             Efficiency           	%
             Gas Flow             	AWCFM
             Inlet Grain Loading  	Grains/AWCFM
             Outlet Grain Loading 	Grains/AWCFM
             Gas Temperature      	       "F.
     6.  Performance approximately four (4) years  after start-up.
             Efficiency           	
             Gas Flow             	
             Inlet Grain Loading  	
             Outlet Grain Loading 	
             Gas Temperature      	
                                                           5.  Please describe any other problem areas:
                       _AWCFM
                       _Grains/AWCFM
                       _Grains/AWCFM
J.   Precipitator Testing:
     1.
                                                             Yes
         Were guaranteed performance tests run on the unit?
         No	
         What type of particulate test do you perform for guarantee?
         (Check one)  Wet impinger              	
                      Dry thimble
                      Dry thimble & glass filter_
                      Other
         Do you routinely test the precipitator? Yes   	 No 	
         If yes, is this weekly, monthly, yearly, or  what? 	
         What type of particulate test do you perform for routine
         precipitator testing, if any?  (Check one)
                      Wet -impinger              	
                      Dry thimble               	
                      Dry thimble & glass filter	
                      Other
K.   Precipitator Operation:  (Please give your opinion)

     1.  uo vou have internal corrosion in your precipitator?
         Y^s"	  iic.   	
     2.  .lava yuu experienced any corrosion or deterioration of your
         shall that you consider serious?  Yes 	  No	  If
         yes, please explain. 	

     3.  If a dry bottom unit, do you have any plugging problems in
         conveying salt cake to salt cake mix tank? Yes 	 No 	
     4.  Do you consider any of the following to be problem areas?
         (Yes or NO)  Wire breakage
Collecting plate
   ment
                                         discharge electrode align-
                      Salt Cake Buildup
                         If yes, explain where buildup occurs
                      Wet bottom agitators
                      Dry bottom hopper 	
                      Rapper controls
                      Transformer-recti fiers
                      Transformer-rectifier controls
                      Shut-off gates 	
                      Rappers 	
Is precipitator showing a problem on your unit?  Yes  	
No 	
Was your precipitator adequately sized for your require-
ments?  Yes ___  No 	  If no, is this because your
boiler is operated above rated capacity?  Yes 	No  	
                                                           Miscellaneous:
                                                               Did the precipitator vendor erect your unit?  Yes  	
                                                               No 	
                                                               Do you believe the precipitator vendor should erect the
                                                               precipitator?  Yes 	No	Makes no difference  	
                                                               Did you obtain a satisfactory erection job?  Yes    No
                                                           4.  Did the precipitator vendor stand behind his unit? Yes 	
                                                               No 	
                                                           5.  Approximately how many hours per year is one or more of your
                                                               precipitator chambers out of service because of the pre-
                                                               cipitator?  	hours
                                                           6.  Approximately what have you averaged spending per year for
                                                               precipitator maintenance?                $	
                                                           7.  Precipitator Location:  (Check one)
                                                               On Bui Idi.ng .Roof 	  On Ground.	 In Between 	
                                                           8.  Approximate stack height: Above Precipitator Roof 	 Feet
                                                                                         Above Grade             	 Feet

                                                           Comments:

                                                           1.  What suggestions would you offer to improve precipitator ocr-
                                                               formance and reliability? 	
                                                            2.  Other  Comments:

-------
                               CHAPTER   8

                       SITE INSPECTION-ENFORCEMENT PROCEDURE
8.1  GENERAL
     The data to be collected and the procedures to be followed are determined
     by the purpose of the inspection and whether this is an initial or a
     subsequent, inspection.

     Specific procedures, especially the citation of violations will depend
     on the control program and policies of the air pollution agency involved.
     In general, the inspector performs the following functions:  (1) Reporting
     or verifying progress made by the mill in meeting compl iance plan schedules.
     .(2)  Verifying any changes from the conditions of the permit.  (3)  Assuring
     that day--to-day operation and maintenance practices serve to minimize pol-
     lution wherever possible.  (4)  Reporting breakdown, shut down, or bypassing
     of process equipment and changes in pulp production schedules or cooking
     and chemical recovery procedures.! (5)  Citing violations that are clearly
     flagrant in nature.  (6)  Correlating public complaints with air quality
     measurements, emission rates, and control practices.  (7) Noting any new
     sources, new or modified control devices, and changes in pollution control
     personnel since the last visit.  (8)  Reviewing the emission data collected
     by the plant staff and comparing it with reports submitted to the control
     agency.

     In all cases certain general procedures should be followed including:  (1)
     off-site observations, (2) interview with plant personnel, (3) in-plant
     observations, (4) critique and meeting with plant management, and (5) ob-
     serving safety precautions.

8.2  OFF-SITE OBSERVATIONS    •      '   ;

     Before entering the plant, the inspector should observe and note any
     visible emissions and odors, dustfall in the surrounding area, possible
     vegetation damage, and/or effects on materials and paint.  These findings
     should be correlated with public reactions in neighboring communities and
     with specific mill operations wherever possible.. ,

     The inspector should note wherever possible wind directions, wind speed,
     humidity, and atmospheric stability in his observations, and he should
     develop a systematic procedure for patrolling and noting the location,
     quality and intensity of the odor.  Odors may be noted on an^intensity
     scale or a scentometer may be used.  The inspector may organize a com-
     munity odor panel consisting of carefully selected citizens who may
     help to establish the significance of day-to-day ground level variations
     within the normal odor intensity range.  An expert odor panel working under
     controlled, closed room conditions may also help to isolate the effect of
     possible changes in mill operations (1).                                   .

     Sulfur compounds (particularly FLS) can discolor and damage lead based paints
     and.paints containing mercury-based fungicides and may accelerate tarnishing
     of silver and copper.  Discoloration usually takes the form of browning or
     blackening of materials and is enhanced if the surfaces have been moistened


                                       -201-

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or weathered, depending on the lead content.  Fungi will also darken un-
protected paints, so the inspector should, in doubtful cases, have the
cause of damage verified by experts.  Vegetation damage also may result
from sulfur dioxide emitted from boiler equipment, as well as from hydrogen
.sulfide.

Deposits of particulates may result from the fallout of saltcake particles,
fly ash, soot, burned particles, and lime, which are usually confined to
within 1/4 to 2 miles from the plant.  Some of the.fallout is of a compara-
tively caustic nature and can damage vegetation, materials and painted sur-
faces particularly on vehicles located near the plant.  Particles may be
sampled and taken to the laboratory for analysis to help identify the process
sources responsible.  Particles high in calcium are generally emitted from
the lime kiln; particles high in sodium may originate from the recovery
furnace and smelt tank; charred or insoluble material originates from hog
burning equipment.  Sodium salts, which tend to be more volatile than other
particulates, may be due to flocculation of particles in the electrostatic
precipitator.  These consist of fluffy aggregates up to 1 millimeter in
diameter (5).  The largerraggregates are largely responsible for damage to
paint and vegetation.


All observations should be carefully documented including the date and time,
and weather conditions  (especially wind speed and direction).  In reading
visible emissions, the  recommended procedures regarding location of observer
in relation to plume and sun must be followed.

Points of emissions in  a pulp mill include stacks and vents at roof level,
the recesses between plant structures, inside the structures, and ground
level.  The obvious emissions are the stream plumes and mists, particularly
from the recovery furnace.  These can be voluminous and may travel over
great distances and altitudes..  The steam and vapor emissions make it dif-
ficult to isolate and read the dry portions of the plumes.  Long plumes, how-
ever, are always suspect in view of the relatively rapid dissipation of steam.
Reading visible emissions,.while.taking into account the dry and liquid
contaminants is tenable, but the practice will depend on the policy of the	
air pollution control agency involved.

The inspector should become familiar with the.quality and intensities of
odors and the visual character of mill emissions as they vary through the
day and with weather conditions.  Where abnormal conditions occur, source
testing should be requested.  Where a. large number of public complaints
are reported, the possibility of odors being released with intermittent
emissions from starting up and shutting down of equipment, opening of
digesters, condenser or heat recovery system failure, and overloading of
recovery furnace, should be investigated.  Vents on bleaching and other mill
operations, also, should not be ignored, .as chlorine gas can be accidentally
released.                         ,  .
                                  -202-

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8.3  INTERVIEW WITH PLANT PERSONNEL

     Direct discussion with both management and operating personnel  will
     enable, the enforcement officer to gain a complete understanding of the
     plant schedule and operation, and allow plant personnel  to understand
     the officer's purpose for this inspection.  If a violation has  already
     occurred, the responsible persons should be notified and the reason
     for the violation determined.

     Establishing a good rapport with the plant staff will  be most important
     in obtaining process operating information, descriptions of start-up
     conditions, number and extent of upsets, equipment breakdown problems,
     and related information.

    .In pulp mills, the interview is usually conducted with staff that has
     been permanently assigned to the air pollution .problems  of the  plant.
     The interview should be primarily directed at ascertaining factors which
     affect process emissions, control progress and changes in operating
     procedures which cannot be noted during the physical inspection.  Record-
     ing charts, logs and charts relating to process performance and emissions
     can be examined in the office with the air pollution staff of the mill.
     The inspector should clearly establish normal operating  procedures in
     order to be able to identify abnormal or changing conditions.  A pro-
    • cedure should be adopted and practiced by which the mill reports upsets
     and outages to the enforcement agency.  Scheduled maintenance,  especially
     if it involves taking control equipment out of operation,should be an-
     nounced in advance.

     The exact nature of an interview will vary with the purpose of  the visit..
     For an initial visit an extensive review of the process  equipment, layout,
     and operating schedule will be required.  Subsequent visits will require
     less time and consist only of a review to make sure nothing has changed,
     or if changes have occurred, to check their effect on emissions.

     Information obtained by interview should include: .

         1.  Type of Wood Used:  resinous content, softwood,  hardwood
             extent of use of saw dust, etc.  The methyl  group con-
             tained in certain sulfur.based emissions derive  from the
             methoxyl content of woods.  Hardwoods contain more methoxyls
             than softwoods, arid have greater process odor potential (7).

         2.  Cooking Variables..  Malodorous emissions can be  increased
             when cooks are shortened and pressure and temperatures  are
             increased.

         3.  Pulping Capacity of the mill should be determined in terms
             of tons of unbleached air dried pulp.  The inspector
             should become familiar with variations in pulping capacity.
             Substantial increases in pulping output may cause the capaci-
             ties of existing process equipment to be exceeded, including
             overloading of the recovery furnace, and excessive emissions
             from power plant and other supporting equipment.


                                   -203-

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         4.  Plant program for monitoring emissions.   The inspector
             should be familiar with the mill  schedule for conducting
             source testing and maintenance of continuous monitors,
             such as the titrator, discussed later.   It is extremely
             important that the equipment be kept in  good working
             order.  The inspector should clearly establish any
             modifications made by the plant to the  instrumentation,
             and. should assure that a formal procedure for maintaining
             the accuracy of continuous monitors be  adopted.

         5.  Emission inventories, negotiated compliance plans and
             permits.  The inspector should have available with him
             information concerning the equipment and emission inven-
             tories of the plant to determine if significant changes
             have been made in any of the major sources that will
             affect emissions and odors.  It is desirable to compare
             operating permit, inventories, process  flow diagrams, and
             plot plans on file with existing conditions.  This can
             be accomplished either before or after  the tour through
             the plant.  The liquor flow, the exact  points of-emission
             and firing rates to the recovery furnace, the lime kiln
             and the power boilers and hog burners,  in particular,
             should be noted.

         6.  Frequency of conditions under which excessive emissions
             might occur, such as start-up, soot blowing, ash removal,
             peak loads, etc. should,be discussed and noted.

             Interviews also present a good opportunity to discuss future
             plans for changes in the operation such  as expansions and/or
             major modifications.  The personnel interview is also an excellent
             time to review emergency action plans and discuss the feasibility
             and time schedule required to implement  the plan.

8.4  IN-PLANT OBSERVATIONS
          i

     The field enforcement officer upon entering the  plant property should
     ask for the plant manager and state his name, affiliation, and purpose.
   •  In most cases, his visit will have been prearranged and he will have a
     firm appointment.  However, on occasion, a random visit or a visit based
   .  on an off-site observation will be made.   During such times, the plant
     manager may not be available and a. lower ranking member of management or
     technical staff should be requested.

     While inside the plant boundary, the inspector  should again note the
     general "housekeeping" practices within the plant; i.e., is the plant
     equipment well maintained, are the roadways dust covered or littered,
     is equipment kept clean and painted.  These general observations will
     give the inspector a feel for the care taken in  preventing excessive
     atmospheric emissions.
                                   i   '            •
     Additional .visible emissions and/or odor observations can be made on-
     site, especially if vents were not visible from  the plant boundary.


                                   ,-204-

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8.4.1  EQUIPMENT INSPECTION

       The field enforcement officer should visibly inspect the process
       equipment, any control  devices,  and all  'appurtenances.   Nameplate
       data and ratings should be checked and the degree of maintenance
       and operability of all  equipment noted.   Operational  data such as
       temperatures, pressure  drop, steam rates, auxiliary fuel  use,  etc.
       should be noted where available.  He should be especially cognizant
       of unusual operating conditions  such as  excessively high or low load.

       A visual inspection will  also .indicate the operability  and care given
       to the instruments and  control systems used to monitor  and operate  the
       process.

8.4.2  DETERMINATION OF OPERATING CONDITIONS

       An assessment of the operating conditions, and their related effect
       on emissions, can be performed in a,comprehensive manner provided
       adequate preliminary evaluations have been performed, i.e., following
       the pre-survey review of the mill, review of state permit applications,
       and review of the process and control equipment specifications.  If
       these reviews are performed comprehensively in the proper sequence,
       it is conceivable that  in the case of well maintained mills with  good
       operating records, and  with the  assistance of proper data, a site
       evaluation could be performed, requiring  very little time in the process
       areas.1  The source of this information and operating data is the  daily .
       operating statistical report and the operating log sheets from the
       major process areas.

       Figures 8-1 through 8-7 contain  plots of some of the more pertinent .
       measured variables and  their relation to emission levels associated with the
       -kraft recovery furnace  operation.  Similar relationships for other  kraft
       processes, and other pulping processes,  may be found in Chapters  2  and
       3, or may be derived from the discussions contained in  these same
       chapters.  Tables 8-1 and 8-2 have been  prepared to assist field  enforce-
       ment personnel in conducting their surveillance of operating variables
       and conditions relating to atmospheric emissions.


8.4.3 .ASSESSING CONTROL EQUIPMENT OPERATING CONDITIONS

       Pertinent control equipment operating variables are also monitored
       with in-line  instrumentation which are alsp^shown on process flow-
       sheet instrumentation schematics as previously discussed.  The impor-
       tant variable values are also recorded on the appropriate process
       operating log sheets.

       The optimum  level of these variables, as required to maintain maxi-
       mum performances, are normally  stipulated in the formal design
       specifications.  Principles of operation for all types  of control
       devices  have  been discussed ^'n  Chapter 4 and effects of operating
       variables have been  discussed in Chapters 2 and 3.
                                  -205-

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8.4.4  ESTIMATING EMISSION RATES

       The appendix contains a series of graphs developed by NCASI, which relate
       atmospheric emissions from various sources in the kraft pulping process,
       to pulp production rates.  The basis used to derive these relationships
       is clear-ly stated, and correction factors must be applied to these data
       if the basic process basis differs appreciably from that stated.   This
       data can be used effectively to'determine nominal levels, to compare
       operating data and estimate emission levels where data is not available.

8.4.5. SOURCE SAMPLING RESULTS CONDUCTED BY MILLS

       Many pulp mills routinely conduct source sampling tests periodically
       to determine the performance level of their control equipment.  The.
       results of these tests are usually the subject of an informal report
       for inter-company use.  These reports are kept on file in the technical
       department and should be available for review by enforcement officials.
       This is another source of information which may be used to assist
       enforcement officials in developing their site inspection plan.

  8.5  CRITIQUE AND MEETING WITH PLANT;MANAGEMENT

       An effective air pollution control program cannot be conducted at
       a pulp mill unless it has the whole-hearted endorsement of management.
       It is important therefore that the inspector discuss all of his major
       findings both good and bad with; top mill management.  At the least, this
       should include the mill manager and the technical director.  Those
       personnel who accompany this inspector on his inspection should also be
       present.  It is especially important to inform the top management of the
       mill of any adverse findings as well as the need for new equipment or
       new programs.  It is also important to inform them of especially effective
       work done by the mill employees..

  8.6  SAFETY PRECAUTIONS

       The field enforcement officer must obey all safety precautions during
       his visits, whether.or not they are required by the plant.  As a rule
       the enforcement officer should not sign accident waivers when entering
       a plant.  He should, however, have his own personal safety equipment
       such as a hard hat, eye and ear protection, and safety shoes, etc.,
       as detailed previously.  On a first visit to a plant, he should review
       all safety rules with plant personnel.  The inspector should never
       tour the plant without an escort, nor should he open furnace doors,
       manipulate valves or controls, or in any way try to change the operating
       characteristics of the unit.  When observing the combustion chamber
       interior, he should always have the operator open the viewing ports,
       and always use proper eye and face shields.

       Due to a large number of fans,'belt and chain drives, electrical
       motors, etc., the inspector should be especially aware of the hazards
       associated with this type of equipment.


                                  .  -206-

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       The inspector should not climb on ladders,  scaffolds,  etc.  unless
       they meet the appropriate safety standards.

       As a general  rule, the inspector should  not  take any action which  he
       feels could in the slighest way>cause a  safety hazard  to  himself or
       other plant personnel.

  8.7  SPECIAL PROCEDURES FOR KRAFT MILLS      .             .

       The physical  inspection should be organized  around  two  closed  systems:
       (1)  The black liquor system including the  digesters,  relief valves,
       accumulators* oxidation towers (if used), multiple  effect evaporators,
       direct contact evaporator., recovery furance, and smelt  tank.  (2)  The
       lime recycling system including the mud  filter, lime kiln,  and slaker.

       The bleaching plant should also be inspected, particularly the brown
       stock washer, where water vapor and malodorous compounds  may be collected
       by a hood and discharged to the atmosphere.

       The principal odors from a kraft mill are characteristic  in terms  of
       their quality and pervasiveness.  Tables 8-2 and 8-3 illustrate odor.
       thresholds, and qualities of sulfur compounds.(1).   Other odors such
     ;  as terpenes and methanol differ significantly from  hydrogen sulfide
       and mercaptans, and are easily recognized.   These have the odor of
       turpentine  or are "medicinal" ,in character, and tend  to  be localized
       around process equipment, particularly stock washers,  and oxidation
       towers.  The sulfides and mercaptans, by contrast,can  be  detected  many  .
       miles from the plant.

8.7.1  BLACK LIQUOR SYSTEM

       Although the recovery furnace is the most significant  unit from the
       viewpoint of the emission of particulate matter and TRS compounds,
       the inspector should visit all the other units previously described
       for this system.  The inspector should become familiar with the vents,
       valves and. condensers, the type of. condensers, and  associated  odors
       and emissions.  The design., condition, and  operation of all other  units
       should be noted as these have a bearing  on  the release  of odors.from
       the furnace.   Spills, indications of poor maintenance,  and low level
      .odors should be noted at each unit.  It  is  necessary also to deter-
       mine what treatment is applied to malodorous gas streams.
                                     1
       Not only is the recovery furnace the most important source of  emissions
       in the black liquor system, but the operator of the furnace maintains .
       a daily operating log which contains information from  other parts  of
       the system.

       The inspector should become familiar with the specific design  and  oper-
       ation of the recovery furnace in the plant  to which he is assigned.
       Many factors enter into achieving optimum combustion in the furnace
       from an air pollution standpoint, including the firing rate, secondary
       air flow, percent excess oxygen in the flue gas, black liquor  spray
       droplet .size, time, and turbulence.  In  the recovery furnace control


                                     -207-

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       room, the following items (usually entered  hourly)  should  be  checked on
       the operator's  log sheet or by instrument readings:   (1) Sulfidity of
       white liquor (in some mills the sulfidity of the  green  liquor is mea-
       sured), (2) percent solids of the black liquor,  (3)  sodium sulfide
       content of black liquor in and out of the black  liquor  oxidation unit
       (if one is used), (4) excess oxygen in flue gas,  (5)  rate  of  excess
       air and secondary air, (6) black liquor firing  rate,  (7) combustibles,
       (8) TRS emissions (Barton), (9). frequency and time  of soot blowing,  (10)
       steam production, and (11) voltage and amperage  readings of the
       electrostatic precipitator.

       All of the above items should be correlated with recovery  furnace
       emissions, so that overloads can clearly be recognized  from the
       performance data.

       It should be noted that increased sulfidity usually results in higher
       TRS emissions.  Also it is important to note the  relationship of
       TRS, combustibles, and excess oxygen.  When TRS  increases, combustibles
       also show an increase, but excess oxygen will show  a  decrease, and
       vice versa.  Excess oxygen readings below about  3%  may  indicate furnace
       overloading, and/or may indicate an increase in  TRS emissions.

       The inspector should check to see whether the air ports in the recovery
       furnace are regularly rodded to prevent plugging and  that  excess oxygen
       and proper operating temperature (usually around 1100°F) are  main-
       tained in the upper oxidation zone of the furnace.   A decrease in
       secondary air for any reason can cause an  increase  in emissions.  The
       inspector should recognize,however, that steps  may  have to be taken
       on occasion to prevent dangerous situations such as furnace reaction
       explosion..

8.7.2  LIME RECYCLING SYSTEM

       The lime recycling system may be a source of both particulate and
       odorous emissions.  The makeup rate for salt cake (pounds  of  salt
       cake added per ton of pulp produced) indicates  how  much of the sodium
       and salt cake is being lost to the atmosphere and to  wastewater reuse
       or treatment.  A loss of 100 pounds of salt cake per ton.of pulp may
       be reasonable, but the proper figure must be established with each
       plant.  This information generally will be  found in the recovery furnace
       log sheet.  Hydrogen sulfide may be emitted from, a  kiln stack, particu-
       larly in long kilns, due to reactions of carbon  dioxide with  sodium
       sulfide in the carbonate sludge, and to the introduction of carbonate
       at the cooler end of the kiln.  In some plants  non-condensible gases are
       carried to the lime kiln for incineration.
                                      i
       Operational data for this system usually will be found  in  the operators
       log at the lime kiln control room.  The following lime kiln operational
       data should be obtained from the log sheet:  (1) sodium and sulfide  con-
       tent of washed cake (usually taken once per day or  per  shift), (2)
       scrubber water flow rate and source (usually taken  once an hour),(3)
       scrubber pressure drop by manometer, and (4) TRS emissions (Barton).

                                     -208-

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     It should be noted that large variations occur in emissions from different
     mills using the same process, making the same products, from the same
     wood species..  Even in the same mill large variations may occur from
     hour to hour.

8.8  SPECIAL PROCEDURES FOR SULFITE MILLS

     The sulfite segment of the pulp'industry, unfortunately, cannot be as
     readily categorized as the kraft segment.  There are four chemical bases
     for cooking liquor, four pH ranges for the liquor, and about twenty
     schemes for recovery of the cooking liquor.  Thus the number of
    ,possible combinations far exceeds the 33 sulfite mills reportedly
     operating in the United States i,n 1973.

     Whillte (JJL) has published a comprehensive review of sulfite and bisulfite.
     recovery systems.  He concluded that the only proven technology for  •
     recovery of both base and process sulfur is for magnesium base sulfite
     liquors.

     Generally speaking, the principal emissions are sulfur dioxide and
     particulate matter and the major, source of S02 is the blow tank of an
     uncontrolled mill.  In most sulfite mills the SO,, emissions from the
     various sources are recirculated several times tnrough the absorbers to
     boost the sulfite content of the cooking liquor.
                                     i
     For these reasons, an inspection; itinerary which would be applicable-to
     even a majority of the mills is virtually impossible.  Since there are
     no more than 9 or 10 sulfite mills in any state, it is recommended that the
     FEO work closely with the technical 'Staff of each mill to establish an
     inspection protocol.

8.9  SPECIAL PROCEDURES FOR NSSC MILLS
                                    ' I  '              •    .
     As in the case of sulfite mills, there is considerable difference among
     NSSC mills-  In fact, many of the existing mills were converted to
     NSSC from other types of pulping.  Thus, categorization of this segment
     of the chemical pulp industry is virtually impossible.

     Emissions to the atmosphere from NSSC pulping depend largely on the
     method of handling the spent cooking liquor.  Nearly half of the NSSC
     mills is the U. S. sewer the liquor and treat it as a liquid waste.
     Nearly as many mills attempt recovery of heat and chemicals by intro-
     ducing the spent liquor into a smelter or recovery furnace (either its
     own or that of a neighboring kraft mill).  Since the spent NSSC liquor has
     a lower pH than the spent kraft liquor, a mixture of the two results in
     an increase in emissions of S02 and I^S from the kraft recovery furnace.
   .  According to Galeano (1_3_), the principal emissions are particulate matter,
     S0_ and H^S.  The major sources appear to be the recovery furnace or
     smelter, the sulfiting tower, and the blow tank.

     Because of the lack of data on emissions from the NSSC process, especially
     on the variation between mills, an  inspection itinerary which would be   .


                                   " -209-

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applicable to even the majority of the U.S. mills is impossible.   Since
there are no more than 4 mills using the NSSC process in any state
(roughly 40 in the U. S. in 1973), it is recommended that the FEO
work closely with the technical staff at each mill  to establish an
inspection protocol.
                              -210-

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                          TABLE 8-1

                        KRAFT PULP MILL

           PERTINENT NOMENCLATURE AND TYPICAL  VALUES
Active alkali on ovendry wood,  Ib/lb                      0.167
Active alkali concentration, lb/ft3                       7.0
Effective alkali on ovendry wood, Ib/lb                   0.14
Normalizing value of effective  alkali,  Ib/lb               0.15
Capacity of digesters (a.d. tons), tons/batch              14.5
Specific heat of wood solids, Btu/(lb)(°F)                 0.33
Caustic conversion efficiency,  nondimen                   0.78
Evaporator steam economy, nondimen                        4.66
Solids fraction in liquor to furnace, nondimen             0.545
Solids fraction in liquor to evaporator,
,. nondimen  		0._!88
Blow flow rate, Ib/ton a.d. pulp                        1516.'"
Water in liquor from evaporator, Ib/ton a.d.
 pulp                        :                           2519.
Evaporation rate from evaporator, Ib/ton a.d.
 pulp           .                                      10,549.
Water in .liquor to evaporator,  Ib/ton  a.d.
 pulp.                        '                         13,069.
Heat capacity of digester contents, (Btu/°F)/
 ton a.d. pulp                                        11,845
Heat of combustion of lignin, Btu/lb                    8100.
Heat of fusion of smelt, Btu/lb      .                   530.
Heat produced in recovery process, Btu/ton  a.d.
 pulp                                                     7.96 x  106
Total sulfur loss fraction, nondimen                      0.337
Total sodium loss fraction, nondimen                      0.0931
Number of digesters, nondimen                             5.
Production rate, tons a.d. pul-p/day                      500.
Furnace reduction ratio, nondimen                         0.976
Liquor-to-wood ratio, Ib/lb                               2.8
Sulfidity of cooking liquor  '                             0.323
"Effective" sulfide in cooking  liquor,  Ib/lb wood           ,0539
Solids in smelt, Ib/ton a.d. pulp                       1208.
Black liquor solids in liquor to evap., Ib/tons
 a.d. pulp                   .                           3018.
Usage of kiln fuel, MBtu/ton NaOH                         8.84
Usage of makeup lime, Ib/lb NaOH                          0.0276
Volume of black liquor to digesters, ft3/ton
 a.d. pulp                                                13.6   .
Volume of total cooking liquor, ft3/ton a.d.
 pulp                              .    .   .               104.
Volume of white liquor, ft3/ton a.d. pulp                 90.4
Weight of wood fiber, Ib/ton a.d. pulp                   1800.
Weight of wood lignin, Ib/ton a.d. pulp            .     1989
                             -211-

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                        KRAFT PULP  MILL
                          (Continued)
Moisture content of wood (fraction),  Ib/lb
Weight of wood solids,  Ib/ton  a.d.  pulp
Total weight of wet wood,  Ib/ton  a.d.  pulp
Weight of wood water,  Ib/ton a.d.  pulp
Weight of caustic (as  Na20)  in cook,  liquor
 Ib/ton a.d. pulp
Weight of sulfide (as  Na20)  in cook liquor,
 Ib/ton a.d. pulp
Weight of sulfate (as  Na20)  in cook liquor,
 Ib/ton a.d. pulp
Weight of carbonate (as Na20)  in  cook  liquor
 Ib/ton a.d. pulp             '
Weight of makeup salt  cake (as Na20),  Ib/ton
 a.d. pulp                    :
Weight of makeup carbonate (as Na20),  Ib/ton
 a.d. pulp
Pulping yield, nondimen
   0.52
3789.
7895.
4105.

 428.4

 204.4

   5.0

 120.8

  70.58

   0.06
   0.475
                             -212-

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                     Table 8-2

 Pertinent Operating Parameters  Which  May Affect
Atmospheric Emissions from Kraft Pulping Operation

 (To Be Used By FEO In Developing Site Inspection
         Route And Data Collection Format)
        Digester Room Log (Pulp Production)
  Chip weight charged, tons
  White liquor charged, gallons
  Actual cooking time, minutes
  Number of cooks blown per  24 hour period,
                    Hard Stock
                    Soft Stock
  White liquor sulfidity, %
                Recovery Boiler Log


  Steam flow, 1000 Ibs per hour
  Gas temperature boiler outlet, °F
  I.D. fan setting
  I.D. fan speed
  Total air flow, CFM or pounds per  hour
  Primary air flow, CFM or pounds per hour
  Secondary air flow, CFM or pounds  per hour
  Tertiary air flow, CFM or pounds per hour
  I.D. fan inlet draft, inches  water gage
  Precipitator inlet draft, inches water gage
  Dissolver tank vent draft, inches  water gage
  Demister Pads
  Black liquor flow to burners, Ibs  per hour
  Black liquor pressure, Ibs per square inch
  Black liquor solids, percent
  Fuel oil flow, gallons per minute
  Saltcake feed, pounds per hour
  Combustibles, percent
  Excess air, percent
              Precipitator Operation
  Inlet, volts, amperes, milliamps and spark
  Outlet, volts, amperes, milliamps and spark


                        -213-

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             Table 8-2  (Continued)
            Lime Kiln Operating  Log
Feed mud solids, percent
Feed flow, GPM
Mass flow, tons per day
Oil pressure, psi
Cold end temperature, °F
Hot end temperature, °F
I.D. fan inlet vacuum, inches  water  gage
Scrubber inlet pressure, inches water  gage
Scrubber outlet pressure, inches water gage
Fresh lime rate, tons per'day
            Barker Boiler Operation
Steam from oil, Ibs per hour
Steam from bark, Ibs per hour
Oil flow, gallons per minute
Screw feeder speed, RPM
Bin level, feet
C02> percent
Over fire air pressure, inches  water gage
I.D. fan draft at inlet, inches water gage
Gas temperature leaving boiler, °F
            Power Boiler Operation
Fuel oil supply pressure, psi
Under-grate air flow, ration (or oven-fire)
Oil burner windbox pressure, inches  water gage
I.D. fan inlet draft, inches water gage
C02» percent
Gas temperature leaving boiler, °F
                     -214-

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                             TABLE 8-3
               ODOR THRESHOLDS OF KRAFT MILL GASEOUS
                        SULFUR COMPOUNDS IN AIR
                           . ppm. (by volume)
Sulfur Dioxide    1.0-5.0
Hydrogen Sulfide  0.009-0.0085
Methyl Mercaptan  0.0021-0.040
Dimethyl Sulfide,  0.0001-0..0036
                             TABLE 8-4
               CHARACTERISTICS OF KRAFT MILL GASEOUS
                          SULFUR COMPOUNDS  '
   Compound
Characteristic
     Odor
        Explosive Limits (air)
Color     Lower       Upper
Sulfur Dioxide
Hydrogen Sulfide
Methyl Mercaptan
Dimethyl Sulfide
strong, suffocating  none
rotten eggs          none
rotten cabbage       none
vegetable sulfide    none
             Not explosive
          4.3%         46%
          3.9%         22%
          2.2%          9%
                                -215-

-------
to
(O
Q.
Q.
C
O
    800
    600
    400
     200
s-
o
 CVJ

S      o
                                 Figure  8-1


                      EFFECT OF  CHLORINE IN BLACK LIQUOR
                                                                           o
                                                                           c/o
   E

7  
-------
                                   Figure  8-2



                       EFFECT OF BLACK LIQUOR  HEATING VALUE
       2000
       1600  —
to

to

_a


b
•a
a.
a.
c
o
to

to
       1200  —
        800
 CVJ
o
oo
        400  —
           0

           5200
                         5600          6000           6400



                    Heating Value of Solids to Furnace, Btu/lb
6800
                                      -217-

-------
o
GO
fO

en
OJ
o
o
CL)
12


10


 8


 6


 4


 2


 0
                                        Figure  8-3

                     EFFECT OF TOTAL AIR  SUPPLIED TO THE UNIT
              CO
              fO
              -d
                1500
                .1000
              CL
              Q.
              I  500
              CM
              O
100


 80


 60


 40


 20


  0
 OJ
ro
           Tl



           ?
           CD
           DJ
                                                                                      4  o
                                                                                       ro
           cr

           CO
           _i.
           CO
              oo
              in
                  50
                  45
                  40
                   35
                   30
                    100       110       120       130        140


                     Total Air to Unit,  percent of theoretical
                                                                   2000
                                                                         1900
                                                                         1800
                                                                               03
                                                                               n>
                                                                               Q.
                                                                               -3
                                                                               TJ
                                                                               ft)

                                                                               01
                                                                               fD
                                                                150
                                                                   1700
                                         -218-

-------
                                       Figure 8-4


                                EFFECT OF  PRIMARY AIR
o
1/1
Q
to
c
fO
o>
o
(O
 o
 QJ
14



12



10



 8



 6
              1500
            to
            ItJ
            •o 1000
Q.

Q.
            I  500
            (/)
            to
             OsJ

            O
100



 80  ^



 60  ^

      =3'


 40  ".c1

      fD


 20   ^



  0
                45
                40
oo


£•  35


oo
                30
                   35
                   40           45          50           55


                         Primary Air, percent of total
                                                                        2000
                                                                                         03

                                                                                         CD
                                                                                          ft>.
                                                                                          CU
                                                                                    1800
                                                                              60
                                                                        1600
                                          -219-

-------
                                     Figure  8-5
                        EFFECT OF PRIMARY AIR .TEMPERATURE
      600
 l/l
 fO
Q.
Q.
c:
o
1/5

l/l
 CM

O
00
      500
400
300
      200
      100
                                                                                I
                                                                          fa
                                                                          O
                                                                          n>
                                                                               10

                                                                               3
                                                                         O
                                                                         oo
                                                                         O
          100
                   200
300
400
500
                           Primary Air Temperature, °F
                                     -220-

-------
03
    8000
    6000
£  4000

                                                                                      o
                                                                                      C '
                                                                                      -J

                                                                                      CD
                                                                                      o
                                                                                      o>
                                                                                      CO
                                                                                      -s
                                                                                      a>
                                                                                      0
                                                                                      oo
                                                                                      o
OO
OJ
     TOO
      80
      60
      40
      20
                                        I
                   0.2
0.4
0.6
0.3
i.o-
1.2
                           Molar Ratio S/Na2  in  Black  Liquor


                                          -221-
1.4

-------
                          Figure 8-7


         Effect  of. Black Liquor Solids Concentration
1/5
fO
    600
    500
    400
Q.
Q.
°   300
1/5
 
-------
8.5  REFERENCES

     1.  Hendrickson, E.R., J.E. Roberson, and J.B. Koogler.   Control of
         Atmospheric Emissions in the Wood Pulping Industry,  Vol.  1-3,
         Final Report.  Contract No.  CPA  22-69-18.   March 15, 1970.

     2.  A Report to the Washington Air Pollution Control Board Prepared
         in Conjunction with Rules and Regulations for Kraft Pulp Mills
         in Washington Office of Air Quality Control.   Washington State
         Department of Health, Seattle, Washington.  May, 1969.  [Figure
         7.2.1 based on Figure 1 of reference 4, p. 42.]

     3.  Hough, G.W. and L. V. Gross.  Air Emission Control in a Modern
         Pulp and Paper Mill.  Portland, Oregon, Fall  Pacific Coast
         Division Meeting.  Paper Industry Management Association.
         December 5-7, 1968.

     4.  Douglass, I.B. The Chemistry of Pollutant Formation in Kraft
         Pulping.  In:  Proceedings of the International Conference on
         Atmospheric Emissions foom Sulfate Pulping,  E.R. Hendrickson
         (ed.).  PHS, National Council for Stream Improvement.  University
      .   of Florida, April 28, 1966.

     5.  Kenline, P.A., and J.M. Hales.  Air Pollution and the Kraft
         Pulping Industry, and Annotated Bibliography.  Environmental
         Health Series.  DHEW, PHS, November 1963.

     6.  Knudson, J.C. Air Pollution Controls to Meet Washington State
         Kraft Mill Standards.  Department of Ecology, Redmond, State
         of Washington.  Spokane, Washington, International Section,
         Air Pollution Control Association, November 16-18, 1970.

     7.  Major, W.D.  Variations in Pulping Practices which may Affect
         Emissions.  In:  Proceedings of the International Conference
         on Atmospheric Emissions from Sulfate Pulping, E.R.  Hendrickson
         (ed.).  PHS, National Council for Stream Inprovement.  Univer-
         sity of Florida.  April 28, 1966.

     8.  Pulp and Paper Titrator, Model 400,installation and Operation
         Manual.  Barton ITT, Process Instruments and Controls.  Monterey
         Park, California.

     9.  Barton Titrators, Training Manual, Model 400, Installation and
         Operation Manual.  Barton ITT, Process Instrument and Controls.
         Monterey Park, California.

    10.  Knudson, J.C.  Air Pollution Controls to Meet Washington State
         Kraft Mill Standards.  Department of Ecology, Redmond, State of
         Washington, International Section, Air Pollution Control  Associa-
         tion, November 16-18, 1970.

                                   -223-

-------
11.   Ayer, C.   A Report on the Kraft Pulping Industry's Progress  in
     Complying with the Emission Regulations of April,  1969.   Oregon
     Department of Environmental Quality (unpublished).

12.   Hhillte,  D.'J., "Sulfite and Bisulfite Pulp Mill  Recovery Systems,"
     TAPPI, 54., pp. 1074-1088, 1971.

13.   Galeano,  S.F., and Dillard, B.M., "Process Modifications  for Air
     Pollution Control  in Neutral Sulfite Semi-Chemical  Mills,"
     Journ. APCA, 22. 195, 1972.
                               -224-

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                         APPENDIX

       This appendix contains a series of graphical  relationships,
tables, and standard calculations which should be useful  in assisting
the FED to estimate emission quantities.  Insofar as process opera-
tions are concerned, the bulk of th.ese data  pertain  to  kraft pulping
operations.  Further in this regard, these data may only be used for
estimating emission levels relative to the basis indicated.
                               -225-

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                         APPENDIX

                          LIST OF TABLES
TABLE 1.  FLUE GAS PARTICULATE CONCENTRATION AND EMISSION RATE
          RELATIONSHIPS FOR KRAFT RECOVERY FURNACES

TABLE 2.  GAS CONCENTRATION AND SULFUR EMISSION RATE RELATION-
          SHIPS FOR KRAFT RECOVERY FURNACES

TABLE 3.  FLUE GAS PARTICULATE CONCENTRATION AND EMISSION. RATE
          RELATIONSHIPS FOR LIME KILNS

TABLE 4.  FLUE GAS SULFUR CONCENTRATION AND SULFUR EMISSION RATE
          RELATIONSHIPS FOR LIME KILNS

TABLE 5.  VENT GAS PARTICULATE CONCENTRATION AND EMISSION RATE
          RELATIONSHIPS FOR SMELT DISSOLVING TANKS

TABLE 6.  VENT GAS SULFUR CONCENTRATION AND EMISSION RATE RELA-
          TIONSHIPS FOR SMELT DISSOLVING TANKS

TABLE 7.  SULFUR DIOXIDE CONCENTRATIONS IN POWER BOILER FLUE GAS
          AS A. FUNCTION OF SULFUR CONTENT OF FUEL

TABLE 8.  CONVERSION OF DUST LOADING IN BOILER FLUE GAS
                          LIST OF FIGURES
FIGURE 1.  PROCESS WEIGHT AND EQUIVALENT PULP PRODUCTION RELATION-
           SHIPS FOR KRAFT RECOVERY FURNACES

FIGURE 2.  PROCESS WEIGHT AND EQUIVALENT PULP PRODUCTION RELATION-
           SHIPS FOR LIME KILNS

FIGURE 3.  PROCESS WEIGHT AND EQUIVALENT PULP PRODUCTION RELATION-
           SHIPS FOR SMELT TANKS

FIGURE 4.  PARTICULATE EMISSION RATE PER UNIT OF PULP PRODUCTION
           AS A FUNCTION OF CONCENTRATION  IN KRAFT RECOVERY FURNACE
           FLUE GAS
                               -226-

-------
                           LIST OF FIGURES
                             (continued)

 FIGURE 5.   EMISSION RATE IN UNIT TIME AS A FUNCTION OF CONCENTRA-
            TION IN KRAFT RECOVERY FURNACE FLUE GAS

 FIGURE 6.   PARTICULATE EMISSION RATES AS A FUNCTION OF EQUIVALENT
            PULP PRODUCTION AND CONCENTRATION FOR KRAFT RECOVERY
            FURNACES

 .FIGURE 7.   GAS CONCENTRATION AND SULFUR EMISSION RATE RELATIONSHIPS
            FOR KRAFT RECOVERY FURNACES

 FIGURE 8.   PARTICULATE EMISSION RATE PER UNIT OF PULP PRODUCTION AS
            A FUNCTION OF CONCENTRATION IN LIME KILN FLUE GAS

 FIGURE 9.   PARTICULATE EMISSION RATE IN UNIT TIME AS A FUNCTION OF
            CONCENTRATION IN LIME KILN FLUE GAS

FIGURE 10.   PARTICULATE EMISSION RATE AS A FUNCTION OF EQUIVALENT
            PULP PRODUCTION AND CONCENTRATION FOR LIME KILNS

FIGURE 11.   FLUE GAS CONCENTRATION AND SULFUR EMISSION RATE RELATION-
            SHIPS FOR LIME KILNS

FIGURE 12.   PARTICULATE EMISSION RATE PER UNIT OF PULP PRODUCTION AS
            A FUNCTION OF CONCENTRATION IN SMELT DISSOLVING TANK
           .VENT GAS

FIGURE 13.   PARTICULATE EMISSION RATE IN UNIT TIME AS A FUNCTION OF
            CONCENTRATION IN SMELT DISSOLVING TANK VENT GAS

FIGURE 14.   PARTICULATE EMISSION RATE AS A FUNCTION OF EQUIVALENT
            PULP PRODUCTION AND CONCENTRATION FOR SMELT DISSOLVING
            TANK VENTS

FIGURE 15.   VENT GAS SULFUR CONCENTRATION AND EMISSION RATE RELATION-
            SHIPS FOR SMELT DISSOLVING TANKS

FIGURE 16.   PARTICULATE COLLECTION EFFICIENCY AND EMISSION RATE
            RELATIONSHIPS FOR KRAFT RECOVERY .FURNACES

FIGURE "17.   PARTICULATE COLLECTION EFFICIENCY AND EMISSION -RATE
            RELATIONSHIPS FOR LIME KILNS

FIGURE 18.   PARTICULATE COLLECTION EFFICIENCY AND EMISSION RATE
            RELATIONSHIPS FOR SMELT DISSOLVING TANKS

FIGURE 19.   SPECIFIC GRAVITY OF SPENT LIQUORS

FIGURE 20.   CHEMICAL BALANCE IN KRAFT RECOVERY CYCLE
                                -227-

-------
TABLE 1.  FLUE GAS  PARTICULATE CONCENTRATION AND EMISSION RATE
               RELATIONSHIPS FOR KRAFT RECOVERY FURNACES
Grain s/SDCF
0.01
0.02
0.03
.0.04
0.05
0.06
0.07
0.08
0.09
. 0.10
0.20
0.40
0.50
0.60
0.80
1.00
2.00
4.00
6.00
8.00
10.00
Ibs/Ton Pulp
0.473
0.946
1.42
1.89
2.37
2.84
3.31
3.78
4.26
4.73
9.46
18.9
23.7
28.4
37.8
47.3
94.6
189
284
378
473
Ibs/Hour (ONE TON/DAY MILL)
0.0197
0.0394
0.0591
0.0788
0.0985
0.118
0.138
0.158
0.177
0.197
0.394
0.788
0.985
1.182
1.58
1.97
3.94
7.88
11.8
15.8
19.7
 Note:  Interpolate  for values not shown, or  refer  to
        Figures  1, 2  and 3.


                            -228-

-------
TABLE 2.  GAS CONCENTRATION AND  SULFUR EMISSION RATE RELATION-
                   SHIPS FOR  KRAFT RECOVERY FURNACES
     PPfrTby Volume

          1

          5

         10

         20

         40

         60

         80

        100

        200

        400

        600

        800

       1000
Pounds/Ton Pulp as Sulfur

         0.0.274

         0.137

         0.274

         0.548

         1.10

         1.64

         2.19

         2.74

         5.48

        11.0

        16.4  .

        21.9

        27.4
       One pound of Sulfur/Ton pulp =  36.4  PPM
                             -229-

-------
TABLE  3.   FLUE GAS PARTICULATE CONCENTRATION  AND EMISSION RATE
                       REL/iTIONSHIPS FOR .LIME KILNS
Grains/SDCF
0.01
0.02
0.03
0.04
. 0.05
0.06
0.07
0.08
0.09
0.10
0.20
0.40
0.60
0.80
1.00
2.00
4.00
6.00
8.00
10.00
IS. 00
20.00
Ibs/Ton
0.0822
0.164
0.247
0.328
0.411
0.493
0.575
0.658
0.740
0.822
1.64
3.29
4.93
6.58
8.22
16.44
32.9
49.3
65.8
82.2
123
164
Ibs/Hour (ONE TON/DAY MILL)
0.00343
0.00686 .
0.0103
0.0137
0.0172
0.0209
0.0240
0.0274
0.0309
0.0343
0.0686
0.137
0.206
0.274
0.343
0.686
1.37
2.06
2.74
3.43
5.15
6.86
                                      -230-

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TABLE 4.  FLUE GAS SULFUR CONCENTRATION AND' SULFUR  EMISSION RATE
                      RELATIONSHIPS FOR LIME KILNS
         PPM by Volume

              1

              5

             10

             20

             40

             50

             60

             80

            100

            200

            400

            500

            600

            800

           1000
Pounds/Ton Pulp as Sulfur

         0.00476

         0.0238

         0.0476

         0.0952

         0.190

         0.238

         0.286

         0.381

         0.476

         0.952

         1.90

         2.38

         2.86

         3.81

         4.76
           One pound of Sulfur/Ton = 210 PPM.
                                 -231-

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TABLE 5.   VENT GAS PARTICULATE  CONCENTRATION AND  EMISSION RATE
                 RELATIONSHIPS FOR SMELT DISSOLVING TANKS
Grains/SDCF
0.01
0.02
0.03
0.04
0 .' 05
0.06
0.07
0.08
0.09
0.10
0.20
0.40
0.60
0.80
1.00
1.50
2.00
Ibs/Ton Pulp
0.0576
0.115
0.173
0.230
0.288
0.346
0.403
0.461
0.518
0.576
1.15
2.30
3.46
4.61
5.76
8.64
11.5
Ibs/Hour (ONE TON/DAY MILL)
0.0024
. 0.0048
0.0072
0.0096
0.0120
0.0144.
0.0168
0.0192
0.0216
0.0240
0.0480
0.0960
0.144
0.192
0.240
0.360
0.480
                                   -232-

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    Gaseous Sulfur Emissions^

     Table 6 presents gaseous sulfur emission rates expressed as
pounds of sulfur corresponding to concentrations  in parts  per
million parts by volume dry gas.  This vent gas has a mean mois-
ture content of about 40% by volume.  These relationships  'shown
in Table #6 assume that the gaseous molecule contains only  one
atom of sulfur.  An average value of 28 SDCFM/TPD was used in
calculating emission rates.  Figure 15 presents these data in
graphical form.-                    •
TABLE 6.  VENT GAS SULFUR CONCENTRATION AND EMISSION  RATE  RE-
                LATIONSHIPS FOR SMELT DISSOLVING TANKS
PPM by Volume
1
5
10
15
20
25
50 ;
7.5
100
200
500
700
1000
Pounds/Ton as Sulfur
0.0033
0.0167
0.0333
0.0500
0.0667
0.0834
0.167
0.250
0.333
0.667
1.67
2.33
3.33
       One pound of sulfur/ton =300 PPM
                                 -233-

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TABLE 7.  SULFUR DIOXIDE CONCENTRATIONS IN POWER BOILER FLUE
             GAS  AS  A FUNCTION OF SULFUR CONTENT OF FUEL
Fuel Sul
fur Content
Percent
0.
0.
0.
1.
1.
2.
2.
3.
3.
4.
5.
10
25
50
00
50
00
50
00
50
00
00
PPM SO?
20%
Excess
Air
77
190
380
770
1150
1530
1910
2300
2680
3060
,3830
(v/v)
50%
Excess
Air
62
150
300
610
920
1210
1510
1810
2110
2420
3020
- Coal
~12~%
CO?
Content
63
160
310
620
940
1240
1550
1780
2180
2490
3100
PPM SO?
20%
Excess
Air
55
140
280
550
830
1100
1380
1660
1930
2210
2760
(v/v) - Oil
12%
CO 2
Content
51
130
260
510
770
1030
1280
1540
1800
2060
2580
       Note:  Interpolate  for values not shown.
                              -234-

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                            TABLE 7
                          (continued)
1.  Coal

    Heat value - 13,000 BTU/pound


    Carbon Content - 72.8%

    Theoretical combustion air =

        7.6 pounds/10,000 BTU


    Theoretical air = 9.9 pounds/pound of coal

    205 Excess Air = 11.85 pounds air/


                              pound of coal

    At 70°F, 1 Atm., 11.85 pounds of air =

        158 ft3 dry air

    1 pound of coal of 1% sulfur content produces

        0.121 ft3 of SO2  assuming 100%


        combustion and no sulfur discharged with ash

    PPM S02 (1% sulfur) = 0.121/158 x 106 =    .   •

        765 PPM


    Pounds of SC-2 produced =

        (2)  (% Sulfur) (Pounds of Coal)
                   .  100

2.  Oil (No. 6 or "Bunker C")


    Heat value - 18,500 BTU/pound

    Carbon.Content = 88.4%

    Theoretical combustion air =

        7.46 pounds/10,000 BTU


    Theoretical air = 13.80 pounds/pound of oil

    20% excess air - 16.5 pounds/pound of oil

    At 70°F, 1 Atm., 16.55 pounds of air ~



                            -235-

-------
                             TABLE 7
                           (continued)
        220  ft3  dry  air.

1 pound of oil at  1%  sulfur produces

        0.121 ft3  of  S02  assuming 100%

        combustion.

PPM S02 (1%  Sulfur) = 0.121/220 x 106 =

        552  PPM

Pounds of SC>2 produced =

        (2)  (% Sulfur)  (Pounds of Oil).

                      100.0
                              -236-

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                             TABLE 8
          CONVERSION OF DUST  LOADING  IN BOILER FLUE GAS
            FROM GR./SCF TO IB./MM BTU OF HEAT INPUT
                         AND  VICE VERSA
Federal  guidelines  for participate emission rates are expressed in
Ib./MM BTU of heat  input while many  state regulations are expressed
in gr./SCF.  The following  formulas  and curves can be used to relate
these two values.

1.  COAL FIRED BOILER:

    Step 1 :  If percent 02  in flue gas is not known, determine per-
    cent 02 from Figure 1 by assuming percent excess air or percent
    C02-  Generally one of  these  three quantities are known.

    Step 2:  Determine multiplication factor A-| from Figure 2.

    Step 3:  Determine multiplication factor B-| from Figure 3.

    Step 4:  Calculate #/MM BTU from formula below:

             Lb/MM  BTU = (Gr/SCF)  (A1 ) (B^ or
2.  OIL FIRED BOILER:

    Step 1 :   If percent Op  in  flue  gas  is not known, determine per-
    cent Op  from Figure 1 by assuming percent excess air or percent
    C02.  Generally one of  these  three  quantities are known.

    Step 2:   Determine multiplication factor A2 from Figure 4.

    Step 3:   Calculate #/MM BTU from formula below:

             Lb/MM BTU = (Gr/SCF) x (A2) or

             Gr/SCF =  Lb/MM BTU x
3.  WOOD BARK OR BAGASSE FIRED BOILER:

    Step 1 :   If percent Op  in  flue  gas  is not known, determine percent
    Op from Figure 1  by assuming  percent excess air or percent C02-
    Generally one of these  three  quantities are known.
                               -237-
     environmental science and engineering, inc.

-------
    Step 2:   Determine multiplication  factor A3 from Figure 5.

    Step 3:   Determine multiplication  factor 63 from Figure 6.

    Step 4:   Calculate #/MM BTU  from formula below:

             Lb/MM BTU = (Gr/SCF)  (A3)  (63) or

             Gr/SCF = Lb/MM BTU     J-    ]
Results from the above calculations  should be accurate within five
percent of the true answer.   Naturally,  some generalization had to
be made in simplifying the above  calculation procedures which explain
this accuracy range.   Average values were utilized for the approxi-
mate analysis of the fuel  in  deriving  the multiplication factor (A).
Likewise a heat value was  assumed for  the generated steam of 1050
BTU/Lb.  The multiplication  factor (A) originates from thermodynamic
combustion calculations and  are compiled on a strictly theoretical
level.   Boiler efficiency  does not enter into the above calculations
and therefore only minimum assumptions must be made.  Generally,
either the percent oxygen  in  the  flue  gas, the percent carbon dioxide
in the flue gas or the excess air is known, so it was decided that
this would be a good starting point  for  the above computations.  For
oil and coal fired boilers the excess  air would generally be in the
neighborhood of thirty percent while for wood waste fired boilers
this value might be as high  as fifty percent.  Notice that the family
of curves for the coal fired  boiler  in Figure 1 varies with percent
volatile matter.
                               -238-


     environmental science and engineering, inc.

-------
                  Table 8
                 Figure 1
          'ositjion For	
          "acTt'e~anarrfgrffCe
               srcent Vol
                 sture
atile Matter
      Fret
                     Dash Lines wi
                    -fletejrmi nation
                     and Air Weigh
                                    Q_Pe.rcent_
                                                         -a
                                                         cu
                                                         (/I
                                                         fO
                                                         CO

                                                         c
                                                         o
                                                         i.
                                                         O)
                                                         D-
                                                         •a
                                                         c
                                                         o
                                                         a.
                                                         «=c

                                                         o

                                                         il
                                                         O)

                                                         Q.
                                                         to
                                                         o
0  10   20    30   40   50  60    70   80   90  100

                Excess Air-Percent
                   -239-

-------
                          Table 8
O
CQ

Q
LU
cc
'O
C_3
O
I—
o
2     - 4 .      6
                                        8     10
12
                        % Oxygen in Flue Gas


            MULTIPLICATION  FACTOR "A" FOR COAL FIRED BOILER


                              Figure 2
                            -240-

-------
                  Table 8
1.00
                   20     30
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-------
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-------
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-------
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10
                   20        30        40

                   CONCENTRATION,  % SOLIDS

Figure 19.   Specific gravity of spent liquors.
                              -262-

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4.0
3.72 TONS CHIPS 1 TON A. D. PULP
1 @ 48.5% MOISTURE . j 18 Ib Na20 LOSS
DIGESTER
'•
656
557
25% .
PO
CO
FROM SCRUBBER
32.5 Ib CaO
fi.5 Ih NaoO .
47% YIELD
•> WASHING
Ib Na?0
Ibs A A
BULFIDITY
WHITE 802 ..5 Ib
linnnR ^NaoO
CLARIFIER ^00.5 Ib CaO
1
14.5%SOLIDS
Ib Na20
SLAKE R
2.25 Ib INSERTS L
; 2.25]b CaO LOSS
0.5 Ib Na20 LOSS574>5 ]h , T ^
Ih Na 01 (TV DUST

MULTIPLE
EFFECT
EVAPORATORS
, ^165 11
10 Ib
803 Ib Na20
22.5 IbPUR
"""LIME @ 905
ABILITY -!
. COLLECTOR
48.8%SOLIDS
628 Ib Na20
D SOAP
Na20 LOSS
GREEN
LIQUID
CLARIFIER
CHASED
', AVAIL- *~
?0.25 Ib CaO
- 500.5 Ib CaO I @ 84% AVAILABILITY 13.5 1b Na 0
". . T146.51b Na?0 J482.5 Ib CaO ] T8 1b Ca§ L0ss
MUD
WASHER
533 Ib CaO LIME !
10 Ib Na20* KILN
1
- TO WEAK WASH
. 143 Ib Na20
iO.5 Ib CaO
10 Ib Na20
SCRUBBER

* TO MUD WASH '
32.5 Ib CaO
6.5 Ib Na20
96 Ib SALT CAKE MAKEUP
42.0 Ib Na20
,.•• ' u
DIRECT
CONTACT
EVAPORATOR!
CROM WEAK WAJ
163 Tb Na2C
826 Ib Na20.
23 Ib Na20
MAKEUF
i '
DREGS
WASHER
"tt l
f RECOVERY
i BOILER
65% SOLIDS
2794 Ib SOLIDS
PLUS DUST v
PICKUP
.u 666 Ib NaoO
>H | <-
)--y v
nTcc;ni \/TWP. 	 .<«.T n ih NT n i n^r
UlooULVliNU 	 ' '"•O . U ID INUoU LUo^
TANK
TO WEAK WASH
' 20 Ib Na20
T DREGS TO SEWER
3 Tb Na20 LOSS
Figure 20.  Chemical  balance in recovery cycle.

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                                   TECHNICAL REPORT DATA
                            (Please read Instructions on the reverse before completing)
1. REPORT NO.
  EPA 450/3-75-027
                                                            3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
  Field  Surveillance and Enforcement Guide:
  Wood Pulping Industry
             5. REPORT DATE
             Issue:   March 1975
             6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
  S.  Oglesby, E. R. Hendrickson
                                                           8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Environmental Science and  Engineering, Inc.
  Post  Office Box 13454 - University Station
  Gainesville, Florida 32604
                                                            10. PROGRAM ELEMENT NO.
             11. CONTRACT/GRANT NO.

                68-02-0618
12. SPONSORING AGENCY NAME AND ADDRESS
  Environmental Protection Agency
  Research Triangle Park, North Carolina 27711
             13. TYPE OF REPORT AND PERIOD COVERED
                .Final
             14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT           •                 .  • .
  This manual  provides guidelines  and background information for use by personnel
  of state and local air pollution control agencies in  their surveillance and
  enforcement  activities related to the major types of  chemical pulp mills.  The
  three major  types of mills discussed are Kraft, Sulfite,  and Neutral Sulfite
  Semi-Chemical (NSSC).   For each  type of mill, the process is described; the emissions,
  both gaseous and particulate, are characterized; and  the  types of applicable
  control equipment are delineated.   Field enforcement, inspection, reporting and
  enforcement  procedures to be followed in each type of mill by control agency
  personnel  are suggested.
17.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS  c.  COSATI Field/Group
  Emission  Sources, Control Methods,
  Kraft Pulping,  Odors, Black Liquor  Oxi-
  dation, Mercaptans, Sulfur Dioxide  arid
  Paper.Manufacture
 Pulp Manufacturing
13. DISTRIBUTION STATEMENT

       Release Unlimited
19. SECURITY CLASS (This Report!
  Unclassified
                                                                          21. NO. OF PAGES
                                              20. SECURITY CLASS (Thispage)
                                                 Unclassified
                                                                         22. PRICE
EPA Form 2220-1 (9-73)

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                                                t                                        .
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EPA Form 2220-1 (9-73) (Reverse)

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