WATER POLLUTION CONTROL RESEARCH SERIES • 12090DWM 01/71
    Bio-Regenerated
 Activated Carbon Treatment
      of Textile Dye Wastewater
ENVIRONMENTAL PROTECTION AGENCY • WATER QUALITY OFFICE

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              Water Pollution Control Research  Series

      Hie Water  Pollution Control Research  Reports  describe
the  results  and progress in the control  and  abatement  of
pollution  in our Nation's waters..  They  provide  a  central
source of  information  on the research, development, and
demonstration activities in the Water Quality  Office,  in the
Environmental Protection Agency,  through in-house  research
and  grants and  contracts with Federal, State,  and  local agencies,
research institutions, and  industrial organizations.

     Inquiries  pertaining to Water  Pollution Control Research
Reports should  be directed  to the Head,  Project  Reports System,
Water Quality Office, Environmental Protection Agency,
Washington, D.  C. 20242.

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BIO-REGENERATED  ACTIVATED CARBON





             TREATMENT  OF




      TEXTILE  DYE  WASTEWATER
                   by




             FRAM CORPORATION




       East Providence, Rhode Island 02916









               on behalf of





           C.  H. MASLAND & SONS




         Carlisle, Pennsylvania 17013










                 for the




  ENVIRONMENTAL  PROTECTION AGENCY




           Water Quality Office
        GRANT PROJECT NO. 12090 DWM




             January 1971

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                      EPA Review Notice
     This report has been reviewed by the Water Quality
Office of the Environmental Protection Agency and
approved for publication.  Approval does not signify
that the contents necessarily reflect the views and
policies of the Environmental Protection Agency, nor
does mention of trade names or commercial products
constitute endorsement or recommendation for use.
                              ii

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                           ABSTRACT
      A novel approach to treating a highly colored textile dyeing
waste effluent is described.  It comprises the removal by sorp-
tion of color bodies and other organic matter on activated carbon
granules.  Spent carbon granules are then subjected to a virule
aerobic biological culture which desorbs and bio-oxidizes  the
desorbed matter, thereby regenerating the carbon for subsequent
new sorption steps.

      Laboratory confirmation  of the phenomenon is presented.
Field testing of the treatment process  concept in a  50, 000 gpd
plant installed at a yarn spinning mill (C. H. Masland & Sons,
Wakefield, Rhode Island) is reviewed.

      Color removal was virtually complete at two  flow rates
evaluated: 8.5  gpm/ft and 15.6 gpm/ft carbon column bed
flow.  COD removal was  85% or higher at 8. 5 gpm/ft  and only
48% at  15.6 gpm/ft2.

      It was  demonstrated that activated carbon had an adsorption
capacity in excess of  1.6 poundsCODper pound of carbon when the
carbon was reactivated only by  biological means.  The estimated
operating cost for decolorizing  1, 000, 000 gpd is  8.3  cents/1000
gallons not including amortization.

      This report was submitted in fulfillment of Grant No.
12090 DWM between the Water  Quality Office of the Environ-
mental Protection Agency and C. H.  Masland & Sons.
KEY WORDS: Wastewater treatment, industrial wastes, textiles,
               color,  adsorption,  activated carbon, costs,  total
               organic carbon
                                111

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                         CONTENTS

                                                         Page No.

ABSTRACT                                                  iii

SECTION I - CONCLUSIONS                                   1

SECTION II - RECOMMENDATIONS                            3

SECTION III - INTRODUCTION                                5

SECTION IV - BIOLOGICAL REGENERATION                   7

SECTION V - FIELD APPLICATION DEVELOPMENT           11
                  SITE FOR PILOT PLANT                   11
                  PRELIMINARY PROFILE ANALYSIS         11
                  LABORATORY DESIGN CRITERIA           17

SECTION VI - FIELD STUDIES                               21
                  DESCRIPTION OF PILOT PLANT            21
                  PHASE I OPERATION                      2?
                  PILOT PLANT MODIFICATIONS             29
                  PHASE II OPERATION                      30
                  SYSTEM CONTROL                         33

SECTION VII - WASTE TREATMENT SYSTEM                 35
                  DESIGN AND ECONOMICS                  35
                  PROPOSED REDESIGN  OF MASLAND-       35
                  WAKEFIELD TREATMENT PLANT
                  PROPOSED 1  MGD TREATMENT PLANT     37
                  ECONOMICS                               39

SECTION VIII - ACKNOWLEDGMENTS                         41

SECTION IX - REFERENCES                                 43

SECTION X  - APPENDICES                                   45

          APPENDIX A - FIELD DATA, PHASE I
                               OPERATION                 47

          APPENDIX B - ACTIVATED CARBON ADSORPTION
                               ISOTHERMS                  49

          APPENDIX C - FIELD DATA, PHASE II
                               OPERATION                 53

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                                                         Page No.

APPENDIX D - CHEMICAL REGENERATION STUDIES        6l

APPENDIX E - COD, BOD, TOC,  TOD RELATIONSHIPS     69

APPENDIX F - 1 MGD TREATMENT PLANT DESIGN         73
                     PARAMETERS
                      vi

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                           FIGURES
                                                           PAGE

 1   SORPTION-REGENERATION PROCESS                      8

 2   EFFLUENT PROFILE  COD vs. TIME                     12

 3   EFFLUENT PROFILE  COLOR vs. TIME                   13

 4   EFFLUENT PROFILE BOD vs.  TIME                     14

 5   EFFLUENT PROFILE-SUSPENDED SOLIDS vs.  TIME        15

 6   REGENERATION STUDIES                                18

 7   PERFORMANCE OF LABORATORY SCALE
       ADSORPTION COLUMNS
                                                              20
 8   PLAN FOR LOCATION OF FRAM WASTE TREATMENT
        SYSTEM AT C. H. MASLAND & SONS, WAKEFIELD, R. I.   22

 9   WASTE TREATMENT SYSTEM - C. H. MASLAND & SONS -
        ACTIVATED CARBON COLUMNS                         23

10   WASTE TREATMENT SYSTEM - C. H. MASLAND & SONS -
        REGENERANT RESERVOIR                              24

11   SCHEMATIC FLOW DIAGRAM                              26

12   EFFLUENT SAMPLES - OCTOBER 30, 1970                 31

13   POUNDS OF COD REMOVED AS A FUNCTION OF GALLONS
        OF WASTEWATER TREATED                            32

14   SECOND GENERATION SYSTEM                            36

15   PROPOSED 1 MGD SYSTEM                                38

16   ADSORPTION ISOTHERM - MASLAND EFFLUENT            52

17   REMOVAL PROFILE - HO  REGENERATION (25° C. )       64
                            LI £*
18   REMOVAL PROFILE -  K S O  REGENERATION (25° C. )    65

19   SECONDK SO   REGENERATION (25° C. )                 66
               c. e.  8

20    THIRD K,S_O0 REGENERATION (50° C. )                   6?
              Lt L* O

21    REPEAT OF 50° C. K S  O REGENERATION               68
                           228

                              vii

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                                                             Page





22     CORRELATION OF COD TO BOD                         7°





23     CORRELATION OF COD TO TOC                         71





24     CORRELATION OF COD TO TOD                         72
                             vixi

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                            TABLES

No.                                                              Page


  I    Synthetic Waste Formula Used in Original Bio-regeneration  9
         Studies

 II    Masland Dyehouse Raw Waste Profile                       ^

III    Components of Waste Effluent for Each Contamination
         Cycle Plotted in Figure 6                                -^

IV    Pilot Plant Design Features                                 ^5

V    COD and Color Removal Data:  Phase I Operation            28

VI    Masland-Wakefield - Phase I Data  -  June 26, 1969 thru
                                          October 6, 1969         48

VII    Masland-Wakefield - Phase II Data - Week 1                54

VIII   Masland-Wakefield - Phase II Data - Week 2                54

IX    Masland-Wakefield - Phase II Data - Week 3                55

X    Masland-Wakefield - Phase II Data - Week 4                55

XI    Masland-Wakefield - Phase II Data - Week 5                56

XII    Masland-Wakefield - Phase II Data - Week 6                56

XIII   Masland-Wakefield - Phase II Data - Week 7                57

XIV   Masland-Wakefield - Phase II Data - Week 8                57

XV   Masland-Wakefield - Phase II Data  - Week 9               58

XVI   Masland-Wakefield - Phase II Data - Week  10                58

XVII  Masland-Wakefield - Phase II Data - Week  11                59

XVIII Masland-Wakefield - Phase II Data - Week  12                59

 XIX  Masland-Wakefield - Phase IlD'ata - Week 13                60

 XX   Masland-Wakefield,  Phase II Data - Week 14                60
                                 ix

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                         SECTION I

                       CONCLUSIONS
 1.   Exhausted activated carbon can be biologically regenerated, pro-
vided that the adsorbate is biodegradable.

2.   The textile dye wastes can be easily decolorized by a single pass
flow through fixed granular activated  carbon beds at an average flux  of
 12 gpm/ft ,  provided that the color bodies are receptive to adsorption
on the carbon.

3.   A continual adsorption-biological regeneration cycle of the activated
carbon beds  has been achieved  over a four month period resulting in a
continuous decolorization  and organic reduction of a textile dye waste.

4.   Economically, the process is well suited for handling complete
treatment of small volume textile wastes (up to 75, 000 gpd), and for
pretreatment (complete color removal and 50% organic removal) of
large volume textile  wastes prior to discharge to conventional biological
waste treatment systems.

5.   An effluent profile analysis of the Masland-Wakefield dyehouse waste
effluent was  made.  The average COD was 700 mg/1, BOD 350 mg/1,
suspended solids < 40 mg/1 and pH range 4. 0 - 6. 0.

6.   Two test periods were operated as "Phase I" and "Phase II".  Phase
I was conducted from 6/2/69 through  10/6/69.  Phase II was conducted
from 7/21/70 through 10/23/70.  Phase I operation illustrated the need
for mechanical alterations, a better performing activated carbon,  and
the addition of a pH buffering chemical and biological nutrient to perfect
the required biological regeneration step.  Phase II operation including
these alterations and modifications in operating procedures is the basis
for the success  of this  project in meeting the  objectives of this demon-
stration.

7.   A  1. 0 mgd plant  design was developed from the data generated from
the Phase II  operation. For a 50% COD removal, the estimated construc-
tion cost is $230, 000 with an estimated operating cost of  8.3^/1000 gallons.
For a 75% COD  removal,  the  estimated construction cost is $550, 000 with
an estimated operating cost of  23. 1^/1000 gallons.

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                             SECTION II

                        RECOMMENDATIONS
     The Mas land-Wakefield treatment facility was installed as an
experimental pilot plant subject to modifications deemed necessary
during its operational study period.  Although it could be continued
for use as a pretreatment facility providing 50% COD removal prior
to discharge into a proposed regional sewer  system, it is recom-
mended that the plant be further modified as follows:

     1) Installation of an equalization basin

     2) Installation of two  parallel activated carbon column units
       whereby one unit of three columns  is on stream while the
       other unit is on biological regeneration

     Such a modification would increase the level of treatment to an
effluent suitable for stream discharge.

     The complete (over 99%) decolorization  demonstrated by the
Masland-Wakefield pilot plant study warrants the location and selec-
tion of a manufacturing plant discharging a similar colored waste in
quantities approaching or  exceeding one  million gallons  per day.  The
design, construction and operational study of a treatment plant of this
concept under a Federal demonstration grant funding is  recommended.

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                           SECTION III

                        INTRODUCTION
     Biological treatment of wastewater can be markedly improved by
providing a myriad of solid  surfaces upon which biological growth is
accelerated.  The trickling  filter and the rotating biological surface
process are examples of employment of this extended area principle (1).
The increased effect produced by providing considerably greater effec-
tive solid surface area in a  biological reactor has been noted by I. S.
Kugelman (2).  Kugelman describes but does not explain an "unexpected"
biodegradation taking place  in a tertiary granular anthracite filter
used to polish a secondary treatment effluent.

     It is evident then that proper utilization of an adsorbent with a
biological waste treatment process might provide an important step
in designing more effective  and less expensive waste treatment systems.
Studies made along this  line by S.  S. Blecharczyk, E. L.  Shunney and
A.  E.  Perrotti at the Fram Research Laboratories  resulted in a fur-
ther breakthrough in technology -  namely,  the regeneration of an adsor-
bent's capacity by biological means.  The application of this technique
on the waste effluent of a carpet yarn textile mill  is the  subject of this
report.

     Conventional color removal methods for handling textile dyeing
waste discharges have been: (1)  lime coagulation and flocculation;
(2) alum coagulation  and flocculation; and (3) more recently,  activated
carbon columns with external thermal regeneration.   With the exception
of Method 3, only partial success  has been achieved.  Coagulation-
flocculation will adequately  handle insoluble  and/or  dispersed  dyestuffs
reasonably well.  Soluble dyestuffs such as those used in carpet yarn
dyeing are not  removed  by such techniques.  Activated carbon with
cyclic thermal regeneration is probably the most  efficient method for
removing color.  Its  complexity,  the relatively high installation cost,
operating requirements,  and relatively high  operating costs dampen
its  desirability.  The fact that regeneration of the activated carbon's
color removal  characteristics can be accomplished in place by biolo-
gical means makes the method more attractive than Method 3 where
the carbon is regenerated externally.

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    In order to prove out the efficiency of the technique of biological
regeneration of activated carbon as it would apply to color removal,
there was a need to develop the technique at an industrial site.  It
appeared that the most expeditious approach was to apply for a
Federal demonstration grant.  Such a grant was applied for and
awarded.

    The grant project objectives were:

    To conduct effluent profile analyses; to design, construct,
    operate, test and evaluate a pilot facility to treat the entire
    combined plant process  and primary treated sanitary waste-
    waters  (50, 000 gpd) utilizing the Fram Corporation's acti-
    vated carbon modified activated sludge process; to develop
    design criteria for a 1. 0 to 1.5 mgd plant .

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                          SECTION IV

                 BIOLOGICAL REGENERATION
     Organic matter contained in wastewater is adsorbed on an adsor-
 bent contained in a fixed bed  (Figure 1).  Wastewater is fed through
 the adsorbent in a downflow mode until the adsorption capacity is
 exhausted.  The exhausted adsorbent is regenerated by circulating in
 an upflow mode a liquid stream containing an aerobic biological cul-
 ture.  The resultant bio-oxidation of the eluted organic matter con-
 tinues to take place until the adsorbent is reactivated.  The reactivated
 bed is then ready to perform again its  adsorption-filtration function on
 a wastewater stream.

     The bio-culture which is acclimated to the wastewater to be
 treated in many cases receives enough nutrient from the contaminated
 carbon to maintain itself.   When nutrient content is deficient, suffi-
 cient nutrient can be added to the bio-culture to maintain the desired
 bio-chemical activity  required to achieve regeneration.

     Previous to this demonstration project,  two laboratory fixed bed
 adsorbent columns were in operation on a sorption-biological regenera-
 tion repeating cycle for over  fifteen months.   The same adsorbent re-
 moved a quantity of organic matter over 100  times its weight.  In this
 experiment,  the adsorbent was contained in packed columns six feet
 in length and two inches in diameter.   Each column was packed with
 1200 grams of Witco 718 (12 x 30 mesh) granular activated carbon.
 The  carbon was retained by a perforated sheet with 0. 045 inch dia-
 meter holes  in a staggered fashion and with a 26% open area.   Flow
 rate through the system was maintained at 12 gallons per minute per
 square foot of cross-sectional area in  a downflow  mode.

    The regeneration  cycle was accomplished by recirculating a viru-
 lent dispersed bacterial culture in an upflow  mode at 10 gpm/ft .
 The dissolved oxygen in the culture was maintained at a level greater
than 2 ppm by bubbling air into it.  The source of activated sludge was
a municipal secondary treatment plant.  The sludge solids in the regener
tion liquor did not exceed  1000 mg/1 and were generally less than 200 mg

    A synthetic wastewater was prepared in  accordance with the formula
 in Table I and its COD (chemical oxygen demand) was 295 mg/1.  An
average  reduction in COD  of 51% was maintained for the entire fifteen
month period.  The variation in COD reduction was 46 - 58%.

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    WASTE
    WATER
GRANULAR
ADSORBENT
BED
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RESERVOIR
                                       AIR
                          TREATED  EFFLUENT
          SORPTION-REGENERATION  PROCESS

                   FIGURE I
                     8

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                Table I

   Synthetic Waste Formula Used in Original
         Bio-regeneration Studies
Starch, Soluble                  39-4 mg/1

Glucose                          39.4 mg/1

Glycine                          21.0 mg/1

Nutrient Broth                   31.0 mg/1

Leucine                          31.0 mg/1

Glycerine                         5. 5 mg/1

Octanoic Acid                     5. 5 mg/1

Oleic Acid                        5. 5 mg/1

Sodium Acetate                   5. 5 mg/1

COD of Solution                 295 mg/1

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                          SECTION V

               FIELD APPLICATION DEVELOPMENT
SITE FOR PILOT PLANT

    The carpet yarn fiber dyeing facility of C.  H. Masland & Sons,
Wakefield, Rhode Island was well suited for field studies of this
sorption-biological regeneration treatment process.  The waste from
the dyehouse was predominantly a clear,  heavily colored solution
dumped directly into the river downstream of a mill dam.  Its quantity,
50, 000 gallons per  day over a  10 hour dyeing period, was low enough
to permit employment of a pilot plant handling the entire effluent.
Also, a 10 hour adsorption-filtration phase followed by a 14 hour bio-
logical regeneration phase could be maintained without providing an
otherwise duplicate system for continual 24 hour service.
PRELIMINARY PROFILE ANALYSIS

    Analyses pertinent to the pollutant waste content of the Masland-
Wakefield effluent stream were performed. Figure 2 is a plot of
COD (chemical oxygen demand) as a function of time in 15 minute
steps over a 4 hour period.  A relationship of COD to TOD (total
oxygen demand) was established where COD = 0. 98 TOD; further,
COD = 2.51 BOD- (five day biochemical oxygen demand) and also
COD = 2.54 TOC (total organic carbon).  See Appendix E for a de-
tailed  explanation of these relationships.

    For the purpose of clarity,  the chemical oxygen demand (COD)
parameter will be used in the remainder of the text.

    Figure 3 is a plot of color versus time. Tinctorial strength is
ten times the absorbance obtained on a colorimeter at a wavelength
of 450 millimicrons.

    Figure 4 is a plot of BOD versus time.  Figure 5 is a plot of sus-
pended solids versus time.  The mean values and range for each para-
meter evaluated are presented in Table II.

    The profile data as shown graphically in Figures 2, 3, 4 and 5
and summarized in Table II reveals that the wastewater is predominantly
solid-free (suspended solids :  6 - 70 mg/1, mean 27). The contaminants
contributing to high coloration (2.5 color units mean,which is comparable
in intensity to that of  a dark red wine) and a moderate BOD and  COD
concentration are predominantly soluble in nature and well suited for
adsorption column treatment.


                                   11

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  1600
£1400
8l200
gj 1000

Q
UJ
X
o
  BOO
< 600
UJ
I
o
  400
            II     12      I      23

               SAMPLE  TIME  (O'CLOCK)


          EFFLUENT PROFILE   COD vsTIME

                   FIGURE 2
                    12

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              I     2      3
    SAMPLE TIME (O'CLOCK)

EFFLUENT  PROFILE  COLOR vs.TIME
      FIGURE 3

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700
               12     I     2      3
             SAMPLE TIME (O'CLOCK)

           EFFLUENT PROFILE BODjVS TIME
                  FIGURE4
                 14

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     I      12     I      234
       SAMPLE TIME (O'CLOCK)

EFFLUENT  PROFILE-SUSPENDED SOLIDSvsTIME
           FIGURE  5
              15

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                       Table II

          Masland Dyehouse Raw Waste Profile


Parameter                   Mean            Range


Color - units *               2.5           0.7-5.9

pH                           4.3           4.0-6.0

Temperature- ° F.           110           90 - 124

BOD   (biochemical
    5 oxygen demand) mg/1    396           95 - 700

COD (chemical oxygen
      demand) mg/1          700           305 - 1450

Suspended Solids - mg/1       27            6-70
*  Tinctorial Strength.
                             16

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    Before designing an adsorption column treatment system for instal-
lation at the Masland-Wakefield plant, contamination-regeneration re-
cycling tests were performed employing actual Masland dyehouse waste-
water of known composition to contaminate.  Figure 6 shows the de-
crease  of COD removal as the adsorption capacity of the activated carbon
is used up (contamination cycles Cl, C2, etc. ),  with each contamination
cycle followed by a bio-regeneration cycle (Rl, R2,  etc. ).

    Each contamination  cycle (Cl, C2, etc.) was 2-1/2 hours in dura-
tion at 100 gph through two five-inch diameter columns,  each packed
with 5000 grams of granular Witco 718 carbon (12 x 30 mesh).  Columns
were contaminated  in the downflow direction in series, and biologically
regenerated in the upflow direction in parallel.  Hence,  during the con-
tamination cycle, the columns were operated in a packed mode and
during the regeneration each adsorbent bed was fluidized. Although
the natural waste influent varied widely in COD and chemical composi-
tion, the COD level was  generally above 700 mg/1.

    Each plotted point in Figure 6 represents  the per cent COD reduction
over a 30-minute interval.  A gradual decrease in removal efficiency
(first plotted point of each test cycle) can be observed during contamination
cycles Cl through C4.  This was attributed to  regeneration times which
were too short in duration (6 hours).  When the regeneration time was
increased to  12 hours  (R4 and R5), a corresponding  increase in "first
point"  removal efficiency is then achieved.

    Actual contamination experienced on a stated day was a composite
from the dyehouse effluent stream resulting, from the batch  dyeing opera-
tions listed in Table III.  The spectrum of dyeing formulation chemicals
in this test series was widespread.
LABORATORY DESIGN CRITERIA

    The Masland-Wakefield effluent averages 700 mg/1 COD at a flow
of 50, 000 gpd.  At this level, the treatment plant will remove 300 pounds
of COD per day.  Three  sections of two-inch diameter acrylic plastic
columns were each packed with 1, 200 grams of Witco 718 12 x 30 mesh
activated carbon.  A total of 720 liters of composite dyehouse effluent
samples was passed through each column in series at one liter per
minute.  Figure 7 shows the per cent  COD  removed for each column
versus total flow throughput in liters.  From these data, it was  calcu-
lated that 0. 076 pounds of COD were removed per pound of carbon at a
flow rate of 12 gpm/ft .   Based upon a conservative 0.05 pound  of COD
removal per pound of carbon for a 300 pound COD load per day,  6, 000
pounds of carbon would be required.
                                   17

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 100
  80
                                     C-CONTAMINATION CYCLE
                                     R-REGENERATION CYCLE
£60
              1
UJ
£E

O
O
O
  40
$20
      C-l
                C-2  v N  c-3  " M  C-4
           R-l       R-2       R-3       R-4
           6HR.      6 HR.     6HR.       12 HR.
                                                   R-5
                                                   12 HR.
                                                          C-6
                      REGENERATION  STUDIES
                            FIGURE 6
                            18

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                                                  Table III

                              COMPONENTS OF WASTE EFFLUENT FOR EACH
                              CONTAMINATION CYCLE PLOTTED IN FIGURE 6
       CYCLE Cl:  LIGHT RED ACRYLIC

       Calcozine Acrylic Blue HP Cove
       Calcozine Acrylic Red B
 Dyes  Calcozine Acrylic Violet 3R
       Calcozine Acrylic Yellow 3RN
       Astrazon Yellow 7GLL

       Acetic Acid. 56%
       Merpol DA
       Salt
       Retarder 98

       CYCLE C2;  BLUE WOOL

       Alizarine Light Blue  3F
 Dyes  Xylene Mill Green B
       Merpol DA
       Salt
       Acetic Acid, 56%
       Moth Snub
       Sulfuric Acid
       Erioclarite B
       Leveling Agent PD

       CYCLE C3:  BLACK  WOOL

 Dye  Omega Chrome Black ALA
       Acetic Acid, 56%
       Moth Snub
Dyes
Dyes
 Dyes
CYCLE C4:  RUST WOOL

Lanafast Orange RDL
Lanafast Navy NLF
Lanamid Red 2GL
Acetic Acid,  56%
Emkalana WSDC
Moth Snub

CYCLE CS: GOLD ACRYLIC

Astrazon Yellow  7GLL
Astrazon Red GTL
Astrazon Blue 5GL
Acetic Acid,  56%
Merpol DA
Retarder 98
Salt

CYCLE C6:  GREEN ACRYLIC

Sevron Yellow 3RL
Astrazon Red GTL
Aatrazon Blue 5GL
Nabor Blue ZG
Acetic Acid
Merpol DA
Salt
NOTE:  Components which develop color of the wastewater are designated above as "Dyes'.
        The other components are used for stabilization,  leveling, pH control, etc.
                                          19

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100
                                 COLUMN 3
                                 COLUMN 2
                                 COLUMN I
          180     360     540

             LITERS TREATED
720
         PERFORMANCE OF LABORATORY
         SCALE ADSORPTION COLUMNS
                 FIGURE 7
                20

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                         SECTION VI

                      FIELD STUDIES


DESCRIPTION OF PILOT PLANT

    The unit based upon the above discussed design criteria was in-
stalled in a service building (Building #4) on a tidal river bank
(Figure 8).  The dyehouse is across the street.  The waste  effluent
is pumped through a conduit beneath the road bed and through  a pipe
line located in Building #4 and hence  to the tidal estuary outfall.

    Figure 9  shows the waste  effluent line  emerging from the conduit,
the bypass line, the pump,  and three of the four activated carbon ad-
sorption columns.  Figure  10 illustrates the back side of the adsorption
columns, the  biological culture tank used for regeneration,  the air
pump which supplies air to the culture tank, and the recirculation pump
used during the regeneration cycle.  The whole treatment plant occupies
only 150 square feet,  and is no more than 12 feet high.

    The four  adsorption  columns were 3 feet in diameter by 10 feet
high constructed out of mild steel and innerlined with a fiberglass re-
inforced polyester resin and built to withstand 60 psi.   The  regeneration
reservoir was 5 feet in diameter by 8 feet high constructed  out of fiber-
glass reinforced polyester  plastic.  It had an open top and a sloping
bottom.  All piping was 3-inch diameter PVDC plastic.  Tank valving
comprised penton coated  three-way diverter plug valves. Pumps
were  of an all-iron positive displacement type.  The blower was of a
rotary lobe design.  Other  design features of the pilot plant appear
in Table IV.

    Figure 11 is a schematic  flow diagram of the waste treatment
system.   Solid flow lines trace the flow of the dyehouse waste effluent
through the adsorption filter columns during the contamination cycle.
Broken flow lines  trace the flow of the aerobic biological culture
through the columns during the bio-regeneration cycle.  The  biological
culture is prepared from a source of activated sludge and maintained
in a dispersed aerobic phase.
                                   21

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      C.H.MASLAND 9 SONS
          DYE  HOUSE
      SUB FLOOR
       DRAIN
           UNDERGROUND  DYEHOUSE
            WASTE EFFLUENT LINE
PLAN FOR LOCATION
OF FRAM WASTE
TREATMENT  SYSTEM
AT CRMASLAND 5 SONS
WAKEFIELD.R.I.
                                     Ul
                                     111
                                     oc.
                                     t-
                                     
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Waste Treatment System - C. H.  Masland & Sons,
  Wakefield,  R. I.  - Activated Carbon Columns

                    Figure 9
                        23

-------
Waste Treatment System - C.H.  Masland & Sons,
   Wakefield, R. I.  - Regenerant Reservoir

                   Figure 10

-------
                 Table IV
         Pilot Plant Design Features
Activated Carbon




Flow Rate




Carbon Column Flux Rate




Biological Culture  Capacity




Aeration Capacity
Up to 6, 000 pounds





Variable to 120 gpm





Up to 17.0 gpm/ft




1, 000 gallons





40 SCFM
                         25

-------
                     77-1 ACTIVATED
                     PA CARBON
SCHEMATIC FLOW DIAGRAM

        FIGURE  II
         26

-------
    As previously stated,  the equipment operates on a batch sequence
basis: for 10 hours,  the columns are operating on a contamination
cycle (adsorption-filtration) during which time the filtered waste
effluent flows into the river; for  14 hours, the columns are back-
flushed (regeneration cycle) on a recirculation basis with an aerobic
biological culture.  During the contamination cycle, liquid flow is
through each carbon column in series in a downflow mode.  During
the regeneration cycle, the biological culture flows in a parallel pat-
tern through the columns in an upflow mode.
PHASE I OPERATION

    The treatment plant was put on stream to operate without inter-
ruption (except downtime during weekends, holidays, and vacation
period) for 11 months.  Unfortunately,  this operation was plagued
with several mechanical failures.  Originally, the carbon (Witco 718
12 x 30 mesh) was  restrained top and bottom in each tank by screening;
carbon fines blocked the holes in the screen during several regeneration
cycles, and two of the screens ruptured owing to excessive pressures.
The top screens were removed.  It was found that the carbon bed did
not expand sufficiently to pass through the upper outlet port of the
vessel.  Continued regeneration cycling caused eventual plugging of
the bottom screens.  This was resolved by placing liquid distributor
crosses  in the carbon above the bottom screens.

    Because the unit was shut down for relatively long  periods of time
(2 days to 4 weeks  for each difficulty),  the activated carbon was sub-
jected to an erratic contamination and  regeneration operation with the
result that the carbon became deactivated to a state in which it could
not be reactivated. Hence,  it was not possible to attain in practice
the degree of adsorption-reactivation demonstrated in the laboratory
pilot  studies over a sufficient time period to ascertain continued
effluent quality criteria and the operational  economics of the system.

    However, it was shown in this first operational phase that better
than 99% decolorization did take place  and that COD could be re-
moved at a  relatively high level.  Table V lists  some of these results.
During the entire  Phase I operation, which extended over an 8-month
period,  904, 000 gallons of waste effluent  were treated,  and 3, 035
pounds of COD were removed.  Even under  the adverse operating
conditions experienced, this  represents eight times the single ad-
sorption capacity of the carbon.
                                  27

-------
                          Table V

         COD and Color Removal Data: Phase I Operation*

Thousand
Gallons
Dyehouse     Influent     Effluent          %
Wastewater     COD       COD         COD
Treated        mg/liter   mg/liter    Removed  Treated Effluent Coloration
48. 0
25.2
42.0
12.6
48.0
25.2
14.4
1000
917
1054
963
950
988
747
191
251
333
269
213
401
206
80.9
72.2
68.4
72. 1
77.6
59.4
72.4
                                                  No perceptible color

                                                  No perceptible color

                                                  Very slight tinting

                                                  No perceptible color

                                                  No perceptible color

                                                  Very slight tinting.

                                                  No perceptible color
 See Appendix A for complete Phase I data.
                                    28

-------
PILOT PLANT MODIFICATIONS

    The cross distributors in the carbon columns caused poor flow
distribution through the carbon; also, the bottom screens became
plugged with a hard resinlike composite of carbon fines and organic
matter.  Graded stone appeared to be a better carbon support and a
better bioculture liquor diffuser.

    The four carbon columns were refitted to take a graded gravel
support bed, ranging from 3/4" diameter stone to 10 x 10 mesh
gravel in contact with the carbon.  Also,  the top carbon retaining
screens were  removed and this made it necessary to decrease the
quantity of carbon from 1, 500 pounds to 1, 000 pounds in each column.

    The adsorption affinity of Witco 718 activated carbon for organic
matter in the Masland dyehouse effluent had been questioned.   Adsorp-
tion isotherms were conducted on five commercially available activated
carbons (see Appendix B for method of conducting this study and the
results).  Calgon Filtrasorb 400,  Westvaco Nuchar WV-G and Atlas
Darco 12 x 20 all had a greater affinity than Witco 718.  The choice
of Nuchar WV-G was one of availability and apparent better ability
to withstand mechanical fragmentation of the carbon granules. Fresh
activated carbon of a more active grade (Westvaco Nuchar WV-G
Granular 12 x 40 Mesh) replaced the spent carbon of the Phase I
ope ration.

    The dyehouse effluent was found to be deficient in nitrogen and
hence a sufficiently viable aerobic biological culture could  not be
maintained for the carbon regeneration.  During the contamination
(adsorption-filtration) cycle, all dissolved oxygen was removed and
some degree of unwanted anaerobic biological activity took place
accompanied by a  low pH. A desirable pH for an aerobic culture is
pH 7.  When the bioculture was recirculated through the carbon beds,
an acid pH of less than three was  initially encountered.  This shocked
the culture and upset at least three and sometimes all of the 14 hours
of regeneration by inhibiting a  large proportion of the aerobic micro-
organism population.   The addition of sodium bicarbonate on the basis
of 3 pounds/week appeared to buffer the culture sufficiently to withstand
the temporary low pH of the contaminated carbon columns and thereby
prevent an unwanted shock effect.
                                   29

-------
 PHASE II OPERATION

     During Phase I,  the flow rate was maintained at 60 GPM which
 was 54% of the total dyehouse effluent flow (the remainder was by-
 passed).  However, the entire dyehouse effluent was treated during
 Phase H.

     The addition of 5 pounds of available nitrogen per 100 pounds of
 BOD for Phase II operation was accomplished by the further addition
 of ammonium chloride  on the basis of 1.3 pounds/week.   The culture
 tank was reseeded with an acclimated textile dye waste activated sludge
 and buffered on a continuing basis  with sodium bicarbonate to maintain
 a 7-8 pH even when the biological liquor contacted the relatively acid
 residual liquid in the activated carbon tanks.

     Phase II was started on July 20, 1970 and was run continuously
 without shutdown (except for holidays and weekends) for 98 days, with
 no change or make-up of activated carbon.   Daily monitoring of the
 effluent during the adsorption mode took place through October 23, 1970.
 All effluent samples were colorless or very faintly tinted. Figure 12
 is a picture of effluent samples taken on October 30,  1970.   The sam-
 ples are sequential; starting with the untreated dyehouse effluent dis-
 charge on the far left, effluents from Columns  1 through 4 with the
 colorless effluent  of Column 4 as it was being discharged into the
 Saugatucket River.

    Figure 13 is a plot of pounds of COD removed versus gallons of
 water treated for both Phase I and Phase II operations.  Not shown
 in this graphical presentation is the erratic nature of the  Phase I
 operation and the numerous shutdowns.  The Phase II operation was
 continuous for a 98-day period and discharged a colorless effluent to
the Saugatucket River.  Undesirable color breakthrough occurred in
Phase I at about 600, 000 gallons and continued  in a deeper coloration
up to the end of  Phase I.  It should also be noted that the flow rate
during Phase I was 54% of the total dyehouse discharge.   Phase II flow
 rate was 100% of the  dyehouse discharge.

    The average results of the Phase II operation  in terms of COD,
TOC and color are  summarized as follows:

                        Dyehouse         Treatment
                        Wastewater        Plant           %
                        Influent          Effluent      Reduction
       COD - mg/1            550           280          49.0
       TOC - mg/1            220           115          47.8
       Color                  - -            - -          99.5
                                  30

-------
EFFLUENT SAMPLES - October 30,  1970 -
C. H.  Masland-Wakefield Waste  Treatment System
Flasks from Left to Right:  Influent -  Dye House
   Discharge,  Effluent - Carbon Column No. 1,
   Effluent - Column  No. 2,  Effluent  - Column
   No.  3,  and  Effluent -  Column No. 4


                    Figure 12
                            31

-------
»uuv-
6OOO-
KAnn.

MOVED
UJ 	 ~
o
0
°2000
U>
a
1
£L lArtn





_*_>^B
PHASE
CARBO
(6Ogp
^




COLOR
BREAKT
•*l >
N /
«n)X
r ^
X
POUNDS OF COD REMOVED
AS A FUNCTION OF GALLONS OF
WASTE WATER TREATED



HROUGH-7
[^
/




^


FIGURE

S
**~*


13

/




^




0X

^
/ PHASE* 2
^ CARBON
( HO gpm)








/
^)





6      8       10      12       14
    GALLONS TREATED  ( X I05)
16
18
20
         32

-------
       Color was measured by a visual technique set up for on-site deter-
minations.  The  influent was diluted with tap water until it matched the
color of the effluent.  One hundred milliliter graduates were used for
color comparison checks.  If the treated effluent matched a 100 ml
graduate containing only tap water,  the per cent reduction was recorded
as 100%.  For complete data on the Phase II operation, please refer
to Appendix C.

SYSTEM CONTROL

       Naturally, as with any waste treatment system, there  are some
important operational factors over which a certain degree of control is
needed in order to insure good operation.  Consider the system operation
in two parts; namely,  (1) the treatment cycle and (2) the regeneration
cycle:

       TREATMENT CYCLE
          (1)    FLUX - No higher than 15  gpm/ft  with optimum being
                        7 gpm/ft2

          (2)    EQUALIZATION - For discharges less than 100, 000
                       gallons per day:  at least 5 hours equalization
                       with the optimum being one working day.  For
                       discharges 1  mgd or over:  some equalization
                       desirable, but not essential due to continual
                       mixing of multi-dye vat dumping and rinsing

       REGENERATION CYCLE

          (1)    BIO-SOLIDS - maintain the settleable solids in the re-
                        generant liquor at less than 10 ml/1, with
                        optimum being 5 ml/I.

          (2)    pH  -  maintain the pH of the regenerent liquor in the
                     range of 6. 5 -  8. 0.

          (3)   NUTRIENTS- Supply 5 Ibs. of available nitrogen and one
                     pound of available phosphorus for every 100 pounds
                     of BOD treated by the system.

          (4)   DISSOLVED OXYGEN - maintain at least 2 mg/1 D. O. in
                     the regenerent liquor, with optimum being saturation
                     (~ 9 mg/1)
                                    33

-------
                          SECTION VII

                  WASTE TREATMENT SYSTEM
                     DESIGN AND ECONOMICS


PROPOSED REDESIGN OF PILOT PLANT AT WAKEFIELD,  R. I.

      Phase II operation has indicated the following performance
parameters heretofore unknown:

      (1)  At a  system flow rate of 15.6 gpm/ft  during the adsorp-
          tion treatment cycle, 4, 000 pounds of Westvaco Nuchar
          WV-G  12 x 40 mesh activated carbon have a decolorization
          capacity in excess of 3, 000, 000 gallons.
                                                              2
      (2)  The COD removal efficiency for the same 15.6 gpm/ft
          flow  is 48%; the COD removal efficiency at below 8. 5
          gpm/ft  is in excess of 85% (based on original Phase I
          data).

      There were three problems realized during both the Phase I and
Phase II operations:

      (1)  The lack of equalization of dyehouse effluent resulted in slugs
          of dye kettle discharges  being carried directly to the carbon
          columns;

      (2)  Batch adsorption operation required handling the full hydraulic
          load of the dyehouse discharge rather than extending the ad-
          sorption phase operation  over a longer time period;

      (3)  Erratic feeding experienced by the biological culture in the
          regenerant tank due to 10 hours without feeding and 14 hours
          in the carbon regeneration cycle.

      Two parallel systems of adsorption tanks will permit a more
dependable biological  culture because of its  continuous feeding.

      After due consideration of these factors,  a redesign of the treat-
ment system along the direction indicated in Figure 14 is proposed:

      (a)  The dyehouse effluent should be held in an equalization
          tank having a capacity of 50, 000 gallons.

      (b)  The effluent should then pass in series through three 1,200
           pound activated carbon columns at a flow rate of 30 to 40 gpm.


                                   35

-------
 FROM

OYEHOuli
EQUALIZATION
   TANK
                               ADSORPTION  COLUMNS-SYSTEM I
RE6ENERANT
RESERVOIR
                               ADSORPTION  COLUMNS-SYSTEM 2
                             TO
                          RECEIVING
                                                         STREAM
                  FIGURE  14   SECOND  GENERATION SYSTEM

-------
      (c)  A second series of activated carbon columns should be
          undergoing a regeneration cycle while the first series is
          on stream.

      (d)  The two series of columns should then be cycled,  accor-
          dingly, on stream and on regeneration.

      (e)  The biological regenerant tank should be 5, 000 gallons in
          size as opposed to the current 1, 000 - 1, 200 gallon tank.
          This would provide greater  buffering capacity and faster
          regeneration cycles.

      It has been estimated that the modified  plant cost would  be $75, 000
with an operating cost per year of $6,  000. 00.  There  is sufficient room
in the building where the present treatment system is located  to expand
the system to the proposed redesign which would occupy 1, 000 ft .

      The effluent quality of such a system should be tertiary treatment
level with values of:

                 COD Removal           75 + %
                 BOD Removal           95 + %
                 Color  Removal         100%
                 Turbidity                5 Jackson units
PROPOSED 1 MGD TREATMENT PLANT

      Based upon kinetics derived from the Phase II operation (see
Appendix F ), the amount of activated carbon required to remove 50%
and 75% COD was calculated for a one  million gallon per day plant.
Figure 15  is the flow diagram of a proposed 1 mgd plant capable of
removing all color and 47 - 53% COD.  A plant capable of  removing
75% or more COD is considered to be infeasible. Although a 50% COD
removal plant would be insufficient for a total waste treatment system,
the COD reduction coupled with virtually complete  color removal makes
the process very attractive as a pretreatment system for a conventional
biological  waste treatment operation.

      As shown in Figure 15,  raw waste is  pumped through four columns
8 feet in diameter and 16 feet high, each containing 17, 500 pounds of
carbon. A parallel bank of four columns  is on biological regeneration.
The biological regeneration vessel is rectangular 25 feet by 25 feet x
10 feet SWD (side water depth).  Chemical feeders are provided for
feeding nutrient and pH buffers if required for the dye waste to be
treated.  Equalization is not  considered necessary for  a pretreatment
                                   37

-------

RAM



I WASTE f
FE
PI
REGENERATION
VESSEL

~J~
ED
MP



1
1
1
\
1
1
1
1.1
71_
i —
X
V
T
—11
V
_J 	



—^
~*~


-—
1
X
i L —
ps
V



— *


•^-
—
— r
.
A
PS
V
_j —
"

--
•»•
-»

--

. — r_
X
"pu.
— 1 1
^
•1
i
i
i
i
i
i
i
— i.
i
i
i
--i
i
i
i
fc!
i
                                      TREATED
                                      EFFLUNT
PROPOSED I  MGD SYSTEM

      FIGURE 15
 38

-------
 plant of this high flow rate and has not been provided.  A wet sump is
 provided, however, to maintain a head for the pump.  Flow through
 the columns during the treatment phase is automatically controlled
 by demand per the liquid level in the wet sump.

      A decolorization system of this kind is best suited for a pre-
 dominantly soluble colored wastewater where the suspended solids
 are below 75 mg/1 and preferably averaging no higher than 30 mg/1.
 The COD should be below 1, 600 mg/1 and should average no higher
 than 800 mg/1. It is further limited by the ability of the activated
 carbon to decolorize the waste, and the adsorbed color and other
 associated  organic matter to be biologically oxidized.   The techniques
 for determining these important parameters to ascertain the feasibility
 of this treatment  approach are well discussed and described in this
 report.
 ECONOMICS  - 1 MGD PLANT

      Listed below are the economics of the 1 mgd plant operating at
 50% COD removal and at 75% TOD removal efficiency.  The estimated
 daily power and chemical costs are:

            Treatment                Operating Cost

            50% COD Removal        $83/day
                                        or
                                     8.3^/1000 gallons

            75% COD Removal        $231/day
                                        or
                                     23.1^/1000  gallons

      The construction cost of a 1 mgd plant is estimated to be:

           Treatment                Cost

           50% COD Removal        $230, 000
           75% COD Removal        $550, 000

      When amortization  is figured into operating costs (capital
recovery 20 years at 8% per annum), the costs become:
           Treatment                Operating Cost
           50% COD Removal        $147/day
                                        or
                                     14.7^/1000 gallons
                                   39

-------
             Treatment              Operating Cost

               75% COD Removal     $384/day
                                        or
                                      38.4^/1000 gallons

      All these cost estimates include an estimate for replacement or
other regeneration of the carbon on the basis of two changes  of acti-
vated carbon per year.

      Because of the particular or peculiar conditions for each indus-
trial location where such a treatment system might be applicable,
it is difficult to determine accurately costs of wet sumps, pipe lines,
maintenance,  labor, and nutrient and/or buffering chemical additions.
However, estimates have  been included for these costs and, given due
consideration,  small fluctuations in their magnitude would have little
effect on these estimates.
                                   40

-------
                           SECTION VIII

                          ACKNOWLEDGMENTS

     Supervision of the Masland pilot plant operation and back-up
laboratory work was carried out by Edward L. Shunney of Fram
Corporation.  He was assisted by Edward Chase and Anthony
Perrotti of the Fram staff.  The cooperation of Mr. Harold
Burkholder, Masland-Wakefield Plant Manager, and his assistants,
Walter Redmond and Steven Burdick, is also gratefully acknowledged.

     The critical analysis of the biochemical reactions taking
place during the first phase operation of the plant was done by
Professor Calvin P. C. Poon of the University of Rhode Island.
His findings leading to a successful bio-regeneration procedure
are greatly appreciated.

     The design of the one million gallon per day plant was accom-
plished by Dr. Allen Molvar, Philip Virgademo and Charles Kertell
of the Fram staff.  The biological regeneration process is the
development of Dr. Stephen Blecharczyk and is the subject of a pending
patent application assigned to the Fram Corporation.

     The organization, preparation and writing of this report was
the work of Clarke Rodman of the Fram Corporation.

     This is one of a  series of reports on work supported by the
Industrial Pollution Control Branch, Division of Applied Science
and Technology.

-------
                      SECTION IX

                     REFERENCES
1.    Knowles, C-  L.,  Jr.,  Chemical Engineering, 77,
      No. 9,  pp L03-109 (1970).

2.    Kugelman,  I. S., Paper Presentation "Treatment of
      Wastewater by Moving Bed Filtration",  23rd Industrial
      Waste Conference,  Purdue University,  Lafayette,
      Indiana (May  1968).

3.    Hassler,  J. W., Activated Carbon,  Chemical Publishing
      Company, New York,1963.

4.    Johnson,  R. L. et al,  "Evaluation of the Use of Activated
      Carbons and Chemical Regenerants  in Treatment of
      Wastewater", AWTR-11.
      U. S.  Public  Health Service Publication No.  999-WP-13,
      May 1964.

5.    Chemical Engineers' Handbook, J.  H.  Perry, Editor,
      Fourth Edition, McGraw-Hill Book Company, Inc.
      (Section 16).

-------
SECTION X
APPENDICES
      45

-------
       APPENDIX A
FIELD DATA,  PHASE I OPERATION

-------
            Table VI

    MASLAND - WAKEFIELD
         Phase I Data
June 26,  1969 thru October 6,  1969

Daily Flow ,
Date (Gallons x 10")
6/2
6/4
6/9
6/12
7/18
7/21
7/22
7/23
7/24
7/29
7/30
8/5
8/7
8/8
8/12
8/19
8/20
8/25
8/26
8/27
8/28
8/29
9/3
9/4
9/5
9/8
9/9
9/10
9/11
9/12
9/15
9/17
9/18
9/19
9/25
9/26
9/29
10/1
10/2
10/3
10/6
48.0
48.0
42.0
30.0
25.2
14.4
12. 6
25.2
28.8
28.8
25.2
25.2
28.8
25.2
25.2
28.8
14.4
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
18.0
14.4
18.0
Total TOC
In (mg/1)
394
374
415
360
361
294
379
389
480
485
410
325
320
355
237
410
372
249
361
257
399
489
380
297
243
316
301
440
401
445
360
273
229
240
280
268
335
365
366
201
571
Total TOC
Out #4 (mg/1)
75
84
131
129
99
81
106
158
260
374
338
150
204
184
103
252
241
140
229
173
299
312
309
207
175
261
167
297
239
359
218
179
138
168
238
200
264
275
308
157
396
% Reduction TOC
thru #4
80.9
77.5
68.4
64. 1
72.5
72.4
72.0
59.3
45.8
22.8
17.5
53.8
36.2
48.1
56.5
38.5
35.2
43.7
36.5
32.6
25.0
36. 1
18.6
30.3
27.9
17.4
44.5
32.5
40.3
19.3
39.4
34.4
39.7
30.0
15.0
25.3
21. 1
24.6
15.8
21.8
30.6

-------
    APPENDIX B
  ACTIVATED CARBON
ADSORPTION ISOTHERMS
             49

-------
                           APPENDIX B

EXPERIMENTAL PROCEDURE
                                           (3)
ADSORPTION ISOTHERM DETERMINATION
A.  Add prescribed amounts of dry activated carbon (eg. 1, 2, 4, 8,
    16,	gms. } to 500 ml Erlenmeyer flasks and  record com-
    bined weight of each.

B.  Add 400-500 ml distilled water to each flask,  stopper, and wet
    out carbon in a mechanical shaker for one hour.

C.  Decant liquor, including suspended carbon fines.  Caution should
    be exercise'd to prevent loss of granules.  Wash with 400-500
    ml distilled water (stirring with a glass rod).  Allow granules
    to settle.

D.  Decant as much liquor as  possible without loss  of carbon
             Cl\
    granules^ '.   Weigh flask  containing greatest  water residual
    and adjust all others,  including a carbon free control flask, to
    an equivalent amount.
                                                   / *5 \    f\
E.  Immediately after adding 200 ml of contaminant    (100   F. ) to
    each flask, agitate on mechanical shaker for prescribed time.
                                                                 (3)
F.  Filter liquor from each flask through Whatman #1 filter paper
    and analyze filtrate  for TOD.

G.  Prepare a table listing grams of carbon (M) , supernatant selected
    parameter (such as  TOD)  (C), water residual  as determined in
    Step D in order to calculate total volume of solution in liters (V).


    More than one washing may be needed to remove carbon fines,
    depending on type of carbon used.
(2)
    Contaminant  should  be filtered initially if sufficient undissolved
    material is present.
(3)
    If fines are present  in filtrate,  filter through  more appropriate
    material.
                                 50

-------
H.  From the table,  calculate "q"
           =  y
-------
70-
80
     FIGURE 16
 ADSORPTION ISOTHERM
  MASLAND EFFLUENT
  100             200

CONCENTRATION 
-------
             APPENDIX C
FIELD DATA, PHASE II OPERATION
                      53

-------
                                   Table VII
                         MASLAND  - WAKEFIELD
                                Phase IIData
                                  Week 1


Total TOC - In
Out #1
Out #2
Out #3
Out #4
% Reduction thru #4
Total COD - In
Out #1
Out #2
Out #3
Out #4
% Reduction thru #4
Total BOD - In
Out #1
Out #2
Out #3
Out 14
% Reduction thru #4
pH - In
Out #1
Out 12
Out #3
Out #4
% Color Reduction
Thru 1
Thru 2
Thru 3
Thru 4
Total Daily FJow
(Gallons x 103)
Tuesday -
A.M.
130
40
30
20
10
92.3
345
110
69
49
47
86.5
118

41

25
78.6
5.6
8.2
7.7
7.6
7.7







7/21
P.M.
3Z5
140
100
92
86
73.5
945
363
297
246
180
81.0
370

84

57
84.6
4.9
7.7
8.1
8.1
8.1






9.0
                        Wednesday - 7/22
                      A.M.          P.M.
           Thursday - 7/23
           A.M.       P.M.
                         Friday - 7/24
                        A.M.      P.M.
130
40
30
20
10
92.3
345
110
69
49
47
86.5
325
140
100
92
86
73.5
945
363
297
246
180
81.0
280
130
100
86
62
77.8
792
439
345
306
286
64.0
270
160
130
120
110
59.2
835
592
439
419
235
71.9
180
105
82
78
75
58.5






190
145
120
105
90
52.6






210
135
100
85
80
61.9






225
165
130
115
100
55.5






                        282
                         60
                        78.7
                        5.3
                        7.2
                        8.2
                        8.3
                        8. 3
                                     350
165
52.9
4.7
5.9
6.9
7.2
7.4
6.4
6.9
7.1
7.3
7.4
6.2
6.4
6.5
6.8
6.9
5.7
6.4
6.9
7. 1
7.3
                                     15.5
                                                            15.2
                                                                                    14.4
                                  Table VIII
                      MASLAND -  WAKEFIELD
                              Phase II Data
                                Week 2
 Monday - 7/27    Tuesday - 7/28   Wednei
A.M.      P.M.   A.M.     P.M.   A.M.
Total TOC




- In 120
Out #1 52
Out #2 40
Out #3 30
Out #4 25
% Reduction thru #4 79. 0
Total COD




- In
Out #1
out n
Out #3
Out #4
122
60
40
35
30
75.5





% Reduction thru #4
Total BOD




- In
Out #1
Out «f2
Out #3
Out #4





% Reduction thru #4
pH -




In 4.0
Out # 1 5.5
out n 6. 8
Out #3 7.2
Out #4 7. 3
3.9
4.8
6.4
6.9
7.1
220
175
132
105
75
66.0
574



202
65.0
265



120
54.7
5.5
5.8
6.1
6.6
6.7
% Color Reduction




Total Daily
Thru 1
Thru 2
Thru 3
Thru 4
Flow
(Gallon! x 10*)





30.9






190
142
118
105
95
50.0
496
333
278
257
255
48.5
235
128
45.5
5.5
5.7
5.9
6.1
6.4
200
160
150
150
140
30.0
519
425
404
380
380
26.8
320
245
23.4
5.4
5.5
5.8
6.2
6.6
7/29
P.M.
210
160
130
105
95
54.8
419
374
314
253
223
46.8
280
245
12.5
5.2
5.5
5.7
6.0
6.4
Thursday
A.M.
102
73
56
35
30
70.5









5.3
6.0
6.3
6.4
6.5
- 7/30
P.M.
140
115
70
42
30
78.5









3.9
5.0
6.3
6.1
6.4
Friday
A.M.
260
233
190
180
175
32.6









4.2
4.5
5.0
6.6
6.8
- 7/31
P.M.
270
241
180
167
160
40.7









4.2
4.3
4.4
4.7
5.9
                            31.7
                                             41.2
                                                               39.6
                                                                                 39.6

-------


Total TOC -




% Reduction
Total COD -




% Reduction
Total BOD -




% Reduction
pH -






In
Out #1
Out #2
Out #3
Out #4
thru #4
In
Out #1
out #2
Out #3
Out #4
thru #4
In
Out#l
Out #2
Out #3
Out #4
thru #4
In
Out #1
out #2
Out #3
Out #4
Monday - 8/3
A.M. P.M.
130 110
71 62
55 41
52 35
52 35
60.0 57.7












3.7 3.7
5.8 5.1
6.3 5.8
6.6 6.1
6.7 6.2
% Color Reduction




Total Daily
Thru 1
Thru 2
Thru 3
Thru 4
FJow
(Gallons x 10")





32.4
                              Table IX
                    MASLAND  -  WAKEFIELD
                             Phase II Data
                               Week 3
              Tuesday - 8/4
             A.M.     P.M.
Wednesday
\.. M.
220
95
75
60
60
72.7
411
178
126
99
85
79.3
165
76
56
48
44
73.4
4. 1
4.0
4.3
4.6
5.3

60
90
100
- 8/5
P.M.
150
120
105
80
60
60.0












4.8
4.9
4.7
4.6
4.8

60
90
100
Thursday
A.M.
180
155
135
120
110
38.9












5.6
5.6
5.6
5.4
5. 3
80
90
100
100
- 8/6
P.M.
190
185
160
145
130
31.6












5.3
5.3
5.4
5.4
5.5
70
90
100
100
Friday
A.M.
225
195
175
150
140
37.8
692



300
56.6






5.7
5.9
6.1
6.3
6.3

90
100
100
- 8/7
P.M.






768



574
25. 3






6.0
5.9
5.9
5.9
6.0
40
90
100
100
                        31.3
                                         39.0
                                                           35.2
                                                                              22.3
  Tuesday - 8/11
A.M.         P.M.
                                 Table X
                    MASLAND - WAKEFIELD
                              Phase II Data
                               Week 4
Wednesday - 8/12
 A.M.       P.M.
 Thursday - 8/13
A. M.      P . M.
 Friday - 8/14
A.M.        P.M.
Total TOC - In
Out |1
Out #2
Out 13
Out 14
% Reduction thru #4
Total COD - In
Out #1
Out #2
Out #3
Out 14
% Reduction thru #4
Total BOD - In
Out lU
Out 12
Out #3
Out 04
% Reduction thru #4
pH - In
Out #1
Out #2
Out #3
Out #4
% Color Reduction
Thru 1
Thru 2
Thru 3
Thru 4
Total Dally FJow
(Gallon! x 10 )
170
120
100
60
55
67.5
648
532
442
390
347
46.5












60
60
90
100

30.0
            547
            231
            57.7
240
190
105
75
70
70.8






140
130
90
85
80
42.8






215
150
145
100
95
55.9
680
572
501
455
453
33.4
250
170
140

120
52.0
610



378
33.1
260
175
160
145
115
55.7






295
190
160
105
105
64.4






B.5
5.8
6.0
6.2
6.3
60
80
100
100
5.5
5.6
5.8
5.8
5.9
60
80
90
100
5.2
5.2
5.4
5.8
5.9
40
90
100
100
5.4
5.8
5.9
6.2
6.2
50
70
90
100
5.8
6.1
6.2
6.4
6.5
70
90
100
100
5.9
5.9
5.9
6.2
6.4
40
80
100
100
                     31.2
                                            21.6
                                                                 28.8
                                   55

-------
                                                      Table XI
                                          MASLAND  - WAKEFIELD
                                                  Phase II DaU
                                                    Week 5


Total TOC -




% Reduction
Total COD -






In
Out #1
Out #2
Out #3
Out #4
thru #4
In
Out #1
Out #2
Out #3
Out #4
Monday -
A.M.
115
50
45
40
35
69.5





8/17
P.M.
120
90
75
60
50
58.4





% Reduction thru #4
Total BOD -




% Reduction
pH -




In
Out «1
Out #2
Out #3
Out #4
thru #4
In
Out #1
Out #2
Out #3
Out #4






5.7
6.0
6.1
6.2
6.2






5.6
5.B
6.0
6.0
6.0
Tuesday
A.M.
224
173
155
140
120
46.4
491
353
285
244
208
57.5






5.9
6.3
6.5
6.7
6.8
- 8/18
P.M.
212
160
135
130
118
44.3
693



330
52.4






5.0
5.9
5.9
6.0
6.1
Wednesday
A.M.
153
122
70
65
62
59.5
644
580
499
487
479
25.7
195
155
150
118
93
52.3
6.2
6.7
6.8
6.9
7.0
- 8/19
P.M.
264
192
180
150
131
50.4
766



520
32.1
325



192
41.0
6.1
6.9
6.9
6.9
7. 1
Thursday -
A.M.
395
370
354
342
250
36.7












4.6
4.7
5.2
5.5
5.6
8/20
P.M.
333
270
242
223
215
35.5












5.7
5.9
6.0
6.0
6.0
Friday -
A.M.
294
162
151
140
134
54.5












6.2
6.4
6.5
6.5
6.4
8/21
P.M.
298
251
243
214
196
34.2












5.9
6.0
6.0
6.0
6.0
% Color Reduction
            Thru 1    60         60        50
            Thru 2    85         90        80
            Thru 3   100        100        90
            Thru 4   100        100       100
Total Daily Flow
(Gallon! x 10 )                   28.8
             60
             90
            100
            100

             29.2
             60
             90
            100
            100
                80
                90
               100
               100
                                                                       22.0
      100
      100
      100
      100
      80
     100
     100
     100
                                                                                        34.4
      90
     100
     100
     100
        90
       100
       100
       100
                                                                                                        28.8
                                                      Table XII
                                            MASLAND -  WAKEFIELD
                                                   Phase II Data
                                                      Week 6
                      Monday - 8/24   Tueiday - 8/25   Wednesday - 8/26   Thursday - 8/27
                      A.M.     P.M.  A.M.     P.M.  A.M.      P.M.  A.M.     P.M.
                                                  Friday - 8/28
                                                  A.M.      P.M.
Total TOC - In
Out #1
Out #2
Out #3
Out #4
% Reduction thru #4
Total COD - In
Out #1
Out #2
Out #3
Out #4
% Reduction thru #4
Total BOD - In
Out#l
out n
Out #3
Out #4
% Reduction thru #4
pH - In
Out#l
Out #2
Out #3
Out #4
% Color Reduction
ThruHfl
Thru #2
Thru #3
Thru #4
Total Dally Flow
(GalloftB. x 10 )
250
210
195
180
170
32.0












5.7



6.7

80
100
100
100


                               275
                                175
                                40.0
455
395
305
280
245
46.






410
385
370
340
330
19.5






260
230
195
180
165
36.5
612
586
467
418
331
62.3
305



145
52.5
729



331
54.7
285
235
200
190
175
38.6






                               5.5
                               5.9

                               60
                               80
                              100
                              100


                               32.4
                                        4.9
 5.4

 40
100
100
100
                                                4.7
 5.3

 40
 80
100
100


 33.6
                                                       250
                                                       160
                                                       36.0
                                                       5.5
5.8

40
60
80
90
                                                                 320
                          222
                          30.6
                                                                         5.6
 5.8

 40
 60
 80
100
                                                                                  290
                                           180
                                           37.9
                                                                 30.0
                                                                                  5.3
 5.5

 50
 90
100
100


 33.6
                                           260
                                           230
                                           190
                                           180
                                           160
                                           38.5
                                                                                          5.3
 5.6

 40
 60
 80
100
                                                                                                  270
                                            140
                                            48.2
                                                                                                  5.4
 5.6

 40
 60
 80
100


 33.6

-------
                         Table XIII
                MASLAND  -  WAKEFIELD
                         Phaie II Data
                          Week 7
 Monday - 8/31
A.M.     P.M.
Tueiday - 9/1
A.M.       P.M.
 Wednesday
A.M.
- 9/2
 P.M.
 Thur«day - 9/3
A.M.       P.M.
Total TOC - In
Out 11
Out 12
Out 13
Out 14
% Reduction thru 14
Total COD - In
Out 11
Out 12
Out 13
Out #4
% Reduction thru 14
Total BOD - In
Out 11
Out 12
Out 13
Out #4
% Reduction thru 14
pH - In
Out 11
Out 12
Out 13
Out #4
% Color Reduction
Thru 1
Thru 2
Thru 3
Thru 4
Total Dally Clow
(gallons x 10 )
270
190
165
140
125
53.7












6.3



5.7

90
100
100
100


295



130
56.0












6.1



5.6

90
100
100
100

32.4
290
170
140
120
105
63.9












4. 1



5.0

40
90
100
100


170 215
180
155
140
100 120
41.2 44.2
520
394
358
342
330
36.5
195
192
190
178
150
23.0
4.6 5.9



5.3 5.8

40 40
80 80
90 90
100 100

32.8
                                                    405
                                                    210
                                                    48.2
                                                    582
                                                    434
                                                    25.4
                                                    285
                                                    255
                                                    10.5
                                            260
                                            220
                                            200
                                            180
                                            145
                                            44.2
                                                              4.7
                                                               6.3

                                                               50
                                                               80
                                                              100
                                                              100
                                                                         295
                                  195
                                  34.0
                                                    28.8
                                                                         4.3
                                                       6.0

                                                       30
                                                       70
                                                       90
                                                      100
                                                                         32.4
                             Table XIV
                    MASLAND - WAKEFIELD
                          Phase ii Data
                            Week 8


Total TOC - In
Out #1
Out 12
Out 13
Out #4
% Reduction thru 14
Total COD - In
Out #1
Out 12
Out 13
Out #4
% Reduction thru 14
Total BOD - In
Out 01
Out 12
Out #3
Out #4
% Reduction thru 14
pH - In
Outll
Out #2
Out 13
Out #4
% Color Reduction
Thru 1
Thru 2
Thru 3
Thru 4
Total Dally Flow
(Gallont x 10 )

Tueiday - 9/8
A. M. P. M.
150 160
130 150
115 140
100 120
85 105
43.4 34.4


















60 90
80 100
90 100
100 100

27.6

Wednesday
A.M.
130
100
95
80
60
53.7
269
239
131
100
98
63.5
122
80
72
62
56
54.1
5.1



6.S

80
90
100
100



- 9/9
P.M.
210
190
170
140
110
47.6
490



247
29.2
235



145
38.3
5.1



6.7

70
80
90
100

29.2
57
                                          Thurtday - 9/10
                                          A.M.      P.M.
                                              Friday - 9/11
                                             A.M.      P.M.
                                          225
                                          150
                                          130
                                          105
                                           90
                                          60.0
                                           6.4
                                           6.7

                                           80
                                           90
                                          100
                                          100
                                   190
                                   110
                                   42.0
                                                     4.9
                                   6.5

                                   70
                                   80
                                  100
                                  100


                                   28.0
                                                               230
                        115
                        50.0
                                                               4.7
                         6.2

                         80
                         90
                        100
                        100
                                                        190
                        115
                        39.5
                                                                          4.9
                        6.2
                                                                          27.2

-------
                                                      Table XV
                                              MASLAND -  WAKEFIELD
                                                      Pha« e II Data.
                                                        Week 9
Monday - 9/14 Tueaday - 9/15 Wednesday - 9/16 Thursday 9/17 Friday

Total TOG -




A.M.
In 235
Out #1
out #2
Out #3
Out #4 90
% Reduction thru #4 61.7
Total COD -




In
Out #1
Out #3
Out #3
Out #4
P. M. A. M.
260 315



185 175
28.8 44.5





% Reduction thru #4
Total BOD -




In
Out #1
Out #2
Out #3
Out #4





% Reduction thru #4
pH -




In 6.7
Out #1
Out #2
Out #3
Out #4 6. 5
5.5 6.6



6.0 6.8
P.M. A.M.
305 220



140 145
54. 1 34. 1
451
400
398
359
321
28.8
205
178
172
152
130
36.6
5.3 4.7



5.9 6.4
P.M. A.M.
260 245



190 100
27.0 59.2
592



445
24.8
232



215
7.3
5.2 5.5



6.2 6.2
P. M. A.M.
210 205



105 80
50.0 61.0












5.6 5.7



6.1 6.3
% Color Reduction




Thru 1 90
Thru 2 100
Thru 3 100
Thru 4 100
80 90
90 100
100 100
100 100
80 90
90 100
100 100
100 100
90 90
100 100
100 100
100 100
90 80
100 80
100 90
100 100
Total Daily F^owr
(Galloni x 10
)
28.8
28.0
28.8
27.2
                                                                                                  P. M.
                                                                                                    290
                                                                                                    140
                                                                                                    51.8
                                                                                                    5.3
                                                                                                    5.9

                                                                                                    80
                                                                                                    90
                                                                                                   100
                                                                                                   100


                                                                                                    27.2
                                                       Table XVI
                                             MASLAND - WAKEFIELD
                                                      Phaae n Data
                                                       Week 10

                                              Monday - 9/21
                                            A.M.          P.M.
Total TOC - In
            Out #1
            Out #2
            Out #3
            Out #4
% Reduction thru #4
Total COD - In
            Out #1
            Out #2
            Out #3
            Out #4
% Reduction thru #4
Total BOD - In
            Out fl
            Out #2
            Out #3
            Out #4
% Reduction thru #4

pH  -       In
            Out #1
            Out #2
            Out #3
            Out #4
% Color Reduction
            Thru 1
            Thru 2
            Thru 3
            Thru 4

Total Daily FJow
(Gallon! x 10 }
 150
 140
 120
 100
  90
 40.0
 6.9
 6.9

 10
100
100
100
                                                            170
  90
 47.0
                 6.7
 6.9

 80
100
100
100

 24.0

-------
                                                        Table XVII
                                              MASLAND -  WAKEFIELD
                                                    Phase II Data
                                                      Week 11
Total TOC - In
            Out #1
            Out #2
            Out #3
            Out #4
% Reduction thru #4

Total COD - In
            Out #1
            Out #2
            Out #3
            Out #4
% Reduction thru #4

Total BOD - In
            Out #1
            Out #2
            Out #3
            Out #4
% Reduction thru #4

pH   -       In
            Out#l
            Out #2
            Out #3
            Out #4
% Color Reduction
            Thru 1
            Thru 2
            Thru 3
            Thru 4
Total Daily Flow
(Gallons x 10  )
Wednesday
A.M.
320
300
240
210
185
42.2
464
408
340
321
284
38.8
220
200
140
132
105
52.3
- 9/30 Thursday - 10/1 Friday - 10/2
P.M. A.M. P.M. A.M. P.M.
195 Z10 270 290 205



100 135 190 130 85
48.7 35.7 29.6 55.2 58.5
584



316
45.9
234



181
22.6
                                5.2
                                6.7

                                70
                                85
                                90
                               100
                                            5. 1
 6.7

 70
 90
100
100


 42.9
                                                            5.4
 6.6

 90
100
100
100
                                                                         6.2
 6.3

 80
 90
 90
100


 47.9
                                                                                  6. 1
 6.3

 70
 80
100
100
                                                                                              6.5
 6.6

 60
 70
 80
100

 44.6
Total TOC - In
            Out#l
            Out #2
            Out #3
                                                        Table XVIII
                                            MASLAND  - WAKEFIELD
                                                    Phase II Data
                                                     Week 12
                       Monday - 10/5     Tuesday - 10/6    Wednesday - 10/7    Thursday - 10/8    Friday - 10/9
                      A.M.     P.M.    A.M.      P.M.  A.M.        P.M.   A.M.      T,  .....
                       230
                                 180
                                           135
                                                    220
                                                            215
                                                                        150
                                                                                140
                                                                                         P.M.

                                                                                         150
                                                     A.M.

                                                      225
                                               P.M.

                                               190
Out #4 115
% Reduction thru #4 50. 0
Total COD - In
Out #1
Out #2
Out #3
Out #4
% Reduction thru #4
Total BOD - In
Out #1
Out #2
Out #3
Out #4
% Reduction thru #4
pH - In 5.4
Out #1
Out #2
Out #3
Out #4 6. 9
% Color Reduction
Thru 1 70
Thru 2 80
Thru 3 80
Thru 4 100
Total Dally Flow
(Gallons x 10 )
105 65
41.7 51.8












5.7 6.4



6.1 6.5

90 40
100 80
100 90
100 100

38.0
120
45.5












6.1



6.7

80
80
100
100

39.0
100
53.5
273
241
120
101
94
65.6
123



53
56.9
5.3



6.2

75
80
90
100


85 55 85 90 75
43.3 60.7 43.3 60.0 60.5
441



232
47.4
227



136
40.1
6.2 5.3 6.2 5.1



6.6 6.0 6.1 6.8 6.7

75 90 75 50 40
90 90 90 70 60
100 100 100 100 90
100 100 100 100 100

47.9 38.0 47.9
                                                      59

-------


Total TOC - In
Out #1
Out 12
Out »3
Out 14
% Reduction thru #4
Total COD - In
Out#l
Out #2
Out #3
Out #4
% Reduction thru #4
Total BOD - In
Out 01
Out #2
Out 03
Out #4
% Reductionthru #4
pH In
Out*!
Out #2
Out #3
Out #4
% Color Reduction
Thru 1
Thru 2
Thru 3
Thru 4
Total Daily FJow
(Gallon* x 10 )
Monday - 10/12 Tuesdi
A.M. P.M. A.M.
215 150 130



105 105 75
51.2 30.0 42.3












5.5 5.6 6.3



7.0 6.0 6.7

60 70 70
80 100 70
90 100 90
100 100 100

46.2
                                                   Table XIX
                                          MASLAND  -  WAKEFIELD
                                                  Pbaaell Data
                                                    Week 13

                                       Tuesday - 10/13  Wednesday - 10/14  Thursday - 10/15   Friday - 10/16
                                                  P.M.  A.M.        P.M.  A.M.     P.M.   A.M.     P.M.
                                                   140
                                                   105
                                                   25.0
                                                   6.0
                                                   6.2

                                                   60
                                                   80
                                                   90
                                                  100


                                                   39.6
                                                           210
 160
 23.8

 284
 239
 141
  94
  80
 71.8

 134
                                                            62
                                                           53.7

                                                           4.9
 6.1

 70
 80
100
100
                                                                     155
 100
 35.5

 452
                                                                     214
                                                                     52.6

                                                                     218
           140
           35.8
           6.2
 6.7

 70
 80
100
100


 42.9
                                                                             145
  50
 65.5
                                                                             5.4
 6.0

 50
 60
 90
100
                                                                                      210    230
 105
 50.0
                                                                                       5.2
 6.4

 60
 70
 80
100


 47.9
115
50.0
                                   6.2
6.6

50
70
90
90
                                                                                                      160
 95
40.6
                                            5.4
6.3

40
70
80
90


44.6
Tot»lTOC -
            In
            Out #1
            Out #2
            Out #3
                                                      Table XX
                                             MASLAND - WAKEFIELD
                                                    Phatell Data
                                                      Week 14

                        Monday- 10/19   Tueiday - 10/20   Wednesday - 10/21   Thursday -  10/22   Friday - 10/23
                       A.M.      P.M.   A.M.       P.M.   A.M.       P.M.    A.M.     P.M.  A.M.    P.M.
                       155
                                 190
                                         150
                                                   165
                                                           140
                                                                      190
                                                                              190
                                                                                       290
                                                                                             325
                                                                                                       355
Out #4 110
% Reduction thru #4 29. 0
Total COD - In
Outfl
Out #2
Out #3
Out #4
% Reduction thru #4
Total BOD - In
Out#l
Out #2
Out #3
Out #4
% Reduction thru #4
PH - In 4.2
Out 11
Out #2
Out #3
Out #4 6. 4
% Color Reduction
Thru 1 70
Thru 2 80
Thru 3 100
Thru 4 100
Tottl Daily Flow
| Gallon* x 10 )
120 95
36.8 36."












6.2 6.2



6. 5 6. 4

40 70
50 90
60 100
90 100

39.6
100
39.4












6.4



6.5

60
80
100
100

4Z.9
160
33.3
310
262
156
120
119
62.9
190



92
51.6
6.7



6.9

30
60
70
90


105 80 125 130 205
44.7 57.9 56.9 60.0 42.3
362



2Z2
38.7
246



105
57.3
6.3 5.2 6.7 4.8 5.3



7.6 6.1 6.7 6.4 6.8

80 50 70 40 70
90 60 80 60 90
100 90 100 90 100
100 100 100 90 100

42.9 47.9 42. S
                                                          60

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          APPENDIX D
CHEMICAL REGENERATION STUDIES
                   61

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                           APPENDIX D

               CHEMICAL REGENERATION STUDIES
     When the Witco 718 activated carbon during Phase I operation
 became non-regenerable biologically,  consideration was given to
 other methods of regeneration in place (4).  The most feasible
 appeared to be the  use  of a chemical oxidant.  Laboratory studies
 were initiated.  Oxidants such as hydrogen peroxide, sodium hypo-
 chlorite,  potassium persulfate,  sodium peroxide,  and sodium bro-
 mite were evaluated.  Potassium persulfate appeared to be the most
 effective.

     Two  5-inch diameter 3 feet  high plexiglass columns were filled
 with 5, 000 grams of exhausted carbon removed from adsorption
 column No. 1 of the Masland pilot plant. Both columns were washed
 (upflow in a fluidized bed flow) with equal volumes of tap water.
 A reservoir containing 5 gallons of  2% regenerant solution was con-
 nected to one  of the columns and the solution was recirculated upflow
 through the column for 8 hours at 5 1/min.  Both columns were again
 washed with tap water, drained and actual composite samples of
 dyehouse waste liquor were  pumped through the columns upflow in
 parallel with each running at 100 mls/min.  The total test column
 effluent from  each  column was collected in one gallon increments
 and analyzed for  TOD.

     Figure 17 is a plot of the effluent TOD in mg/1 as  the contaminant
 passed through each test column; one column contained exhausted
 carbon which  had not been subjected to an oxidant and the other con-
 tained exhausted  carbon which had  been contacted with a 2% hydrogen
 peroxide solution in the manner  described above.  The same lack of
 regeneration effect occurred for all the other oxidants with the excep-
 tion of potassium persulfate. Figure 18 is a similar plot to that of
 Figure  17 and illustrates that actual regeneration which took place -
 the column effluent of the K_S7Ofi when dye waste was  passed through
 was  considerably lower in TOD than that for the control column.
 Figure 19 is a plot of TOD in the effluent after the first repetition of
 K  S  Og regeneration.  Figure  20 is a plot of TOD in the effluent after
 the third regeneration with K S2Oft.  Also included in Figure 19 is
a plot of the effluent TOD through a third test carbon adsorption
 column  where fresh or "virgin" Witco 718 carbon was  used.
                              62

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    All of the previously discussed K S  O  regenerations were
carried out at 25   C.  When the regeneration temperature was in-
creased to 50 C.,  the degree of regeneration was  markedly in-
creased as shown in Figure 20.  Figure 21 is  a similar plot after
a second K_S?OQ regeneration at 50 C.

    The degree of carbon adsorption recovery by hot K S_OQ
(50  C. } regeneration was  70 - 80%.  It was felt that if this  could be
accomplished on the four columns of exhausted Witco 718 carbon at
the Masland pilot plant installation,  the productive  life of the carbon
could be materially extended.  One column was put on such a re-
generation cycle.  The bronze lining of the recirculating pump was
eaten away and the oxidant played havoc with other  components of the
system.

    For this reason,  no further work was done along these lines in
the laboratory or on the pilot plant operation.  With materials of
construction compatible with K-S^Oo,  chemical regeneration of
activated carbon exhausted by the presence of non bio-degradable
organic matter can be achieved.   The regenerated  columns can then
be put back  in use with bio-regeneration up to the time that color
breakthrough is noticed, and then again chemically regenerated.
                                 63

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900
800
                      3456
                         GALLONS

                    REMOVAL  PROFILE
                 H2 02 REGENERATION (25°C)
                       FIGURE 17
                            64

-------
  800
  TOO
  600
  500
  40O
INFLUENT
Q
o
  300
  200
   100
                         3436
                              GALLONS

                        REMOVAL PROFILE
                     K2 S2 08  REGENERATION (25°C)

                           FIGURE 18
                             8

-------
  90O
  800
  700
  600
N
Ol
E
Q
o
  300
  400
  300
   200
   100
                        345
                            GALLONS

                        SECOND K2S208
                       REGENERATION  (25°C)

                          FIGURE 19
                            66

-------
600
                  THIRD K2S208
                REGENERATION (SO°C)
                     FIGURE  20
                       67

-------
  900
  800
  70t>
  600
  500
  400
a
o
t-
  30O
  200
  IOO
                       REPEAT OF  50°C

                     K2S2Oe  REGENERATION

                         FIGURE 21
                             68

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             APPENDIX E
COD,  BOD, TOG,  TOD RELATIONSHIPS
                    69

-------
  3.00- -
o
o
m
O
o

u.
o

o


<
K
  2.0O- -

                                                                        »•
                                                     AVERAGE* 2.51
  1.00- -
                    I I I I  1
                                     I  I  I  I  I  I  I  I  I  I  I I  I  I  I  I  I  I  I  I  I
                         10         15        20        25        30        35
                            SAMPLE  NUMBER
                      CORRELATION OF COO TO BOO
                             FIGURE 22
                                  70

-------
  3.00- -
X.2.00-
 0s
 o
 o
 p
 o
 I-
 (C
  1.00- -
                                                    -AVERAGE-2.54
                                                                   -\


                         IO
15
20
                                                      25
                             30
                             35
                           SAMPLE NUMBER
                     CORRELATION OF COD TO TOC
                             FIGURE 23
                                  71

-------
 i.oo- -
o
o
O
O
o

u.
O
-4-VV--K-/
o
                   I I  I I I 1  1
                10
                 15
                             20
                  SAMPLE NUMBER
              CORRELATION OF COO TO TOO
                   FIGURE 24
                                         30
                      72

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     APPENDIX F
1 MGD DESIGN CRITERIA
               73

-------
     The scale-up from the pilot plant data to a 1 mgd plant is
accomplished by maintaining dynamic and geometric similarity be-
tween the pilot plant and the full sized plant.  A theoretical analysis
of the kinetics of mass transfer in fixed bed adsorption systems
(Chemical Engineering Handbook,  Perry, 4th Edition,  Section 16)
indicates that

   — . Ve    and  k x T  are the important  similarity groups:
      F            D

       k   =   overall mass transfer coefficient
       V   =   ft   of activated carbon
       e   =   fraction of void volume
       F   =   flow rate
       D   =   distribution ratio  =    QoP P
       f3   =   density of activated   CQ  e
                      carbon
       CJoQ  =   capacity of activated carbon at influent concentration
       C   =   influent concentration
       G°  =   flux (gpm/ft2)
       T   =   time

     Since the same activated carbon,  mass flux rates,  and cycle
duration will be used in the 1 mgd plant,  k,  e and   ^ T  are also
equal for the pilot and full scale plant. Therefore,  scale-up is
approximated through the principle of equal  relative residence times
(V/F).  Analysis of the experimental data indicates the following values:
                                                               2
       Per cent Reduction ( COD)      V/F  (days)    G  (gpm/ft  )

                50                       0.025           12
                75                       0.076           12

     Applying the equal residence time criteria for a 1  mgd plant
utilizing Nuchar WV-G activated carbon ( e = . 4,   P = 32 lbs/ft3),
the amounts  required are:

       Per cent Reduction (COD)      Carbon (Ibs. )       G  (gpm/ft2)

                50                       110,000         12
                75                       330,000         12
                                  74

-------
Determine Carbon Column Size for 50% COD Removal

    Carbon  required for 50% COD removal = 110, 000 Ibs.
    110, 000 @ 27 #/ft3  = 4075 ft3
    with 50% bed expansion
       4075 x 1.5 = 6110 CF Required
    Assume 2 banks of 4 columns each
      -iil°.  =765 ft3 col.
        8
    For 8' diameter   area = 50.3 ft

   Height =  -?|f-3 -  15.2.

    Check the surface area for flux

       Flux  =    6l*Mm   =   13.8gpm/ft2

    13.8  >  12 gpm/ft  :   O.K. for flux

    Use 8 columns 8' diameter x  16' high

Regeneration Vessel Size

    Vol. =  2 x the capacity of columns to be regenerated.
    Vol. =  2 x 4 x 765 = 6110 ft

Use 25' x 25' x 10' SWD  Regeneration Vessel

Determine Carbon Column Size for 75% COD Removal

    Carbon required for 75% removal = 330, 000 Ibs.
       330, 000 @ 27 #/ft  =  12,200ft
       with 50% bed expansion 3
        12,200 x 1.5 = 18,300 ft
    Assume 4 banks of 4 columns
        18, 300      ,  , ... ,,3 /  ,
       — —— -  =  1, 145 ft /col.
          16                     2
    For 9'  diameter, area 63.5 ft
   Height  =      - = 18'
     Check the surface area for flux
                                     2
       Flux=           =10. 9 gPm/ft
       10.9 =   12 gpm/ft2:  O. K. for flux

Use 16 columns 9' diameter x 18' high
Regeneration Vessel Size
     Volume = 2 x capacity  of columns to be regenerated
     V  =  2x 8x  1145 = 18,300 ft3
Use 30' x 60' x  10' SWD Regeneration Vessel

                                  75

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1
•
Accession /V umber
2

Subject Field & Group
05D
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
  c  I Organization
	'       C. Hi Masland & Sons
           Carlisle, Pennsylvania 17013
     Title
           Bio-Regenerated Activated Carbon Treatment
           of Textile Dye Wastewater
 10
Authors)
 Rodman,  Clarke A.
         and
  Shunney, Edward L.
16
   Project Designation
                                         EPA-WQO Grant Project 12090 DWM
                                   21
                                       Note
 22
Citation
 23
Descriptors (Starred First)
* Wastewater Treatment, * industrial wastes,*  textiles
*  Activated Carbon, adsorption,  color, costs
 25
Identifiers (Starred First)
     * Total Organic Carbon
 27
    .Abstract
      A novel approach to treating a highly colored textile dyeing waste effluent is
described.  It comprises the removal by sorption of color bodies and other organic
matter on activated carbon granules.  Spent carbon granules are then  subjected to a
virule aerobic biological culture which desorbs and bio-oxidizes the desorbed matter,
thereby regenerating the carbon for subsequent new sorption steps.
      Laboratory confirmation of the phenomenon is presented.  Field testing of the
treatment process concept in a  50, 000 gpd plant installed at a yarn spinning mill
(C. H.  Masland & Sons,  Wakefield, Rhode Island) is reviewed.                     2
      Color removal was virtually complete at two flow rates evaluated: 8. 5 gpm/ft
and 15.6  gpm/ft  carbon column bed flow.  COD  removal was 85% or higher at 8.5
gpm/ft and only  48% at 15.6 gpm/ft .
      It was demonstrated  that activated carbon had an adsorption capacity in excess of
1.6 pounds  ODD per pound of carbon when the carbon was reactivated only by biological
means.  The  estimated operating  cost for decolorizing 1, 000, 000 gpd is 8.3 cents/
1000 gallons.
      This  report was  submitted in fulfillment of Grant No.  12090  DWM between the Water
Quality Office of the Environmental Protection Agency and C. H. Masland & Sons.	
Ab
         A. Rodman
                             Institution
                               FRAM CORPORATION
 WR:102 (REV. JULY 19681
 WRSIC
                                             SEND TO:
                                               WATER RESOURCES SCIENTIFIC INFORMATION CENTER
                                               U.S. DEPARTMENT OF THE INTERIOR
                                               WASHINGTON, D. C. 20240
                                                                           * CPO : 1971 O - 426- 250

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