WATER POLLUTION CONTROL RESEARCH SERIES • 12090DWM01/71
   Bio-Regenerated
 Activated Carbon Treatment
      of Textile Dye Wastewater
WIRONMENTAL PROTECTION AGENCY • WATER QUALITY OFFICE

-------
             Water Pollution Control Research Series

     The Water Pollution Control Research Reports describe
the results and progress in the control and abatement of
pollution in our Nation's waters.m 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,
Washineton. D. C. 20242.

-------
BIO-REGENERATED ACTIVATED CARBON

             TREAT MENT 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

-------
                      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.

-------
                           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
des orbed 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/ft  .
      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

-------
Page Intentionally Blank

-------
                         CONTENTS

                                                          Page No.

ABSTRACT                                                   hi

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           1?

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

-------
                                                               No.
APPENDIX D  - CHEMICAL REGENERATION STUDIES         61

APPENDIX E  -  COD,  BOD,  TOC, TOD RELATIONSHIPS      6?

APPENDIX F  - 1 MGD TREATMENT PLANT DESIGN          73
                      PARAMETERS
                       VI

-------
                            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
                            £  C->
18    REMOVAL PROFILE - K S  O   REGENERATION (25  C. )    65
                            2  2 o
19    SECOND K SO  REGENERATION (25° C. )                  66
                L  iL  g

20    THIRD KS-O  REGENERATION (50° C.)                   6?
              ^ £  O

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

                              vii

-------
                                                           Page




22     CORRELATION OF COD TO BOD                         7°




23     CORRELATION OF COD TO TOC                         71




24     CORRELATION OF COD TO TOD                         72
                            Vlll

-------
                             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                                 25

 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 IlData  - Week 13                60

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

-------
Page Intentionally Blank

-------
                          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 1 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.

-------
Page Intentionally Blank

-------
                                       II

                        RECOMMENDATIONS
    The Masland-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.

-------
Page Intentionally Blank

-------
                           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 "unexpected11
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-  Perrorti 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.

-------
    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 .

-------
                          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%.

-------
    WASTE

    WATER
GRANULAR

ADSORBENT

BED
                 r
0po30W&* t*Ofey£3ja*
»§g o**oo *•»»•**•*'
%0jn>oee> o erf coo'

%$ss.T'*£*>'«'&

a£?!J* &<&>?*
            r*
      AEROBIC

      BIOLOGICAL

      CULTURE

      RESERVOIR
                                   AIR
                        TREATED  EFFLUENT
         SORPTION-REGENERATION

                 FIGURE I
PROCESS

-------
                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

-------
Page Intentionally Blank

-------
                           SECTION V

               FIELD APPLICATION DEVELOPMENT
SITE FOR PILOT PLANT

     The carpet yarn fiber dyeing facility of C. H.  Mas land & 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

-------
  1600
£1400
8 1200
  1000
LU
x
o
  800
3 60°
UJ
  400
            11     12     I      23

               SAMPLE  TIME  (O'CLOCK)



          EFFLUENT  PROFILE  COD vsTIME


                   FIGURE 2
                    12

-------
 II      12     I      2      3
    SAMPLE TIME (O'CLOCK)

EFFLUENT PROFILE  COLOR vs.TIME
      FIGURE 3
         13

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

           EFFLUENT PROFILE BODj-vs TIME
                   FIGURE 4
                  14

-------
    II      12     I      234
       SAMPLE TIME (O'CLOCK)

EFFLUENT  PROFILE-SUSPENDED SOLIDSvsTIME
           FIGURE  5
              15

-------
                       Table II
          Masland Dyehouse Raw Waste Profile
Parameter
Mean
Range
Color - units *                2.5
pH                            4.3

Temperature-   F.            110

BOD   (biochemical
      oxygen demand) mg/1    396

COD (chemical oxygen
      demand) mg/1           700

Suspended Solids -  mg/1       27
               0. 7 - 5.9

               4. 0 - 6.0

               90 - 1Z4


               95 - 700


               305 - 1450

               6-70
*  Tinctorial Strength.
                              16

-------
     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 dyehou.se  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

-------
 lOO
  80
£60
                                    C-CONTAM (NATION CYCLE
                                    R-REGENERATION CYCLE
LU
CE

O
o
o
40
                                                         i
                      c..  t><3
C-l
R-l
6HR.
              C-Z
              R-2
              G HR.
                        C-3
                           R-3
                           6HR.
                                       R-4
                                      12 HR.
R-5
I2HR.
                                                    C-6
                      REGENERATION  STUDIES
                            FIGURE 6
                            18

-------
                                                    Table III

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

       Calcozine Acrylic Blue HP Cove
       Calcozme Acrylic Red B
 Dyes Calcozine Acrylic Violet 3R
       Calcozme Acrylic Yellow 3RN
       Astraaon Yellow 7GLL
       Acetic Acid, 56<7C
       Merpol DA
       Salt
       Retarder 98

       CYCLE C2_.  B LUE WOOL

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

       CY_CLE C3   BLACK WOOL

 Dye  Omega Chrorpe Black ALA
       Acetic Acid, 56%
       Moth Snub
Dyes
Dyes
Dyes
CYCLE C4-  RUSTJVOOL

Lanafast Orange PDL
Lanafast Navy NLF
Lanamid Red 2GL
Acetic Acid, 56%
Errikalana WSDC
Moth Snub
      CYCLE C5-
                   jOLD ACRYLIC
A.strazon Yellow 7GLL
Astrazon Red GTL
Astrazon Blue SGL
Acetic Acid, 56%
Merpol DA
Retarder 98
Salt

CYCLE C6   GREEN ACRYLIC

Sevron Yellow 3RL
Astrazon Red GTL
Astrazon Blue 5GL
Nabor Blue  2G
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

-------
                        COLUMN 3
                        COLUMN 2
                        COLUMN I
180    360    540

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

-------
                         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

-------
      C.HMASLANO  9 SONS
           DYE  HOUSE
      SUB FLOOR
       DRAIN
           UNDERGROUND DYEHOUSE
            WASTE EFFLUENT LINE
PLAN FOR LOCATION
OF FRAM WASTE
TREATMENT SYSTEM
AT C.H.MASLAND ft SONS
WAKEFIELD.R.I.
                TREATED
                WASTE
                OUTFLOW
MAIN STREET
                            FIGURE 6
                               22

-------
Waste Treatment System - C. H. Masland &• Sons,
  Wakefield,  R, I.  - Activated Carbon Columns
                    Figure 9

-------
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

                 2
Up to 17. 0 gpm/ft


1, 000 gallons


40 SCFM
                         25

-------
REGCNERANT
RESERVOIR
                                      77-3 ACTIVATED
                                      VA 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 Appendbc A for complete Phase I data.

-------
 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
 operation -

     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 dyehou.se effluent flow/ (the remainder was by-
passed).  However,  the entire dyehouse effluent was treated during
Phase II.

    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 froin 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

-------
 7000
                         POUNDS  OF COD REMOVED
                       AS A FUNCTION OF GALLONS OF
                           WASTE WATER TREATED
                                 FIGURE 13
                                                       CARBON
                                                       (110 gpm)
Q
U

O
|sooo.
a
a
o
u
v>
a
z
200O-	
      PHASE
      CARBON
      ( 60gpfn)
                              8      10     12

                           GALLONS TREATED ( X iO9)
                                                   14
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 w.ere 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/1.

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

          (3)   NUTRIENTS - Supply 5 Iba. 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

-------
Page Intentionally Blank

-------
                          SECTION VII

                  WASTE TREATMENT SYSTEM
                     DESIGN AND ECONOMICS


PROPOSED REDESIGN Or 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)  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
DYEHOUSE
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, ZOO  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

-------
RAW WASTE
        FEED
        PUMP
 REGENERATION
  VESSEL
                  A
   i	•—r
      ^7\
                                      •'
                             -L._.».
      ^-
                !    I
                r?s
           _ r i
i^\

FA
       VOJ
                                         TREATED
                                         EFFLUENT
                   PROPOSED I MOD 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                Ope rating 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               Qperatuig Cost

               75% COD Removal      $384/day
                                         or
                                      38.4C/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.

-------
                           SECTION VIII

                          ACKHOWIEDGMENTS

     Supervision of the Masland pilot plant operation and back-up
laboratory work was carried out by Edward L. Shunney of Fran
Corporation.  He was assisted by Edward Chase and Anthony
Perrotti of the Fram staff.  The cooperation of Mr. Harold
Burkholderj 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.

-------
Page Intentionally Blank

-------
                       SECTION IX

                     REFERENCES
1.    Knowles,  C. L. , Jr., Chemical Engineering,  77,
      No. 9, pp 1J03-109 (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,19£>3.

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).

-------
Page Intentionally Blank

-------
SECTION X
APPENDICES

-------
Page Intentionally Blank

-------
       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
B/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
46.0
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

                                       60.9
                                       77.5
                                       68.4
                                       64. 1
                                       72.5
                                       72.4
                                       72.0
                                       59.3
                                       45.8
                                       22.8
                                       17. 5
                                       53. 8
                                       36
                                       48
                                       56
                                       38
                                       35.2
                                       43.7
                                       36.5
                                       32.6
                                       25.0
                                       36. 1
                                       18.6
                                       30.3
                                       27.9
                                       17.4
                                       44
                                       32
                                       40
                                       19
                                       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 a"s possible without loss of carbon
    granules^ '.   Weigh flask containing greatest water residual
    and adjust all others, including a  carbon free control  flask,  to
    an equivalent amount.
                                                   (2)     o
E-  Immediately after adding 200 ml  of contaminant   (100  F.  ) to
    each flask,  agitate on mechanical shaker for prescribed time.

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 "q1

               „ (C   - C )
                     M

    where V = total volume of solution in liters.
          C   =  concentration of influent in mg/1 of TOD.
          C  =  concentration of supernatant in mg/1 of TOD.
          M  =  grams of carbon.

I.   Plot ''q" versus  C (Figure 16).
                                  51

-------
                                                         r
   70-
   60-
                     FIGURE 16

                 ADSORPTION  ISOTHERM

                  MASLAND EFFLUENT
                                                       CALGON FILTRASORB 400
   30-
                                                                     WV-G
CD
ct
z
4
a.
o
o
tc
o
in
o
<
Q

e
o
40
                                                                  \ZHZQ
   30-
                                                                      -NUCHAR WV-L
20


    io-

                                                                        •-WITCO 71 § IZX3O
                   100              200


                 CONCENTRATION (mg/1 TOD)
                                                       300
                                                                        400

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

-------
             Table VII
   MASLAND  -  WAKEFIELD
          Phaac II Data
            Week  1


Total TOC -




% Reduction
Total COD -




% Reduction
Tola! BOD -




"7o Reduction
pH -






ID
Out (U
Out #2
Out 13
Out #4
thru #4
In
Out #1
Out 42
Out #3
Cut #4
thru #4
In
Out #1
Out 1*2
Out #3
Out #4
thru #4
la
Out 01
Out #2
Out |3
Out #4
Tuesday
A M
130
40
30
20
10
92.3
345
110
69
49
47
B6.5
118

41

25
78.6
5.6
8.Z
7.7
7.6
7.7
- 7/21
P. M
325
140
100
92
86
73.5
945
363
297
246
180
81.0
370

84

£7
84. 6
4.9
7 7
3 1
3. 1
9 1
Wednesday -
A M.
280
130
100
86
62
77. S
792
439
345
306
286
64.0
282



60
78.7
5.3
7 2
a 2
8.3
a 3
7/22
P M.
27C
I6G
130
120
110
59. Z
335
592
439
419
235
71 9
350



165
52.9
4,7
5.9
6.9
7.2
7.4
Thursday -
A M.
180
105
82
76
75
58 5












6.4
6,9
7. 1
7.3
7.4
7/23 Friday - 7/Z4
P M AM P M
ISO 210 225
145 135 165
I2C 100 130
105 85 115
90 80 100
52. 6 61,9 55 5












52 57
64 6.4
65 69
68 7.1
6.9 73
% Color Reduction




Thru 1
Thru 2
Thru 3
Thru 4




Total Da.ly Flow
(Gallons x 10 )




9.0









15. 5









15.2 14-4
             Table VIII
MASLAND  - WAKEFIELD
        Phase U Data
          Week 2


Total TOC -




% Reduction
Total COD -




% Reduction
Total BOD -




% Reduction
pH -






In
Out f 1
Out #2
Out 13
Out *4
thru #4
In
Out #1
Out (fZ
Out #3
Out #4
thru #4
In
Out It I
Dot f»2
Out J?3
Out #4
thru #4
In
Out #1
Out «Z
Out 43
Out #4
Monday
A.M.
120
52
4C
30
25
79 0












4.0
5.5
& B
7 2
7-3
- 7/27
P.M.
122
60
40
35
30
75.5












3.9
4.3
6.4
6.9
7. 1
Tiieec
A.M.
220
175
132
105
75
66.0
574



202
65.0
265



120
54.7
5. 5
5. 8
6. I
6.6
6.7
% Color Reduction




Total Daily
Thru 1
Thru 2
Thru 3
Thru 4
FJow





(Gallons x 1 0~)





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
IfrO
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
28C
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
6.1
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.
2fcC
233
ISC
ISO
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

-------
                                                      Table IX
                                            VASLAND  - WAKEF1ELD
                                                     Phase H Data
                                                       Week 3
                      Monday - 8/3     Tuesday - 8/4
                   A.M.      P.M.  A.M.     P.M.
Total TOC - In
            Out HI
            Out IZ
            Out i»3
            Out M
% H eduction thru 04

'I otBl COD - In
            Out fl
            Out (S2
            Out (»3
            Out #4
?» Reduction thm #4

Total BOD • In
            Out* I
            Out »2
            Out #3
            Out #4
% Reduction thru *4
130
 71
 55
 52
 52
60.0
uo
 u
 41
 35
 35
57,7
pH -




% Color




Total Da
(Gallons
In
Out 
-------
                                  Table XI
                      MASLAND  - WAKEF1ELD
                             Phase II Data
                                Week S


Total TOC -




% Reduction
Total COD -




% Reduction
Total BOD -




% Reduction
pH -






In
Out nil
Out 02
Out #3
Out 14
thru H
In
Out #1
Out #2
Out U3
Out f 4
thru *4
In
Out «]
Out »2
Out 03
Out #4
thru *4
In
Out #1
Out *Z
Out #3
Out #4
Monday
A.M.
115
50
45
43
35
69.5












5,7
6.0
6. 1
6.2
6,2
- 8/17
P. K
120
90
75
63
50
SB, 4












5,6
5.8
6.0
6.0
6.0
Tuesday
A M.
224
m
155
140
120
46.4
491
353
285
244
208
57,5






5.9
6. 3
6.5
6.7
6.8
- B/ia
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
449
487
479
25.7
195
155
ISO
118
93
52.3
6.2
6.7
6.8
6.9
7.0
- 8/19
P.M.
264
192
183
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
- «/zo
P. M
333
270
242
223
215
35.5












5.7
5.9
fc. 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.C
6.0
6.0
% Color Reduction




Thru 1
Thru Z
Thru 3
Thru 4
60
85
100
100
to
90
1DO
100
50
80
90
100
63
90
100
100
60
90
100
100
80
90
100
100
100
100
100
100
80
100
100
100
90
100
100
100
90
100
100
100
Total Daily Flow
(Galloni x 10 )
28.8

29.2

22.0

34 4

28. H
Total TOC - In
            Out til
            am n
            Out #3
            Out H
% Reduction thru #4
Total COD - In
            Out #1
            Out |H2
            Out |J
            Out #4
% Reduction thru #4

Total BOD - In
            Out |1
            Out |S2
            Out #3
            Out #4
% Reduction thru C4
pH    -      In
            Out PI
            Out l«2

            Out *4
% Color Reduction
            Tnru  #1
            Thru  i»2
            Thru  «3
            Thru  04
Total Daily Flow
(Gallons, x 10 j
                                  Taole XII
                       MASLAND -  WAKEFIELD
                               PhaseII Data
                                  Week 6
 Monday - B/24   Tuesday - 8/25   Wednesday - B/26   Thursday - 8/27   Friday -
 A M.     P.M.   A.M.      P.M   A.M.       P  M.  AM,     P.M.   A.M.
250
210
195
180
170
32 0
 5 7
 6.7

 80
100
IOC
100
           275
           175
           40.0
           5.5
         5.9

         60
         80
         100
         100


         31.4
455
395
305
280
245
46









4.9
5.4
40
100
100
100
410
385
370
34C
330
19,5









4.7
5.3
4D
80
100
loo
260
Z30
195
180
165
36.5
612
586
467
418
331
62 3
250
160
36.0
5.5
5.8
40
60
80
90
                                              305
145
52 5
                                              729
                                              331
                                              54.7
                                              320
                                              222
                                              30 6
285
235
200
190
175
38.6
                                                      5.6
        5.8

        40
        60
        80
       100
                                                                290
180
37 9
                                                                53
260
230
190
ISO
160
38 5
                                                                        5.3
         5.5      5, 6

         50       40
         90       60
         100       80
         100      100
                                                                                                     8'28
                                                                                                        P M
140
48.2
                            33, 6
                                              30.0
                                                                                5.4
                5.6

                40
                60
                60
               ICO


                33.6

-------
          Table X11I
MASLAND -  WAKEF1ELD
         Phase n Data
           Week 7


Total TOC -




% Hcduction
Total COD -






In
Out 01
Out />2
Out |»3
Out i»4
thru ((4
In
Out (11
Out #2
Out S3
Out 04
Monday
A.M.
Z70
190
165
HO
U5
53.7





- 8/31
F.M
295



13D
56,0





1 uesday
A. M.
290
170
140
120
105
63.9





- 9/1
P M.
170



100
41.2





% B eduction thru £4
Total BOD -




"^ P eduction
pH -




In
Out fl
Out »2
Out (13
Out (14
thru 1*4
In
Out (fl
Out #2
Out (13
Out H






6.3



5.7






6.1



5.6






4. 1



5 0






4.6



5 3
Wednelday - 9/2
A.M. P.M.
215 405
180
155
140
120 210
44.2 48.2
520 582
394
358
342
330 434
36.5 Z5.4
195 285
192
190
178
150 Z55
23.0 10.5
5.9



5. a
Thursday - 9/3
A. M P. M
260 295
220
200
180
145 195
44.2 34. 0












4.7 4.3



63 6-0
& Color Reduction




Total Daily
Thru 1
Thru Z
Thru 3
Thro 4
Flow
90
100
100
100

(gallons x 1C')
SO
100
100
100

32.4
40
90
100
100


40
80
90
100

32.8
40
60
90
100

28,8
50 30
80 70
100 93
ICO 100

32.4
             Table XIV
   MASLAND  -  WAKEFIELD
          Phase n  Data
            Week 8


Totil TOC -




% Reduction
Total COD -




% Reduction
Total HOD -




% Reduction
pH






In
Out f 1
Out *2
Out l»3
Out #4
thru 44
In
Oat #1
Out #2
Out #3
Out #4
thru #4
In
Out #1
Om #2
Out ft
Out M
thru M
In
Out H
Out #2
Out 03
Out »4
Tuesday - 9/8
A.M. P.M.
150 160
130 ISO
115 140
100 120
85 105
43.4 34.4

















Wsdnei
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



t. 5
iday - 9/9
P.M.
210
190
170
L40
110
47 6
490



247
29.2
235


"
145
38.3
5. 1



6.7
Thursday - 9/10 Friday -9/11
A.M. P- M A .M P. M
225 190 230 190
150
130
105
90 110 115 !15
60. 0 42, 0 50 0 39 5












6.4 4.9 4.7 4.9



6,7 6,5 6. Z 6.2
% Color Reduction




Total Dally
Thru 1
Thru 2
Thru 3
Thru 4
Flavu
(Gallons x 1 0')


60 90
80 100
90 100
100 100

27.6

80
90
100
100



70
80
90
100

29- 2
57
80 70 80
90 80 90
100 100 100
100 100 100

28 0 27.2


-------
                                                        Tatle XV
                                                MASLAND  -  WAKEFIELD
                                                        Phase II Data
                                                          Week 9


Total TOC -




% Reduction
Total COD




% Reduction
Total BOD -




% Reduction
pH -




Monday
A.M.
la 235
Out #1
Out #2
Out #3
Out #4 90
thru f4 61.7
-In
Out #1
Out #2
Out #3
Out *4
thru fl>4
In
Out #1
Out |*2
Out 1*3
Out 1*4
thru #4
In 6.7
Out #1
Out 1*2
Out 1*3
Out #4 6. 5
. 9/14
P.M.
260



185
28. B












5 5



A 0
Tuesday - 9/15
AM. P M.
315 305



175 140
44 5 54. 1












6.6 5.3



6,8 59
Wednec
A M.
ZZO



145
34. 1
451
400
396
359
321
28. B
205
178
172
1 52
130
36.6
4.7



6 4
iday - 9/16
P.M
260



190
27. D
592



445
24. B
232



215
7.3
5.2



6.2
Thursday 9/17 Fridaj
A.M P, M A. M.
245 210 205



100 105 80
59.2 50.0 61. D












S.S 5.6 5.7



6.2 6. 1 63
% Color F eduction




Thru 1 90
Thru 2 100
Thru 3 100
Thru 4 100
80
90
100
100
90 80
100 90
100 100
100 100
90
100
100
100
90
100
100
100
90 90 30
100 100 80
100 100 90
100 100 100
Total Daily FJow
(Gallons x 10 )
28. 8
28.0

28 8
27. 2
                                                                                                     P M.
                                                                                                       29C
                                                                                                        140
                                                                                                        51.8
                                                                                                        5, 3
                                                                                                        80
                                                                                                        90
                                                                                                       100
                                                                                                       100
                                                                                                        27.2
Total TOC - In
            Out j»l
            Out #2
            Out l»3
            Out rf/4
^ Reduction thru M4
Total COD - la
            Out #1
            Out rfZ
            Out 1*3
            Out #4
% Reduction thru #4
Total BOD - In
            Out *1
            out n
            Out #3
            Out it
% Reduction thru tf4

pH   -      In
            Out +1
            Out n
            Out +3
            Out *4
% Color Reduction
            Thru 1
            Thru 2
            Thru 3
            Thru 4

Total Daily Flow
(Gallons K 10 )
                                                        Table XVI
                                               MASLAND  - WAKEFIELD
                                                       Phase H Data
                                                         Week 10
A  M.

 150
 140
 120
 100
  90
 40 0
                                                Monday - 9/21
 6.9
 6.9

 70
100
100
100
                                                            P.M.

                                                              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 41
out n
Out #3
Out #4
% Reduction thru #4
Total COD - In
Out #1
Out 02
Out 13
Out #4
% Reduction thru #4
Total BOD - In
Out #1
Out n
Out #3
Out #4
% Reduction thru fr4
pH - In
Out *1
Out *2
Out #3
Out 44
% Color Seduction
Thru 1
Thru 2
Thru 3
Thru 4
Total Daily Flow
(Gallons x 10 )
Wednei
A.M.
320
3CO
240
210
185
42.2
464
40 fi
340
321
284
38.3
Z20
200
140
132
105
52.3
5.2



6, T

70
85
90
100


iday - 9/30 Thursday - 10/1 Friday - 10/2
P M. A.M. P.M. A. M P. M
195 210 270 290 205



100 135 190 130 85
48.7 35.7 29.6 55.2 58.5
5B4



316
45 9
234



131
22.6
5. 1 5.4 6.2 61 6. 5



6.7 6.6 6. 3 6.3 66

70 90 80 TO 60
93 100 90 80 70
100 100 90 100 BO
100 100 100 100 100

42 9 47 9 44 6
            Table XVIII
MASLAND  - WAKEFIELD
        Phase II Data
          Week 12


Total TOC - In
Out #1
Out #2
Out fi
Out 04
% reduction thru (*4
Total COD - In
Out 01
Out #Z
Out #3
Out #4
% Reduction thru i(4
Total BOD - In
Out #1
Out #2
Out #3
Out #4
% Reduction thru #4
pH - In
Out #1
Out #2
Out S3
Out #4
% Color Reduction
Thru 1
Thru 2
Thru 3
Thru 4
Totil Daily Flow
(Gallone x 10 )
Monday - 10/5
A. M. P M.
230 ISO



115 105
50.0 41.7












5.4 5.7



6.9 6.1

70 90
80 IOC
8C 100
100 100

36.0
Tuesday - 10/6
AM P. M.
135 220



65 120
51. B 45.5












64 6. 1



6.5 6.7

40 BO
30 80
90 100
100 100

39.0
Wednesday .
A. M
215



100
53.5
273
241
120
101
94
65.6
123



53
56.9
5.3



6.2

75
80
90
too


10/7 Thursday - 10/B Friday - 10/9
P.M. A M. P.M. AM. P M.
!50 140 150 225 190



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 62 51



66 60 61 68 67

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

47,9 38-0 47 0
         59

-------


Total TOC - In
Out #1
Out #2
Out *}
Out 44
% Reduction thru *4
Total COD - In
Out fl
Oul fr2
Out *3
Out M
% Reduction thru #4
Total BOD - IE
Out #1
Out #2
Out #3
Out *4
% Reductionthru #4
pH - In
Out 01
Out #2
Out 13
Out 44
% Color Reduction
Thru 1
Thru 2
Thru 3
Thru 4
Total Daily Flow
(Gallons x 10 >
Monday - 10/12 Tuesdi
A.M. P.M. A.M.
Z15 15Q 130



!05 105 75
51.2 30.0 42 3












5.5 5.6 6.3



7.9 6.0 6.7

60 70 7C
80 100 1C
90 100 90
100 100 100

46.2
            Table XIX
   MASLAND  -  WAKEFIELD
           PhaseD Data
             Week 13

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

            60
            80
            90
           100

            39.6
                    Z10
 160
 23.8
 294
 239
 141
  94
  BO
 71.8
 134
                     62
                    53 7
                    4.9
 6.)

 70
 SO
1QD
100
                               155
 100
 35.5
 452
                               214
                               52 6

                               218
            140
            3S 8
            6.2
 6.7

 70
 BO
ICO
100


 42.9
                                       145
  50
 65.5
                                       5 4
 6.0

 50
 60
 90
100
                                                210
 105
 50 0
                                                5  I
 6.4

 60
 70
 SO
100


 47.9
                                                      230
115
so.. D
                                                      6.2
6 6

50
70
90
90
                                                                160
 95
40 6
                                                                5  4
6. 3

40
70
80
90


44.6
              Table XX
      MASLAND  - WAKEFIELD
             PhaseII Data
              Week 14


Total TOC -




% Reduction
Total COD -




% Reduction
Total BOD -




% Reduction
pH -






. In
Out fl
Out #2
Out 13
Out 04
thru #4
. In
Out #1
Out tZ
Out #3
Out #4
thru *4
. In
Out #1
Out #2
Out 83
Out #4
thru «4
In
Out #1
Out +Z
Out #3
Out #4
Monday - 10/19
AM P.M
155 190



11C IZO
29.0 36. B












4.2 6.2



6.4 66
Tuesday - 10/20
A.M P.M.
150 165



95 100
36.' 39.4












62 64



6.4 65
Wednesday
A M.
Z40



160
33.3
310
262
156
120
115
62.9
190



92
51.6
6.7



6.9
- 10/21 Thursday - 10/22 Friday - 10/23
P.M. A M, P.M. A.M. P M.
190 190 290 325 355



105 80 125 130 205
44.7 57.9 56.9 60.0 42.3
362



222
3B.7
246



m
S^. 3
6. 3 5.Z 6. 7 4.8 53



7.5 6. 1 67 64 6.8
% Color Reduction




Total Daily
Thru 1
Thru i
Thru 3
Thru 4
Flow
(Gallons K 10J)
70 40
80 50
ICO 60
100 90

39.6
70 60
90 80
100 100
100 100

4Z.9
30
60
70
90


80 50 70 40 70
90 60 30 60 90
100 90 100 90 100
ICO 100 190 90 100

42.9 47.9 4Z.9
                   60

-------
          APPENDIX D
CHEMICAL REGENERATION STUDIES
                  61

-------
                           APPENDIX D

               CHEMICAL REGENERATION STUDIES
     When the Witco 718 activated carbon during Phase 1 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  S O  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  Oft regeneration.  Figure 20 is a plot of TOD in the effluent after
the fhird regeneration with K S2On-  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

-------
    All of the previously discussed K S O  regenerations were
carried out  ato25  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^OR regeneration at 50  C.
          £ L*  O

    The  degree of carbon adsorption recovery by hot K S Oft
(50  C. )  regeneration was 70 - 80%.  It was felt that if Ihis  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^O,,, 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

-------
900
800
700
600
500
40O
3OO
200
 IOO
                     REMOVAL  PROFILE
                  H2 02  REGENERATION (25°C)
                        FIGURE 17

-------
aoo
700
                            INFLUENT
100
                      REMOVAL PROFILE
                   K2 S2 Og REGENERATION (25°C)
                          FIGURE  18
                          65

-------
  90X3
  800
  700
  600
   500
                            INFLUENT
O
o
   400
   300
   200
   100
                         SECOND  K2S208
                        REGENERATION  (25°C)

                           FIGURE 19
                             66

-------
600
 EDO
                 THIRD K2S208
               REGENERATION (50'C)
                     FIGURE 20
                       67

-------
  900
  aoo
  TOO
  600
  5OO
  400
a
o
  300
  200
  IOO
                       REPEAT OF 50°C
                     K2S2Oe REGENERATION

                         FIGURE 21

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

-------
  3.00-
o
o
CD

\
O
o
o

u.
o
2.00- -
                                                                            • <
   1.00- -
         i i  i  i  i  i  ill  1  I  I  i  i I   L  I  i  I  I  i  i  I  I  I  I  ]  I  i  I  i  i  i   i  i 1
                 I  '  '  '  '  I
                           10
                                     15         20        25         30
                                                                              35
                             SAMPLE  NUMBER
                        CORRELATION OF COD TO BOD
                               FIGURE  22
                                    70

-------
  3.00- -
                 ;—*\
o
o

•\z,oo-
o
o
p

o

                                                    ~AVERAGE- 2.54
                                                                      ,/
4
DC
  1.00-
        1  I I  I II L 1  I  I  I  \  I  1  |  I  I  I  I  I  I  I  I  I  I  1  I  I J I   I |  |  L I  I

               5         10         13        20        25        30        35


                           SAMPLE  NUMBER

                     CORRELATION  OF COD TO  TOG

                             FIGURE 23
                                  71

-------
  1.00- -
o
o
I-
X
o
o
u
u.
O

o

<
K
        I  I  I  I  I  I  I  I  I I  I I  I  I  t  I  I  I  I  I  I  I  1 I  I  I  I  I  I  I  I  1  1

                5         10         13        20        25        30

                            SAMPLE NUMBER
                      CORRELATION  OF COD TO TOD
                             FIGURE  24
                                  72

-------
     APPENDIX F
1  MOD 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

   	—  and  *• x T  are tne 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
       Qoo  =    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 . *    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'

       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-

       P e r c ent R e duct i on(COD)      Carbon (Ibs. )       G jgpm/ft2)

                50                       110,000        12
                75                       330, 000        12

-------
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
       6110     _,K   3
       	  = 765 ft  col.
                                    2
     For 8' diameter   area = 50.3 ft

   Height =  ?-5    =  15.2'

     Check the  surface area for flux
                  694 gpm               ,  2
       Flux   =    cn V	  =   13. 8 gpm/ft
                   50.3 2
     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' 5WD 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
       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  = JJJ1  = 18'
     Check the  surface area for flux
      Flux=       SJpL =10. 9 gpm/ft2
      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  =  2 x 8 x 1145 = 18, 300  ft
Use 30'  x 60' x 1(V SWD Regeneration Vessel

                                 75

-------