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
------- |