EPA-600/2-78-047
March 1978
Environmental Protection Technology Series
HYPERFILTRATION FOR RENOVATION
OF COMPOSITE WASTE WATER AT
EIGHT TEXTILE FINISHING PLANTS
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
-------
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental Protec-
tion Agency, have been grouped into nine series. These nine broad categories were
established to facilitate further development and application of environmental tech-
nology. Elimination of traditional grouping was consciously planned to foster technology
transfer and a maximum interface in related fields. The nine series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
6. Scientific and Technical Assessment Reports (STAR)
7. Interagency Energy-Environment Research and Development
8. "Special" Reports
9. Miscellaneous Reports
This report has been assigned to the ENVIRONMENTAL PROTECTION TECHNOLOGY
series. This series describes research performed to develop and demonstrate instrumen-
tation, equipment, and methodology to repair or prevent environmental degradation from
point and non-point sources of pollution. This work provides the new or improved tech-
nology required for the control and treatment of pollution sources to meet environmental
quality standards.
REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/2-78-047
March 1978
HYPERFILTRATION FOR RENOVATION OF
COMPOSITE WASTE WATER AT EIGHT TEXTILE
FINISHING PLANTS
Craig A. Brandon, John J. Porter,
and Donald K. Todd
South Carolina Textile Manufacturers Association
Suite 1700, Bankers Trust Towers
Columbia, South Carolina 29201
Grant No. S802973
ROAP21AZT/8
Program Element No. 1BB036
EPA Project Officer: Max Samfield
Industrial Environmental Research Laboratory
Office of Energy, Minerals and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
-------
ABSTRACT
This research program was conducted to evaluate hyperfiltration for
the renovation of composite wastewater at selected textile plants. Eight
plants were selected to include several EPA guideline categories. The
primary objective was to assess the feasibility of utilizing hyperfiltration
as a general treatment method for the textile industry. The assessment
required results of membrane performance evaluations conducted in the field,
reuse evaluations by textile plant operators, and evaluations of the
treatability of the wastewater concentrates by conventional means.
The program was conducted in two phases. Initially, as a screening
test phase, samples of the wastewater from twelve plants were transported
to Clemson University for processing by hyperfiltration. Reuse was evaluated
by the central dye laboratory of a cooperating textile corporation. Results
indicated no preferences among the twelve plants, so the selection of eight
plants for involvement in the on-site evaluations was made on the basis of
guideline categories. The on-site testing phase was accomplished with a
mobile laboratory.
The results of the membrane performance evaluations indicated the
technical feasibility of both cellulose acetate and dynamic membranes for
textile wastewater treatment. The quality of renovated product water, after
hyperfiltration, was satisfactory for reuse in scouring, bleaching, dyeing,
and finishing when 90% of the wastewater was recovered.
The residual concentrate, 10% by volume, contained significant quanti-
ties of dyes and chemicals but direct reuse was not generally demonstrated.
The treatability of the residual concentrate by conventional means was,
however, established in bench-scale tests as equivalent to that of the
current composite plant effluent.
Recycle and the resulting conservation of water, energy (hot water),
and chemicals led to the conclusion that hyperfiltration is a very promising
technology for wastewater renovation. The chemical removal efficiency
suggests hyperfiltration may be useful in the control of toxic emissions.
The high-temperature capability of some membranes suggests a major role in
energy conservation by direct recycle of that water prior to discharge to
the plant drains. Chemical recovery may also be enhanced when process
drains are treated individually. However, a major reservation about hyper-
filtration remains in the uncertainty of cost because of the lack of a
full-scale operating facility.
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CONTENTS
Page
Abstract 11
Figures IV
Tables V
Acknowledgements Vl
1. Introduction 1
2. Conclusions 6
3. Recommendations 7
4. Textile Plant Characteristics. . . .„ 8
Fibers Processed and Chemicals Used .... 8
Wastewater Characteristics 8
5. Equipment and Procedures 17
Mobile Laboratory 17
On-site Test Procedures 19
6. Reuse and Treatability 22
Reuse Sample Generation 22
Product Water Reuse 22
Reuse Summary 36
Treatability 36
7. Membrane Performance 41
Flux Decline and Rejection 41
8. Cost Estimates 46
References 52
Appendices
A. Screening Test Results 53
B. Plant #50. 62
C. Plant #60 81
D. Plant #70 105
E. Plant #40 125
F. Plant #80 148
G. Plant #81 , 167
H. Plant #82 185
I. Plant #83 201
J. Chemical and Biological Treatability of
Hyperfiltration Concentrate 221
111
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FIGURES
Number
Schematic drawing of hyperfiltration loops in the
mobile hyperfiltration laboratory 18
Flow schematic for equipment set-up at Plant #40 .... 21
Flux decline and conductivity rejection of dynamic
membrane Modules #4, #10, and #19 with untreated
textile wastewater with feed velocities (V) as
indicated. 43
Flux decline and conductivity rejection of spiral-
wound cellulose acetate membranes with untreated
textile wastewater 44
iv
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TABLES
Number Page
1 comparison of Hyperfiltration Module Configurations. . . 2
2 Plants, Fibers Processed, and Effluent Guideline
Subcategories Involved in Field Testing 4
3 Production Capacity Parameters 9
4 Potential Conservation by Recycle for the Textile
Industry 11
5 Process Characteristics of the Mills Involved in
On-site Tests. .......... 12
6 Plants, Guideline Subcategories, and Effluent
Characteristics 14
7 Chemical Analyses of Selected Wastewater Grab
Samples - Plant #40 16
8 Membrane Evaluation Schedule ... 20
9 Chemical Analyses of Spiral-wound Cellulose Acetate
Membrane Product Water Evaluated for Reuse 24
10 Chemical Analyses of Selas Dynamic Membrane Product
Water Evaluated for Reuse 26
11 Chemical Analyses of Tubular Cellulose Acetate Membrane
Product Water Evaluated for Reuse 28
12 chemical Analyses of Spiral-wound Cellulose Acetate
Membrane Concentrate Evaluated for Reuse 30
13 Chemical Analyses of Selas Dynamic Membrane Module
Concentrate Evaluated for Reuse 32
14 Chemical Analyses of Westinghouse Tubular Cellulose
Acetate Membrane Module Concentrate Evaluated for
Reuse 34
15 A Summary of Overall Best Results for Treatment Methods. 38
16 Concentrate Waste Characterization ..... 39
17 Tabulation of Membrane Evaluation Tests and Test
Duration 42
18 Costs of Cellulose Acetate Membranes Processing
Composite Waste at Eight Mills 47
19 Costs of Dynamic Membranes Processing Composite Waste
at Eight Mills 50
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ACKNOWLEDGEMENTS
Any project of this scope is obviously indebted for its success to
many individuals. The guidance of the Finishing Plants Committee was
vital. In particular, the work of Mr. George Cocoros was very instrumental
in the timely completion of the testing phase of this study. The parti-
cipation of many individuals at each of the twelve finishing plants was
very important in the planning, operation, and evaluation of test results.
Dr. J. S. Johnson, Jr., of the Oak Ridge National Laboratory provided
invaluable consultation about membrane performance. Mr. Gary Westmoreland
and Mr. Warren Sissen of ORNL provided valuable assistance with the
operation of the mobile laboratory. The cooperation in time and material
support provided by membrane manufacturers is also acknowledged with
gratitude, in particular, ROGA Division of UOP, Union Carbide, and Selas
Flotronics. The guidance and direction of Mr. T. N. Sargent and Dr. Max
Samfield, EPA Project Officers, was most valuable during the course of
the study.
VI
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SECTION 1
INTRODUCTION
The more stringent requirements for the discharge of industrial waste-
water necessitates the evaluation of treatment technologies which provide
recycle capabilities. Hyperfiltration1'2 (reverse osmosis) is a separation
technique which yields for textile wastewater a relatively pure product
water for recycle and energy conservation when the recycled water is hot.
The resulting concentrate, if recycled, effects chemical recovery.
The hyperfiltration process selectively filters soluble and insoluble
chemicals from water. This technology has been used successfully in
selected industrial applications^~5 where the recovered chemicals have
significant value. The application of hyperfiltration to renovate composite
wastewater was demonstrated in a pilot plant at La France Industries.^ The
La France study found that up to 95% by volume of the composite wastewater
could be recycled as process water with no effect on dyeing quality. The
technical feasibility of recycling the concentrated chemical residue was
also determined in a number of full-scale production dyeings. These results
were obtained with each of the four basic types of hyperfiltration units
listed in Table 1.
The current study investigated hyperfiltration for renovation of
composite plant effluent for twelve textile plants. The reuse of 90 - 95%
of the composite water, after purification by hyperfiltration, as general
plant process water was confirmed by laboratory tests at each mill. The
recovery of chemicals from the concentrate would usually require additional
study and process modifications. However, the treatability of the concen-
trate by conventional means was confirmed in bench-scale reactor tests. The
results of this study are in agreement with the results from the pilot plant
at La France Industries.
Recycle, and the resulting conservation of energy and chemicals, makes
hyperfiltration a very promising technology for wastewater renovation.
However, a major reservation about hyperfiltration is the cost. While
recycle will achieve some savings, the preliminary cost estimates suggest
a positive return on capital, there exists no experience with large-scale,
long-term operation. In addition to equipment costs, the effect of long-
term recycle on plant production quality and costs are also not known.
Since the potential of hyperfiltration is very promising, we recommend
additional study to establish the economics of plant-scale operations and
the effects of recycle on textile production. The additional studies should
include process modifications to accomodate recycle and to reduce the liquid
effluents from dyeing and finishing processes.
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TABLE 1. COMPARISON OF HYPERFILTRATION MODULE CONFIGURATIONS
Membrane Material
Production Rate,
m3/m2/day
Method of Membrane
Replacement
High Pressure
Limitation
Parti culates
in Feed
Permissible Feed
Range , pH
Maximum
Temperature, °F (°C)
Spiral
cellulose
acetate
67 - 1000
module
(on-site)
membrane
compaction
filtration
required
5.5 - 7.5
100 (38)
Tubular
cellulose
acetate
13 - 200
tubes
(on-site)
membrane
compaction
no problem
5.5 - 7.5
100 (38)
Hollow-fine
Fiber
polyamide
27 - 2000
module
(on-site)
fiber collapse
filtration
required
2-10
100 (38)
Dynamic
hydrous Zr(IV)
oxi de-poly acrylate
200 - 2000
in-situ
no problem
no problem
4-11
>195 (>90)
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This report summarizes the results obtained in this study under the
general categories of textile plant characteristics, wastewater reuse and
treatability, membrane performance, and cost estimates. The detailed
results and data obtained at each plant are given in the appendices of this
report.
PURPOSE AND SCOPE
The purpose of this study was to evaluate hyperfiltration for the re-
novation of composite wastewater at selected textile plants. The selection
was made to include a variety of textile manufacturing processes. Consequent-
ly, the selection involved examples of several of the EPA guideline cate-
gories.7 The primary objective of this study was to obtain results that
when combined with the results obtained from the La France pilot plant will
permit a feasibility assessment of hyperfiltration as a general treatment
method for the textile industry. The study involved the measurement of
membrane performance with minimum pretreatment, the evaluation of reuse of
both the purified product water and the concentrated residue, and the
determination of the treatability of the concentrate by conventional means.
Even though pretreatment may be a method to improve the cost effective-
ness of membrane systems, it was not in the scope of this study to develop
pretreatments, beyond the minimum requirements for pH control, temperature,
and coarse filtration Cx-25-micron) as specified by the membrane manufacturer.
Likewise, it was not within the scope of this study to develop membrane
cleaning procedures, even though there is a potential to decrease signi-
ficantly the costs of membrane systems.
PROGRAM PLAN
This study was conducted by Clemson University for the South Carolina
Textile Manufacturers Association and the twelve textile mills who parti-
cipated in the study (Table 2). The Oak Ridge National Laboratory (ORNL)
loaned the mobile hyperfiltration test trailer to Clemson for this study
and assisted in its operation and maintenance. ORNL also provided con-
sultation regarding membrane performance. Membrane equipment companies
cooperated in this study by providing units for tests and evaluation. The
study was partially funded by a grant8 from the Environmental Protection
Agency.
The program plan included a four-month screening test phase. The
screening tests (Appendix A) consisted of membrane performance evaluations
conducted at Clemson with 0.4 m^ (100-gallon) samples of wastewater from
each mill. No significant differences were detected in membrane performance
with any of the composite waste streams. Laboratory-scale tests of recycle
were conducted both at the central dyeing laboratory of Deering Milliken
Research Corporation and by the laboratory at each mill. The test dyeings
all indicated that the renovated water was completely satisfactory as
process water even when the recovered fraction was greater than 90% of the
original wastewater volume.
The initial program schedule allowed for six plant sites. The program
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TABLE 2. PLANTS, FIBERS PROCESSED, AND EFFLUENT GUIDELINE
SUBCATEGORIES INVOLVED IN FIELD TESTING
Plantb
Plant #50
Plant #60
Plant #70
Plant #40
Plant #80
Plant #81
Plant #82
Plant #83
Plant #41
Plant #42
Plant #43
Plant #44
Fibers
Cotton
X
X
X
X
X
X
X
X
X
X
X
Processed
Synthetic Wool
X X
X
X X
X
X
X
X X
X X
X
X
X X
X
Waste
No.
5
6
7
4
8
8
8
8
4
4
4
4
a
Discharge Subcategory
Description
Knit fabric finishing
Carpet mill
Stock and yarn dyeing
Woven fabric finishing
Commission finishing
Commission finishing
Commission finishing
Commission finishing
Woven fabric finishing
Woven fabric finishing
Woven fabric finishing
Woven fabric finishing
. Reference 7.
Code number of individual plant.
-------
was later amended to include two additional plants. The field tests were
conducted using the ORNL mobile laboratory operated by Clemson University
and plant personnel.
Laboratory-scale evaluations of the reuse of both the purified water
and the concentrated chemical residue were conducted at each mill by plant
personnel. Because the recycle of the chemical residue is not always
immediately practical, Texidyne, Inc. was contracted by SCTMA to. evaluate
the conventional treatability of the concentrate from six of the plants.
This study began in August, 1974. The screening tests were completed
by December, 1974, with initial field testing beginning in January, 1975,
after a brief period of equipment modification due to extremely cold
weather. The field tests were concluded in October, 1975. Evaluation of
the reuse test dyeings and preparation of cost estimates were done during
the spring of 1976. Review and discussion of the results with the textile
mills was delayed by the energy crisis of 1976 - 1977.
-------
SECTION 2
CONCLUSIONS
The conclusions of this study relating to reuse are:
• The quality of product water, purified by passing through a
hyperfiltration membrane, was satisfactory for reuse in scouring, bleaching,
dyeing, and finishing.
• The residual concentrate contains significant quantities of dyes
and chemicals in a mixture, but will require specific study programs at
each individual mill to develop reuse.
The conclusion about the treatability of the concentrate is:
• The treatability of the residual concentrate by conventional means
was established in bench-scale tests to be equivalent to the treatment used
at each plant for treating the composite plant effluent.
The conclusions of this study relating to membrane performance are:
• The technical feasibility of both cellulose acetate and dynamic
membranes, with corresponding pretreatments, to renovate textile wastewater
was established.
• Preliminary cost projections for full-scale systems utilizing
cellulose acetate membranes to treat the composite wastewater indicate a
total cost range of $1.17 to $1.47 per 1000 gallons, including pretreatment
and amortization.
The preliminary cost projections did not include any credits for
recycle. Water supply costs will be reduced if 90% recycle is employed.
Energy savings are also possible since the recycle water is significantly
warmer than the current supply. Chemical recovery will be realized in
some situations.
-------
SECTION 3
RECOMMENDATIONS
Recycle, and the resulting conservation of energy and chemicals, makes
hyperfiltration a very promising technology for wastewater renovation.
However, a major reservation about hyperfiltration is the cost. While
recycle will achieve some savings, and preliminary cost estimates suggest
a positive return on capital, there exists no experience with large-scale,
long-term operation. In addition to equipment costs, the effect of long-
term recycle on plant production quality and costs are also not know. Since
the potential of hyperfiltration is very promising, we recommend additional
study to establish the economics of plant-scale operations and the effects
of recycle on textile production. The additional studies should include
process modifications to accommodate recycle and to reduce the liquid
effluents from dyeing and finishing processes.
It is strongly recommended that these evaluations be made before
irrevocable decisions are required regarding large expenditures of capital
to meet the national environmental protection goals of 1983 - 1985.
-••'? - ' '
Since the cost of the membrane modules is a significant factor in the
determination of the economic practicality of this technology, the following
general recommendations relate to improvements in the equipment performance
with textile wastes.
(1) Development of membrane cleaning procedures to periodically
restore flux.
(2) Development of physical and chemical pretreatment methods to
reduce membrane fouling to increase average flux and to prolong membrane
life.
(3) Development of membrane module designs to reduce costs and to
minimize horsepower requirements.
(4) Evaluation of the potential for chemical reclamation from the
residual concentrate.
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SECTION 4
TEXTILE PLANT CHARACTERISTICS
Parameters characterizing the production operation at the eight
plants involved with the on-site testing phase of this study are presented
in Table 3. The data tabulated are for the period of the on-site testing
phase of this study (1975). Obviously, these data do not necessarily
reflect the present status of these plants. This information is included
solely to assist the reader in judging the applicability of the results
and conclusions to a particular situation. In this section the range of
parameters involved in this study are presented. The details for each
plant are included in the appendices.
In every case, 85 - 95% of the composite wastewater comes from the
preparation, dyeing, and finishing unit operations within the plant. The
principal materials potentially involved in recycle from composite waste-
water renovation are the water, salt, auxiliary chemicals, and dyes. Some
energy conservation will be realized when the warm recycle water reduces
the need for heating. In the case of high-temperature membranes, signi-
ficant energy conservation may be realized by direct recycle at, or near,
process temperature. An indication of the amount of resources discharged
with the wastewater and the corresponding potential savings are given in
Table 4. The data indicate that savings may average $2.63/kgal (69
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TABLE 3. PRODUCTION CAPACITY PARAMETERS
vo
QUANTITIES USED
Water (total to plant)
m^/day
( gallons /day )
Effluent evaluated for
reuse during on-site tests
Dyes
kg/ day
(pounds /day)
Auxiliary Chemicals
kg/day
(pounds /day)
Energy (for process steam)
j oules/day
(Btu/day)
UNIT COSTS
Water
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TABLE 3. (continued)
QUANTITIES USED
Water (total to plant)
mVday
(gallons/day)
Effluent evaluated for
reuse during on-site tests
Dyes
kg/day
(pounds/ day)
Auxiliary Chemicals
kg/day
(pounds/day)
Energy (for process steam)
j oules/day
(Btu/day)
UNIT COSTS
Water
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TABLE 4. POTENTIAL CONSERVATION BY RECYCLE FOR THE TEXTILE INDUSTRY
Study Total3
Industry Total
Recycle Potential
Estimated Annual Savings
Water
Discharge
(103 kgal/d)
31
706°
635
$79 x 106
Materials Used
Dyes Auxiliary Salt
(103 #/d) (103 #/d) (103 #/d)
60 28b 27
1291 594 581
129 489 481
$95 x 106 $24 x 106 $3 x 105
Process Thermal
Energy
(109 Btu/d)
38
784d
3526
$264 x 106
* EPA Grant No. S802973.
Exclusive of 176,000 pounds
of NaOH used
daily at these plants.
, 1972 census of manufacturers, assuming 250 days/year on stream.
Industry estimate of 50 x 105 barrels/yr; 70% in wet finishing.
15 x 106 barrels/yr.
Unit costs: water @ $0.5 kgal; dye @ $3/#; auxiliary chemicals @ $0.2/#?
salt @ $44/ton; process steam @ $2/106 Btu.
-------
TABLE 5. PROCESS CHARACTERISTICS OF THE MILLS INVOLVED IN ON-SITE TESTS
Plant
Types of Processes
Fabrics Processed
Plant #50
jet dyeing,
atmospheric
becks
polyester 65%
rayon 20%
wool 15%
Plant #60
carpet dyeing,
atmospheric
becks
acrylic 10%
nylon 80%
polyester 10%
Plant #70
high-temperature
package dyeing
machines, atmos-
pheric skein-dye-
ing equipment
acrylic 10%
nylon 1%
wool and
mohair 1%
Plant #40
scouring,
bleaching,
dyeing, and
finishing in
continuous
ranges
cotton ; cotton-
polyester blends
Chemicals and Dyes Used
Plant Classification
for the Purpose of
Waste Effluent
Limitations
disperse, acid
direct dyes
Subcategory 5
Knit fabric
finishing
acid, premetal-
lized, disperse
dyes
Subcategory 6
Carpet mill
basic dyes
Subcategory 7
Stock and yarn
dyeing
sulfur, vat,
fiber reactive,
napthol dyes
Subcategory 4
Woven fabric
finishing
-------
TABLE 5. (continued)
Plant
Plant #80
Plant #81
Plant #82
Plant #83
u>
Types of Processes
Fabrics Processed
Chemicals and Dyes Used
Plant Classification
for the Purpose of
Waste Effluent
Limitations
scouring,
bleaching,
dyeing,
finishing in
continuous
ranges
cotton; cotton-
polyester blends
sulfur, vat
fiber reactive,
napthol dyes
Subcategory 8
Woven fabric
finishing
scouring,
bleaching,
dyeing,
finishing in
continuous
ranges
cotton; cotton-
polyester blends
sulfur, vat
fiber reactive,
napthol dyes
Subcategory 8
Woven fabric
finishing
scouring,
bleaching,
dyeing,
finishing in
continuous
ranges
cotton; cotton-
polyester blends
sulfur, vat
fiber reactive,
napthol dyes
Subcategory 8
Woven fabric
finishing
scouring,
bleaching,
dyeing,
finishing in
continuous
ranges
cotton; cotton-
polyester blends
sulfur, vat
fiber reactive,
napthol dyes
Subcategory 8
Woven fabric
finishing
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TABLE 6. PLANTS, GUIDELINE SUBCATEGORIES, AND EFFLUENT CHARACTERISTICS
Waste Discharge Characteristics
Plant
#50
#60
#70
#40
#80
#81
#82
#83
#41
#42
#43
#44.
Guideline
Subcategory
5
6
7
4
8
8
8
8
4
4
4
4
Flow
106 GPD 103m3/d
2.4
0.7
1.0
4.4
3.0
12.0
2.0
8.3
2.0
4.8
6.0
1.4
9.1
2.7
3.8
16.7
11.4
45.4
7.6
31.4
7.6
18.2
22.7
5.3
Temperature
°F °C
140
100
130
95
107
120
91
99
110
88
81
84
60
38
54
35
42
49
33
38
43
31
27
29
PH
7.0
4.0
4.0
12.4
9.8
11.0
7.3
11.4
11.0
11.0
11.6
11.3
COD
(mg/£)
450
na
700
1200
1284
1780
670
na
2400
890
1033
na
TDS
(mg/A)
350
430
800
3000
na
1750
1130
1850
3600
980
2580
na
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During the on-site testing, grab samples were taken to characterize
the wastewater feed to the membrane units. As an example of these results,
Table 7 presents the grab sample results for Plant #40. Complete results
of analyses for grab samples taken at each plant are given in the appendices
of this report.
15
-------
TABLE 7. CHEMICAL ANALYSES OF SELECTED WASTEWATER GRAB SAMPLES
PLANT #40
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conduct ivi ty
Phenol
pH
Mercury
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a """
, Grab samples of
633
4/2/75
1360
270
534
1549
13
4000
2920
768
350
6.0
6400
0.004
11.7
0.43
2.0
0.2
0.1
13
2.2
0.4
1.9
total plant effluent.
648
4/3/75
1520
330
620
1424
15
3140
2888
910
250
10
5800
0.097
11.7
0.43
2.5
0.2
0.1
0.15
1.3
0.2
2.0
654
4/7/75
1860
380
563
1158
13
3812
3634
1020
300
5.5
4500
0.053
11.5
0.04
1.5
0.2
0.1
31
3.2
0.4
1.8
All results are in mg/Si, except for color (APHA units), turbidity
(mg/£ SIO2), conductivity (ymho/cm), pH (unitless), and mercury (yg/£)
16
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SECTION 5
EQUIPMENT AND PROCEDURES
The evaluation of membranes for treatment of textile wastewater was
conducted in two phases: a series of laboratory screening tests, and
on-site evaluations. Both phases of testing used the mobile hyperfiltration
laboratory loaned by ORNL. The screening tests were conducted at Clemson
University with 0.4 m3 (100-gallon) samples of wastewater. The screening
tests (Appendix A) were primarily useful in selecting plants for the on-site
testing phase.
In both phases of the test program evaluation was made by plant
personnel of the potential for reuse of the product water and the concentrate.
The particular emphasis of the on-site testing phase was the evaluation of
membrane performance over a significant period of operation (approximately
250 hours).
MOBILE LABORATORY
The mobile laboratory was loaned to Clemson by ORNL for this study.
The laboratory was housed in a 9.1 m x 2.4 m (30 feet by 8 feet) Dorsey
trailer. The laboratory was transported to the textile finishing plants
by tractors provided by the host company.
The mobile hyperfiltration laboratory was equipped with two independent
systems shown schematically in Figure 1. The low-pressure system utilized
a multistage centrifugal pump capable of delivering 3.4 m3/hr (15 gpm) at
3.4 MPa (500 psig). Pressure, flow rates, and temperature were controlled
manually- The internal pump parts limited the temperature of operation to
71°C (160°F).
The high-pressure loop utilized a positive displacement diaphram feed
pump. The circulation velocity was maintained with a canned-rotor centri-
fugal pump capable of delivering 23 m3/hr (100 gpm) at 1.03 MPa (150 psid)
differential. Pressure was controlled automatically. Temperature and
circulation flow rates were controlled manually. The system is constructed
of 300-series stainless steel. Complete details of the facility are given
in Reference 9.
The pH of the incoming feed was controlled automatically by a reagent
addition system. Temperatures were recorded on a multipoint recorder.
Pressures were indicated by boudon tube gauges and flow rates by rotameters
or venturi tubes. Conductivities were measured with a dip-type cell,
17
-------
CONCENTRATE RETURN
PRESSURIZING
CIRCULATING PUMP
KXL__v CONCENTRATE
IX * BLEED
PRODUCT
BLEED
00
FEED
IN
LOW PRESSURE LOOP
CONCENTRATE RETURN
PRESSURIZING PUMP
(POSITIVE DISPLACEMENT)
.. A _ . CONCENTRATE
PQ - r BLEED
PRODUCT
BLEED
hM*
PRESURE CONTROL VALVE
CIRCULATING PUMP
HIGH PRESSURE LOOP
Figure 1. Schematic drawing of hyperfiltration loops in the mobile hyperfiltration laboratory.
-------
optical density by a spectrophotometer, and pH by a dip-type probe. Flow
rates for membrane flux measurements were made with a graduated cylinder
and clock.
ON-SITE TEST PROCEDURES
The goals of the on-site tests were (1) to obtain samples of re-
novated composite wastewater for evaluation of reuse, and (2) to obtain
engineering data on membrane performance with composite wastewater. Tests
were made, when time allowed, with unmixed effluents from unit manufacturing
processes within the plant.
The schedule called for a four- or five-week stay at each of the eight
mills. The schedule was extended at some sites due to equipment problems
and plant holidays. One-half week on arrival and one-half week at departure
were devoted to utilities connection and equipment check-out.
Membranes were selected for use at each site based on availability
and the waste characteristics. The membranes evaluated are indicated in
Table 8. All wastewater was prefiltered through 25-micron cartridge filters
before entering the laboratory trailer. The pH was adjusted when necessary
to meet module manufacturers specified ranges. A typical equipment arrange-
ment during on-site testing is shown in Figure 2.
To achieve the project objectives, a three-phase on-site testing
program was undertaken: (1) reuse test sample generation, (2) 200-hour
engineering test of membrane performance, and (3) special tests (when
time allowed). During each phase a number of water samples were taken for
detailed chemical analyses. Complete details of the procedures followed
at each mill are given in the appendices.
19
-------
TABLE 8. MEMBRANE EVALUATION SCHEDULE
to
o
/
Plant
Plant #50
Plant #60
Plant #70
Plant #40
Plant #80
Plant #81
Plant #82
Plant #83
Test
12/3/75
1/15/75
2/26/75
3/26/75
4/23/75
5/21/75
6/25/75
7/30/75
Period
- 1/15/75
- 2/26/75
- 3/26/75
- 4/23/75
- 5/21/75
- 6/25/75
- 7/30/75
- 9/04/75
Dynamic
Zr-PAA
X
X
X
X
X
X
X
X
Membrane Type
Spiral-wound Tubular
Cellulose Acetate Cellulose Acetate
X X
X X
X
X
X
X
X
-------
OVERFLOW
1
SUMP
TANK
25//m
RLTER
TANK ^- TANK
PRODUCT
CONCENTRATE
SPARGE
a
pH ADJUST
SELAS
WESTINGHOUSE
HYPERRLTRATION
LABORATORY
V V
r "I TOTALIZING
*+* FLOW METER
TO SUMP I Y
«-WASTE-
Figure 2. Flow schematic for equipment set-up at Plant #40.
-------
SECTION 6
REUSE AND TPEATABILITY
The recycle of up to 90% of the composite wastewater renovated by
hyperfiltration was confirmed at each of the plants involved in this study.
Initially, during the screening test phase of this study, water samples
from each mill were evaluated at the Deering Milliken central dye laboratory
for reuse with basic and disperse dyes. Reuse tests were also conducted by
plant personnel during the on-site test phase of the study- The details of
the tests at each mill are included in the appendices.
The recycle of the concentrate, ^10% of the wastewater volume, was
evaluated. Reuse of the concentrate is technically feasible in some cases,
but often impractical without process modification. Consequently, the
conventional treatability of the concentrate was evaluated for six of the
mills and found to be equivalent to the treatability of the normal plant
effluent. The reduced volume suggests lower treatment costs. The results
of the reuse evaluations and the treatability are summarized in this
section. Details of the tests are included in the appendices.
REUSE SAMPLE PREPARATION
The initial testing at each plant was to determine the reusability of
the renovated wastewater. Three hyperfiltration membranes were studied:
spiral-wound cellulose acetate membranes1, dual-layer dynamic membranes on
Selas ceramic tubes2, and tubular cellulose acetate membranes.^
A sample of composite wastewater was drawn from the plant sewer, and
pumped through a 25-micron filter into the mobile laboratory. The hyper-
filtration was conducted until 90% (by volume) of the water was recovered
as purified product water. Dyes, salts, etc., were concentrated in the
remaining 10% of the water. Samples of both the product water and the
concentrate were collected at 75% recovery, and also at the final 90%
recovery level.
Both the 75% and the 90% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course, re-
present the more severe test of reuse.
PRODUCT WATER REUSE
The direct recycle of renovated wastewater as plant process water was
confirmed by each plant in this study. A water quality standard for textile
22
-------
process water is not available. These data do not define chemical analyses
limits for reuse either. No test results were reported for reuse of hyper-
filtration product water from the treatment of textile wastewater.
The results of chemical analyses of the water evaluated for reuse are
tabulated for each membrane type in Tables 9-11. In general, the product
water contains more dissolved solids, inorganics and organics, than normal
tap water but is low in metals. Because membranes do not separate 100% of
the dissolved material, the 10% by volume residue is only about eight times
as concentrated as the plant composite wastewater (instead of the volumetric
factor of 10) . The purified product water contains some chemicals, also
because the membranes do not reject 100% of the dissolved materials. The
samples of purified product water evaluated for reuse were obtained just
at the end of the concentration test, and thus contain more chemicals than
the average mixed product water would have if it had all been collected.
In fact, for the membranes tested the mixed product water from a full-scale
hyperfiltration plant would contain only about one-third the contaminant
levels of these reuse samples.
Because the question of water recycle is very important in this study
brief summaries of the tests conducted by each mill are included here as
well as in more detail in the appendices.
Plant #50
The samples were misplaced in transit from the mill site to the corpora-
tion central laboratory and hence no reuse evaluations were conducted.
Plant #60
Laboratory dyeings, including tricolor carpet shades, were conducted
by the plant laboratory with no significant differences in results obtained
with normal tap water.
Plant #70
The product water was evaluated for reuse in a laboratory dyeing using
basic dyes. The product water was found to be equivalent to normal process
water.
Plant #40
The product water was used in the laboratory with reactive dyes on 100%
cotton fabrics. It was also used in a padding formulation containing no dye
to determine if any background color would interfere with continuous pad-dry-
thermosol-steam operation. No problems were encountered in the test dyeings
and the color fastness was the same as obtained with normal plant water.
Plant #80
Laboratory evaluation for continuous range dyeings were run using
product water to make up the dyebath. A control run was made using regular
23
-------
TABLE 9. CHEMICAL ANALYSES OF SPIRAL-WOUND CELLULOSE ACETATE
MEMBRANE PRODUCT WATER EVALUATED FOR REUSE
PLANT
% RECOVERY
PARAMETER3
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#50
90%
72
10
22
5
' 1
10
8
4
10
2
44
0.52
6.7
<0.01
<0.01
0.46
0.35
<0.01
<0.1
0.10
0.1
0.14
#60
92%
64
5
13
10
<1
10
10
4
8
2
37
-
6.5
<0.01
0.01
0.38
0.27
<0.01
-
-
<0.1
0.11
#70
90%
368
80
84
-50
<0.3
144
144
80
10
-
135
0.05
4.6
0.002
<0.01
<0.01
0.57
<0.1
<0.01
0.01
0.17
2.56
#40
90%
178
40
25
32
<1
1222
1222
122
30
20
1650
0.22
6.4
<0.001
<0.1
<0.01
1.79
<0.1
<0.1
0.133
<0.1
1.77
24
-------
TABLE 9. (continued)
PLANT
% RECOVERY
a
PARAMETER
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#80
90%
208
105
42
-52
5
472
472
96
-
-
830
0.055
4.0
<0.001
0.05
<0.01
2.68
0.41
0.11
1.09
0.15
2.10
#82
90%
66
26
14
27
1
82
82
38
-
-
65
0.07
6.5
<0.001
<0.01
<0.01
0.66
<0.01
0.04
0.33
0.03
0.04
#83
90%
53
11
43
200
10
74
74
48
10
0.5
83
0.14
6.0
<0.001
<0.01
0.73
<0.01
<0.01
<0.01
0.16
0.05
0.62
a All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
25
-------
TABLE 10. CHEMICAL ANALYSES OF SELAS DYNAMIC MEMBRANE
PRODUCT WATER EVALUATED FOR REUSE
PLANT
% RECOVERY
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#50
90%
84
15
20
10
<1
42
42
4
-
-
66
0.44
7.2
<0.01
0.01
0.68
0.40
<0.01
0.19
0.08
0.1
0.18
#60
92%
120
2
28
19
<1
62
62
18
10
-
55
0.03
6.8
<0.01
0.03
0.55
0.47
<0.01
-
-
<0.1
0.15
#70
90%
226
56
88
35
<0.3
272
272
126
-
-
250
0.06
8.5
<0.001
<0.01
0.01
0.79
<0.1
<0.01
0.08
0.1
1.72
#40
90%
218
58
27
73
3
1440
1432
140
20
10
2200
0.01
7.0
<0.001
0.27
0.36
1.76
<0. 1
<0. 1
0.30
0.112
1.97
26
-------
TABLE 10. (continued)
PLANT
% RECOVERY
a
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#80
90%
144
52
22
102
1
634
634
254
-
-
800
0.08
9.0
<0.001
0.13
0.47
2.48
0.35
0.11
0.46
<0.1
1.57
#81
90%
328
>105
-
72
2
500
500
250
-
-
350
0.04
8.6
<0.001
0.01
0.1
0.47
0.20
0.1
0.07
0.1
0.01
#82
90%
94
11
17
31
2
1140
1135
130
5
8
1300
0.015
6.8
<0.001
<0.01
<0.01
0.17
0.09
<0.01
0.18
0.04
0.04
#83
90%
103
8
39
64
10
886
885
76
15
1.0
1550
0.015
6.8
<0.001
0.09
0.51
<0.01
<0.01
<0.01
0.71
0.09
0.71
All results are in mg/l, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
27
-------
TABLE 11. CHEMICAL ANALYSES OF TUBULAR CELLULOSE ACETATE
MEMBRANE PRODUCT WATER EVALUATED FOR REUSE
PLANT
% RECOVERY
a
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#50
90%
468
24
800
50
1
274
267
144
180
30
270
0.59
6.7
<0.01
0.04
0.82
0.25
<0.01
0.27
1.41
0.1
0.26
#60
92%
284
14
63
5
3
186
181
80
40
10
140
0.03
5.6
<0.01
<0.01
0.66
0.30
<0.01
-
-
0.1
0.11
;a
All results are in rag/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
28
-------
plant water on the same fabric style. A critical shade was chosen in
disperse/vat, disperse/sulfur, and disperse/reactive combinations. Reuse
of product water in the dyebath did not affect the shade. Shade variation
was not more than is expected when repeating the same dyeing with regular
plant water.
Plant #81
The product water was used in the plant laboratory with disperse/fiber
reactive dye mixtures and disperse/vat dye mixtures on 65%/35% polyester/
cotton fabric. No problems were encountered in the laboratory test dyeings
and the color fastness was the same as obtained with normal plant water.
Plant #82
The product water was used in the laboratory with disperse, acid, and
premetallized dyes on polyester/wool blends and 100% textured polyester
fabric. The dyeings were conducted in atmospheric pressure becks to simulate
plant equipment. No problems were encountered in the test dyeings and the
shade obtained was the same as obtained with normal plant water.
Plant #83
Laboratory dyeings using product water and concentrate water were
made on 54/45 polyester avril fabric, 100% T-65 polyester fabric, and 100%
orlon fabric and multifiber test cloth.
CONCENTRATE REUSE
Samples of concentrate, ^10%, containing about eight-fold concentrations
of the wastewater constituents, were evaluated for chemical recovery. The
concentrate, of course, contained the many chemicals associated with scour-
ing, desizing, dyeing, and finishing. The straight-forward recycle of the
concentrate from total plant composite wastewater without especially
developed procedures was not expected. The chemical analyses of the con-
centrates obtained are tabulated in Tables 12 - 14.
Brief summaries of the tests conducted by each mill to evaluate
concentrate reuse are included here as well as in more detail in the
appendices.
Plant #50
The samples taken for reuse evaluation were misplaced in transit from
the site to the corporate central dye laboratory; no reuse evaluations were
conducted.
Plant #60
The attempts by the laboratory to use the concentrate in standard
production procedures had limited success. The composite waste concentrate
29
-------
TABLE 12. CHEMICAL ANALYSES OF SPIRAL-WOUND CELLULOSE ACETATE
MEMBRANE CONCENTRATE WATER EVALUATED FOR REUSE
PLANT
% RECOVERY
a
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#50
90%
5233
285
1570
390
10
3250
3182
1764
2000
250
2500
0.65
7.1
<0.01
0.12
1.48
2.09
<0.01
0.11
0.88
0.12
0.70
#60
92%
7650
1800
1800
160
50
6314
6303
3504
1500
60
2700
-
5.8
<0.01
1.32
3.77
8.48
<0.01
-
-
0.50
1.30
#70
90%
3300
260
750
-70
70
3620
3608
1680
450
50
2500
0.08
4.9
0.003
0.56
2.25
1.37
0.21
0.21
9.22
0.73
1.19
#40
90%
5020
1800
1200
270
105
12210
12120
2698
2500
400
13600
0.21
6.4
<0.001
0.25
0.74
3.80
0.10
3.60
9.30
5.50
2.17
30
-------
TABLE 12. (continued)
PLANT
% RECOVERY
PARAMETERa
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#80
90%
468
120
78
-85
170
4650
4645
370
65
20
5500
0.03
3.6
<0.001
<0.01
0.72
7.75
0.76
0.58
9.91
1.78
1.62
#82
90%
3620
760
729
170
140
10710
10683
1440
450
70
14500
0.09
6.6
<0.001
0.39
2.74
11.74
1.41
0.33
18.32
2.01
12.23
#83
90%
2700
210
2000
220
220
7030
6987
1770
1400
770
6800
0.08
7.0
<0.001
<0.01
1.62
0.98
<0.01
0.07
0.39
<0.01
10.5
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (umho/cm), and pH (unitless).
31
-------
TABLE 13. CHEMICAL ANALYSES OF SELAS DYNAMIC MEMBRANE
MODULE CONCENTRATE EVALUATED FOR REUSE
PLANT
% RECOVERY
a
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#50
90%
4880
170
1371
95
30
2352
2276
1328
2800
300
1250
7.9
6.7
<0.01
0.09
3.55
2.66
<0.01
0.20
1.44
0.20
1.78
#60
92%
4560
66
1457
70
14
3148
3109
2138
1800
100
1000
0.02
6.4
<0.01
0.30
1.42
0.94
0.06
-
-
0.11
1.03
#70
90%
4850
840
480
400
45
5790
5786
2050
960
50
4500
0.22
7-4
<0.001
0.49
3.16
1.06
0.49
<0.01
0.56
0.21
1.09
#40
90%
5020
1800
1200
270
105
12210
12120
2698
2500
400
13600
0.21
6.4
<0.001
0.25
0.74
3.80
0.10
3.60
9.30
5.51
2.17
32
-------
TABLE 13. (continued)
PLANT
% RECOVERY
a
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#80
90%
1128
300
282
320
70
4880
4807
1380
750
580
4600
0.27
8.0
<0.001
0.07
0.01
3.80
0.58
0.44
1.77
0.58
1.43
#81
90%
17800
6200
-
1300
210
18010
17810
10870
4000
900
6800
1.40
7.1
<0.001
3.97
6.31
9.02
2.12
1.38
7.76
1.59
11.36
#82
90%
3620
760
729
170
140
10710
10683
1440
450
70
14500
0.09
6.6
<0.001
0.39
2.74
11.74
1.41
0.33
18.3
2.01
12.23
#83
90%
2700
210
2000
220
220
7030
6987
1770
1400
770
6800
0.08
7.0
<0.001
<0.01
1.62
0.98
<0.01
0.07
0.39
<0.01
10.5
All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU) , conductivity (lamho/cm) , and pH (unitless) .
33
-------
TABLE 14. CHEMICAL ANALYSES OF WESTINGHOUSE TUBULAR CELLULOSE ACETATE
MEMBRANE MODULE CONCENTRATE EVALUATED FOR REUSE
PLANT
% RECOVERY
a
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conduct! vi ty
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
#50
90%
5233
285
1570
390
10
3250
3182
1764
2000
250
2500
0.65
7.1
<0.01
0.12
1.48
2.09
<0.01
0.11
0.88
0.12
0.70
#60
92%
7650
1800
1800
160
50
6314
6303
3504
1500
60
2700
-
5.8
<0.01
1.32
3.77
8.48
<0.01
-
-
0.50
1.30
All results are in mg/SL, except for color (Pt-Co units) , turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
34
-------
contained a complex mixture of dyes which dyed the carpet fabric a dull
or dark shade.
Plant #70
The attempts by the laboratory to use the concentrate in standard pro-
duction procedures were not successful. The composite waste contained only
small quantities of dye. No attempts were made to determine special
formulations and corresponding dye savings.
Plant #40
The concentrate from the composite wastewater was very strong, contain-
ing 12,210 mg/£ total solids, and 5020 mg/fc of COD. The total solids are
mostly salts as indicated by the high (78%) percentage of non-volatile
substances in the concentrate.
The concentrates resulting from both 70% and 95% recoveries were
evaluated in the laboratory for a pad-dry-thermosol-steam procedure. Minimal
dye concentration was obtained on the treated fabric giving evidence of small
concentrations of a mixture of dyes and chemicals in the concentrate. No
value could be observed from reuse of the concentrate obtained from the
composite waste stream.
A sample of indigo rinse water was concentrated by the hyperfiltration
membranes to evaluate the recovery of indigo dye. The concentrate obtained
was then evaluated by plant laboratory personnel. The results indicated
that the concentrated indigo rinse water could be used to formulate a
dyeing solution suitable for reuse with equivalent fastness properties to
the original dye. A significant savings of indigo was indicated by the
laboratory results.
Plant #80
There was the possibility of recovering chemicals from isolated process
streams and because of this rinse water from the desizing, mercerizing, and
continuous dye ranges were subjected to hyperfiltration concentration.
The concentrates were evaluated by running white fabric through the
concentrate in the dye pad, but omitting dyestuff. All dyeing chemicals
were included. Samples were taken after the thermosol to check yellowing
at this point.
Recycling of dyestuff in the concentrate was not possible as we
received them in this evaluation. It is not known if special handling of
the concentrate and/or further processing would bring this into the realm
of possibilities. The precipitation or agglomeration of the dyestuff in
the concentrate caused "dye spots" on several of the fabrics when run on
the Benz range using dyeing chemicals only. Yellowing of the fabric after
thermosol fixing would also have to be considered.
35
-------
Plant #81
The concentrate resulting from 75% and 90% recoveries were evaluated
in the laboratory for a pad-dry-thermosol-steam procedure. The concentrate
from the total waste composite was not suitable for all dyebaths as dinginess
and slight discoloration were noted on the dye blank in the dyeing sequences:
sulfur, brine (reactive), and caustic/hydrosulfite. No value could be
observed from reuse of the concentrate obtained from the composite waste
stream.
There is the possibility of recovering dye from isolated process waste ,
streams. Because of this possibility, steamer water overflow from the
continuous dye range was subjected to hyperfiltration concentration.
Steamer water overflows from the processing of sulfur/disperse, disperse,
vat/disperse, and fiber reactive/disperse dye systems were treated to 95 -
97.5% recovery (concentrating the dyes by factors of ^15 to 30). Test
dyeings made with these concentrates resulted in much lighter color values
than the original dye system and light fastness was not satisfactory.
Disperse dyes were apparently fixed during the thermosol process and there-
fore were not available in the steamer rinse. Vat dyes were concentrated
satisfactorily, however.
Plant #82
The concentrates resulting from 75% and 90% recoveries were evaluated
in the laboratory for a package dye system. The staining caused by the
chemicals and dyes present in the concentrate made the final yarn unsuitable
for commercial use. Without process modification it was adjudged impossible
to recover the dyes or chemicals in the concentrate.
Plant #83
The attempts by the laboratory to use the concentrate in standard
production procedures were not successful. The composite waste contained
only small quantities of dye. No attempts were made to determine special
formulations and corresponding dye savings.
REUSE SUMMARY
In all the plants studied it was observed that it is possible to
eliminate some of the auxiliary chemicals. For example, with direct dyeing
of cellulose, salt can be eliminated by using higher concentrations of dye
in the dyebath. Excess dyestuffs will be recovered by the membranes for
reuse in the next cycle. Depending on the amount of fiber dyed and range
of colors, this modification may or may not be practical. Water, chemical,
and energy prices will play a major role in the selection of dyeing process-
es, including recovery/reuse techniques, used in the future.
TREATABILITY
Most of the dyes, salts, and other chemicals are concentrated by
36
-------
membranes into the 10% of the wastewater not recovered as purified product
water. Reuse of this concentrate may be technically feasible in some
instances with process modification. However, disposal of the concentrate
is of significant concern.
The treatability of the concentrate was examined in a bench-scale
biological reactor. The treatment efficiency of chemical coagulation and
of carbon adsorption were also evaluated. The results of these tests are
summarized in Table 15. The characteristics of the concentrated wastewater
for six plants are presented in Table 16. A discussion of the results for
each mill is included in the appendices.
From the treatability results in Table 15 for six plants, it is
concluded that hyperfiltration of the composite waste streams produces a
concentrate that is as treatable as the raw plant effluents. Therefore,
the existing biological treatment system operating at the plants studied
could be utilized with hyperfiltration concentrate. Because the volume
flow of concentrate would be about one-tenth of the present flow, horsepower
requirements for aeration would be decreased, and suspended solids removal
would be improved significantly.
37
-------
TABLE 15. A SUMMARY OF OVERALL BEST RESULTS FOR TREATMENT METHODS
OJ
03
Percent Removal
Plant
Biological Study
BOD5
COD
Color
Biological Study with
Carbon Added
BOD5
COD
Color
c
Alum Treatment
BOD5
COD .
b
Color
Powdered Activated Carbon
BODs
COD ,
b
Color
#60
86
44
16
97
72
56
9
10
0
61
73
62
#70
89
60
0
92
63
0
27
23
9
29
19
67
#40
396
29
0
36
35
0
14
23
0
76
69
67
#80
95
83
27
99
88
51
60
78
76
72
60
71
#81
98
65
75
99
66
76
15
14
48
35
32
80
#82
97
64
0
95
63
0
38
45
65
23
52
53
Percent removal based on
1000 mg/jl carbon addition
feed.
Unfiltered or "apparent"
the results
Removal
color.
for the
based on
J_l_ 1^ _ __ A.
entire period
including time
decantate sample compared to
J . J A. f t
before
the raw
and after
reactor
V. 1
Data for the alum treatment based on the best treatment, 500 mg/fc in all cases. Removal
based on decanted sample after floe settling compared with the feed.
Data for the carbon treatment based on the best overall treatment, 5000 mg/A in all cases.
Removal based on a treated filtered sample compared with the untreated filtered raw feed.
Probably the result of grab sample for this test since waste treatment plant functions
normally.
-------
TABLE 16. CONCENTRATE WASTE CHARACTERIZATION
VO
Non-metal Analyses3
COD
Filtered COD
TOC
BOD
BOD
BOD
BOD
BOD
Solids
Total
Dissolved
Suspended
Volatile
PH
Color (Pt-Co units)
Turbidity (FTU)
Conductivity
Alkalinity
Hardness
Ammonia Nitrogen
Total Kjeldahl
Nitrogen
Phosphorus
Phenols
#60
2500
935
270
415
515
560
820
3760
3000
760
2030
6.7
1250
43
2000
140
32
24
25
160
1.0
#70
3720
1410
1078
1600
1800
1600
2200
5028
4803
225
2104
6.0
1000
3
3900
456
57
5
11
4.2
0.40
#40
15285
5753
1547
2200
3500
4500
5000
10028
9853
175
4050
6.6
12044
opaque
9000
587
74
3
6
15
0.52
#80
4032
707
561
300
475
700
425
9870
9785
85
1254
6.8
2618
0.38
9600
182
135
3
6
6
0.1
#81
8871
7942
4140
3745
4800
4450
4700
3000
8702
8347
355
5074
7.0
5618
opaque
5000
341
75
4
10
41
0.1
#82
2496
2487
1606
860
925
1175
1100
450
4334
4106
228
1714
5.0
1826
15
4000
65
97
12
14
3.0
0.1
-------
TABLE 16. (continued)
Metal Analyses
Calcium
Chromium
Copper
Iron
Magnesium
Manganese
Mercury (ng/£)
Nickel
Zinc
#60
2.4
0.13
0.2
1.3
1.0
0.53
-
0.33
2.9
#70
4.0
0.19
1.2
1.3
6.0
0.08
6.0
0.17
3.4
#40
2.1
8.1
8.6
10.3
12.0
0.28
-
1.2
5.2
#80
5.9
3.1
0.64
12.0
13.0
0.43
5.5
1.9
5.0
#81
3.7
1.4
0.66
7.0
24.0
1.8
6.0
0.1
3.0
#82
8.5
-
6.2
2.9
-
0.27
1.0
0.56
20.0
Unless otherwise indicated, all units are in mg/Jl with the exception of pH, which
is unitless.
-------
SECTION 7
MEMBRANE PERFORMANCE
Following the accumulation of water samples for reuse evaluation, the
performance tests of membranes were conducted. The duration of each test
was about 200 hours to allow equilibration of operating conditions and
membrane performance. The duration of each test is tabulated in Table 17.
The performance of membranes is characterized by the flux and the
rejection. In all tests with wastewater, the flux initially declined sharply
but equilibrated to a nearly constant value. The rejection, however, was
usually constant or increased. The productivity of the membrane units were
designed using the equilibrium value of flux.
An important parameter effecting the membrane performance is the
temperature of the wastewater. The influence of temperature was evaluated
for the high-temperature membranes after the stable flux was reached at each
plant. The strong increase of flux was observed in each case.
FLUX DECLINE AND REJECTION
For all membranes evaluated in this study a significant decline in
flux was observed during the initial portion of the 200-hour performance
tests. In Figures 3 and 4 examples of the observed flux declines are
presented. In Figure 3 for the dynamic Zr-PAA membranes on three modules
(#4, #10, and #19) of ceramic tubes, the flux decline is quite severe. The
flux does quickly achieve what is apparently a stable equilibrium value.
(The equilibrium value is used in the cost projections in Section 8.)
It may be important to note that the two to one range in fluid
velocities does not appear to effect the flux decline. Also, the rejection
increases significantly indicating an improvement in the quality of the
permeate. This increased rejection suggests some self-forming membrane
layer. The lack of a significant velocity effect and the increasing
rejection indicates that the flux decline is not simply a classical fouling
by particulates. Similar results are shown in Figure 4 for a spiral-wound
cellulose acetate membrane.
Two points can be made from the observations about flux decline. First,
design flux based on the equilibrium values yields much higher cost estimates
than would result from the initial flux characteristics of new membranes
evaluated in laboratory systems with just salt water. The potential improve-
ment in economics of membranes if flux decline could be presented in very
large. Second, the flux decline may be of a different nature than the
41
-------
TABLE 17. TABULATION OF MEMBRANE EVALUATION TESTS AND TEST DURATION
to
UOP Spiral-wound Westinghouse Tubular Westinghouse Tubular
Selas Dynamic Cellulose Acetate Cellulose Acetate Polysulfone
Plant
#50
#60
#70
#40
#80
#81
#82
#83
Test Duration, hours
270b 250 250
450° 450 450
200 200
200 200
200
200
200 200 200
200 87
Membranes evaluated depended on availability.
Two test sequences of 200 and 70 hours were conducted.
Two test sequences of 110 and 340 hours were conducted.
-------
100.0
z
o
UJ
80.0
LU <
(T
60.0
[ &s
b*
1 1 1
1 1
120.0
80.0
V)
c
£
o
40.0
0.0
O NO. 4, V = 3.9 m/*
A NO. 10,V= 4.2 "H and 2.27 m/& BEFORE AND AFTER 7 HR
3 NO. 19, V = 3.5
TO 4.5
45
90 135
TIME (hours)
180
225
4.0
3.0 \
CM
2.0 t
l.(
0.0
Figure 3. Flux decline and conductivity rejection of dynamic
membrane Modules #4, #10, and #19 with untreated
textile wastewater with feed velocities (V) as
indicated.
43
-------
100.0
85.0
o
UJ
UJ
QC
70.0
45.0
--- SPIRAL, REJECT FLOW = 9.8-l3dm?min (2.6-3.4GPM)
•O
CM.
m
O
o
o»
30.0
g 15.0
0.0
46
I
92 138
TIME (hours)
184
230
1.5
1.0
\
0.5
0.0
Figure 4. Flux decline and conductivity rejection of spiral-wound
cellulose acetate membranes with untreated textile wastewater.
44
-------
classical particulate fouling studied for deslating of natural waters. In
almost every case the quality of the permeate, as evidenced by increased
membrane rejections, increased as the flux declined.
TEMPERATURE EFFECT
Because of the significance of membrane flux on capital and operating
costs, the strong influence of temperature was studied at each plant. All
the data are empirically correlated by
i ,J \ n fl IT
ln (__) . k !_.__]
where J^ is the flux at reference temperature Tj in degrees K. The constant,
k, is determined empirically for each plant. Twenty-five temperature scans
were performed using Zr(IV)-PAA membranes during the course of on-site
evaluation of membrane performance at the eight mills. Values of k determined
from the excursions varied widely depending on the feed being processed and
past exposure of the membranes. The mean value is k = 3280°K with variation
from 5310°K to 1860°K. For example, the flux at 90°C is from four to ten
times the flux at 25°C. The data indicate that qualitatively the temperature
effect is not altered by flux decline.
Two benefits can be realized from processing high-temperature wastes
with membranes: (1) the exponential rise in flux with temperature results
in a reduced capital expenditure for membrane units capable of handling the
flow, and (2) energy savings can be realized by returning hot reusable
water to the process and heating only the made-up fraction. The net
advantage of the above benefits may be reduced by the tendency of high flux
membranes to foul more quickly, i.e., higher circulation velocity (and
therefore more pumping power) may be required to prevent flux declines at
higher fluxes.
45
-------
SECTION 8
COST ESTIMATES
The equipment performance data are used in the following cost projections
for full-scale treatment plants. The cost projections include pretreatment,
i.e., pH control, temperature control, and suspended solids removal, as
required for the two membrane types. However, no allowance is included for
storage reservoirs, nor for the 10 - 20% makeup water (10 - 15% due to
evaporation and drying), nor for treatment of the concentrate. Cost pro-
jections presented are incremental costs that may be useful in a more
detailed economic analyses. Because cost for taxes, insurance, and overhead
may vary widely from plant to plant and from time to time, no estimates for
these costs are included.
The cost projections presented in Tables 18 and 19 are based on the
more detailed cost study for La Prance.6 This current study assumed that:
(1) pretreatment (operating and capital) cost, auxiliary equipment, engineer-
ing, and electrical costs are proportional to the volume of water processed,
(2) the membrane housing, maintenance, and membrane replacement costs are
inversely proportional to the flux and proportional to volume of water pro-
cessed, and (3) labor costs are assumed at three man-years/year for each
system. These cost-scale factors are the result of the modular character
of membrane equipment. Of course, some economy of size may be realized in
terms of labor costs and instruments and controls.
Amortization costs, included in total operating costs, were determined
by converting capital costs to equivalent annual costs assuming 10% interest
for ten years with no salvage value. The lifetime for cellulose acetate
membranes was assumed to be three years. Lifetime of dynamic membrane
supports was assumed to be ten years, with membrane replacement performed
in-situ annually.
Table 18 summarizes the costs of cellulose acetate membranes for pro-
cessing composite waste. The flux data obtained in the La France project6
are the basis for determining the required membrane area. The total cost
ranges from ^$1.17/kgal to ^$1.47/kgal (^31
-------
TABLE 18. COSTS OF CELLULOSE ACETATE MEMBRANES
PROCESSING COMPOSITE WASTE AT EIGHT MILLS
PLANT
INSTALLED CAPACITY, m3/d
CAPITAL COSTS, $ X 10~3
Pretreatment:
P re filter
Cooling
pH Control
Membrane Housings
Auxiliary Equipment
Engineering
Contingency (10%)
TOTAL
OPERATING COST, $/d
Pretreatment
Labor (3 man-years/year)
Maintenance
Electric Power (2CAWh)
c
Membrane Replacement
Amortized Capital
TOTAL
TOTAL COST6, C/1000 gal
<=/m3
#50
9,470
$ 44
300
b
267
148
375
113
$1,247
56.25
126.28
68.60
357.00
1,776.65
811.80
$3,196.58
127.90
33.80
#60
3,788
$ 18
a
b
110
59
150
34
$371
22.50
126.28
28.43
142.80
735.80
241.52
$1,297.33
129.70
34.20
#70
1,892
$ 9
60
b
52
29
75
23
$248
11.30
126.28
13.48
71.40
349.50
161.45
733.41
146.80
38.80
#40
20,833
$ 96
660
22
588
324
825
252
$2,767
123.80
126.28
151.00
785.00
3,919.67
1,801.32
$6,907.07
125.60
33.20
47
-------
TABLE 18. (continued)
PLANT
#80
INSTALLED CAPACITY, m3/d 11,364
CAPITAL .COSTS , $ X 10" 3
P re treatment :
Prefilter
Cooling
pH Control
Membrane Housings
Auxiliary Equipment
Engineering
Contingency (10%)
TOTAL
OPERATING COST, $/d
P re treatment
Labor (3 man-years/year)
Maintenance
Electric Power (2C/kWh)
C
Membrane Replacement 2 ,
d
Amortized Capital
TOTAL $3,
TOTAL COST6, C/1000 gal
<=/m3
a
Cellulose acetate membranes
Cellulose acetate membranes
c
$ 53
360
12
321
117
450
131
$1,444
67.50
126.28
82.66
428.40 1
141.48 5
940.04 2
786.36 $11
126,20
33.30
#81
30,303
$ 140
960
32
855
472
652
311
$3,422
180.00
126.28
219.86
,142.40
,696.32
,227.72
,571.58
144.60
38.20
can operate at up to
have a pH range of 4
#82
7,576
$ 35
a
b
218
118
140
51
$562
45.00
126.28
56.16
285.60
1,454.74
365.86
$2,333.64
116.70
30.80
38°C (100°F) .
- 8.
#83
24,409
$ 131
a
30
802
442
521
193
$2 , 119
168.80
126.28
206.00
1,071.00
5,343.75
1,379.47
$8,295.30
128.70
34.00
Assuming: 3 yr membrane life, 10% interest over 10 yrs, no salvage value,
250 d/yr.
Assuming: 10 yr life, 10% interest, no salvage value, 250 d/yr.
Does not include costs for taxes, insurance, or overhead.
48
-------
upon an assumed membrane life of three years, as recommended by the manu-
facturer. Longer or shorter life will have a major influence on the operating
cost. Pretreatment costsa are based on the La France study.
Table 19 summarizes the costs of dynamic membranes for processing
composite wastewater. The flux data obtained in the 200-hour tests at each
mill are used to determine the required membrane area. The costs range
from ^$2.36/kgal to ^$5.59/kgal (^64<=/m3 to ^$1.47/m3). The major cost item
is the amortization of capital. However, the reoccurring cost for membrane
replacement is insignificant.
A combined membrane system design is possible where the more expensive
dynamic Zr(IV)-PAA membranes with high-temperature capability are used on
the hotter (^25%) of the effluent flow and the less expensive cellulose
acetate membranes are used on the cooler (^75%) of the effluent flow. In
such a combined system no cooling of the wastewater is necessary before
being processed by the cellulose acetate membranes. In addition, the
dynamic membranes will produce a small volume of hot water for recycle and
may lead to significant energy conservation. Any possible advantages of a
combined membrane system are dependent on the temperature of the effluent
being processed, and the needs for recycled hot water.
No attempt was made to optimize the condition of the wastewater by
pretreatment. It was recognized, however, that there is a potential to
reduce hyperfiltration costs significantly by maintaining the initially-
high membrane flux. The restoration of flux by washing must be taken into
account with the subsequent flux decline to establish a frequency of cleaning
and a corresponding time-average flux. The operation of membranes at the
highest temperature is a strong influence on achieving high membrane flux.
Of course, treatment of "hot" wastewater also maximized the value of thermal
energy recycle.
Information presented by Dr. K. C. Channabasappa at the Membrane Separation
Technology Seminar at Clemson University in August, 1977, indicates pre-
treatment costs approximately equal membrane costs for spiral-wound and
hollow-fiber systems used in desalination of natural water. Pretreatment
may be expected to be even higher for industrial wastewater.
49
-------
TABLE 19. COSTS OF DYNAMIC MEMBRANES PROCESSING
COMPOSITE WASTE AT EIGHT MILLS
PLANT
INSTALLED CAPACITY, m3/d
CAPITAL COSTS, $ x 10~3
Pre treatment:
Pre filter
Cooling
pH Control
Membrane Housing
and Supports
Auxiliary Equipment
Engineering
Contingency (10%)
TOTAL
OPERATING COST, $/d
Pretreatment
Labor (3 man-years /year)
Maintenance
Electric Power (2
-------
TABLE 19. (continued)
PLANT
INSTALLED CAPACITY, m3/d
CAPITAL COSTS, $ x 10" 3
P re tre atmen t :
Prefilter
Cooling
pH Control
Membrane Housing
and Supports
Auxiliary Equipment
Engineering
Contingency (10%)
TOTAL
OPERATING COST, $/d
Pre treatment
Labor (3 man-years/year)
Maintenance
Electric Power (2^/k.Vlh)
c
Membrane Replacement
d
Amortized Capital
TOTAL
TOTAL COST6, C/1000 gal
C/m3
#80
11,364
$ 38
a
b
5,753
117
450
642
$7,059
7.50
126.28
435.55
1,872.00
34.83
4,595.41
$7,071.57
235.70
62.20
#81
30,303
$ 100
a
32
16,419
472
1,200
1,822
$20,045
20.00
126.28
1,242.97
4,832.00
99.40
13,049.30
$19,369.95
242 . 10
63.90
#82
7,576
$ 25
a
b
5,753
118
300
620
$6,816
5.00
; 126.28
435.55
1,248.00
34.83
4,437.22
$4,286.88
314.30
83.00
#83
28,409
$ 94
a
b
44,950
442
1,125
4,664
$51,305
18.80
126.28
3,403.00
4,680.00
272.00
33,399.56
$41,899.64
558.70
147.50
Dynamic membranes require no temperature control.
Dynamic membranes have a pH range of 4 - 10.
Assuming: 1 yr membrane life, 250 d/yr.
Assuming: 10 yr life, 10% interest, no salvage value, 250 d/yr.
Does not include costs for taxes, insurance, or overhead.
51
-------
REFERENCES
1. Kraus, K. A., A. J. Shor, and J. S. Johnson, Jr. Hyperfiltration
Studies X: Hyperfiltration with Dynamically-formed Membranes.
Desalination, 2:243-266, 1967.
2. Brandon, C. A., and T. N. Sargent. Renovation of Textile Dyeing
and Finishing Wastewaters by Hyperfiltration for Pollution Abatement
by Resource and Energy Recovery through Complete Recycle. Proceedings
of the 18th Chemical Engineering Exhibition/Congress, ACHEMA 1976,
Frankfurt (Main), West Germany, 1976.
3. Brandon, C. A., and J. J. Porter. Complete Recycle of Composite
Textile Dyeing and Finishing Wastewater Renovated by Hyperfiltration.
Presented at the Environmental Symposium, Textile Technology/Ecology
Interface of the American Association of Textile Chemists and
Colorists, 1975.
4. Bansal, I. K. , and W. S. Young, Jr. Progress in Developing Membrane
Systems for Treatment of Forest Products and Food Processing Effluents.
Presented at the Membrane Separation Technology Seminar, Clemson
University, Clemson, SC, 1976.
5. Goldsmith, R. L. , and H. A. Fremont. Color Removal from Kraft Mill
Effluents by UltrafiItration. Presented at the Membrane Separation
Technology Seminar, Clemson University, Clemson, SC, 1976.
6. Brandon, C. A., and J. J. Porter. Hyperfiltration for Renovation of
Textile Finishing Plant Wastewater. EPA-600/2-76-060, US Environmental
Protection Agency, Washington, DC, 1976. 147 pp.
7. Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-
440/1. 74-022-a, US Environmental Protection Agency, Washington,
DC, 1974. 241 pp.
8. US Environmental Protection Agency Grant No. S802973, Dr. Max
Samfield, Project Officer, Industrial Environmental Research
Laboratory, Research Triangle Park, NC.
9. Dahlheimer, J. A., D. G. Thomas, K. A. Kraus, and J. R. Love.
Applications of Hyperfiltration to Treatment of Municiple Sewage
Effluent. FWQA Report ORD-17030EOH01/70, 1970. 71 pp.
52
-------
APPENDIX A
SCREENING TESTS
Each of the twelve plants involved in the study sent 0.4 m3 (100-gallon)
samples of total plant effluent to Clemson University for laboratory-scale
tests. These screening tests were conducted to provide preliminary indica-
tions of (1) membrane performance, and (2) reusability of the renovated
water and residual concentrate. These preliminary results provided part
of the basis for the selection of the mills to be included in the on-site
test program.
MEMBRANE PERFORMANCE
A series of hyperfiltration tests were performed at Clemson to provide
preliminary data to evaluate membrane performance when applied to total
plant effluent from each of the twelve participating plants. These data
were considered when selecting the plants to participate in the on-site
testing phase of the program.
Each of the twelve participating mills shipped a 0.4 m3 (100-gallon)
sample of their plant outfall to Clemson. Plant #81, Plant #40, and Plant
#80, in addition to the combined effluent, sent 0.4 m3 samples of selected
waste from inside the mill to be evaluated.
Membranes tested were the dynamically formed Zr(IV)-PAA on Selas
ceramic tube supports, the Westinghouse (now Union Carbide) tubular cellulose
acetate, and the UOP spiral-wound cellulose acetate.
Tables A-l through A-4 show a summary of the screening tests by
membrane type. Reference parameters indicate membrane performance with a
1000 mg/SL NaCl solution prior to each screening test. Wastewater performance
parameters are the final values at the end of each test. Table A-4 shows
results of tests performed utilizing a Selas Zr(IV)-PAA membrane exposed
to over 3000 hours of operating time prior to these screening tests.
Results of screening tests on composite effluents show 85 - 90%
conductivity rejections, indicative of high quality reusable product water
and near total removal of color in every case. Due to the limited time
exposure membrane flux results were considered inconclusive. There were no
catastrophic experiences with the flux decline even though pretreatment was
limited to just pH adjustment (where required for cellulose acetate membranes)
and 25-micron filtration.
53
-------
TABLE A-l. PERFORMANCE OF NEW DYNAMIC HYPERFILTRATION MEMBRANES DURING SCREENING TESTS
ui
a b
Reference • Performance with Wastewater
Plant
#83
#43
•X
#81 (PVA)
#81 (PVA)
#81 (PVA)
#81
#81
#80d (2)
#40d (1)
#80d (3)
Flux Rejection Temp. Flux
(m3/m2-d) (%) (°C) (m3/m2-d)
3.1 87.0 30 1.4
- - 1.3
0.1
- - 0.1
0.1
13.3
10.2
5.1
2.3 92.5 38 3.1
7.9 95.2 47 3.5
Temp.
(°C)
50
50
81
81
81
64
65
66
60
62
Conductivity
Rejection(%)
93
93
48
67
67
72
51
62
97
93
Color (%)
Rejection
99
99
-
-
-
99
99
99
99
99
PHC
8.5
8.7
6.9*
6.9*
6.9*
11.0*
11.0*
11.0*
6.6
8.2*
-------
TABLE A-l. (continued)
m
a
Reference
Plant
#408 (2)
#42
#82
#50
#60
#70
#44
#80d (5)
#41
#81 (PVA)f
Flux
(m3/m2-d)
3.8
3.5
-
3.7
3.7
4.1
3.7
4.1
4.5
-
Rejection
91.0
95.4
94.0
92.0
90.0
90.0
90.0
91.0
90.0
-
Temp.
35
32
-
33
50
55
53
53
55
-
b
Performance with Wastewater
Flux Temp.
(m3/m2-d) (°C)
3.9
3.7
4.2
4.5
4.2
3.8
3.5
4.5
3.0
1.3
55
60
65
61
61
61
61
55
64
65
Conductivity
Rejection(%)
96
93
91
82
94
93
91
94
93
27
Color (%)
Rejection
99
99
99
99
99
95
99
99
99
99
PHC
8.8
8.6
8.5
6.4*
6.7
7.0
7.8*
6.8
8.2
6.7*
Sodium chloride solution, 1000 mg/A.
Operating conditions: Pressure = 6.55
up to 300 hours.
pH of raw feed adjusted prior to test
MPa (950
except as
t f*
psig) ; recovery = 77%; membrane age =
indicated by asterisk.
4 - mercerizing, 5 - composite.
Plant #40 effluents: 1 - preparation, 2 - composite.
Ultrafiltration membrane used.
-------
TABLE A-2. PERFORMANCE OF UOP CELLULOSE ACETATE MEMBRANES DURING SCREENING TESTS
Ul
Plant
#83
#43
#82
#50
#81
#44
#80d (5)
#42
#80d (4)
#70
#40
#80d (3)
#80d (2)
#80d (1)
#60
#41
Reference
Performance of Wastewater
Flux Rejection
(m3/m2-d) (%)
0.68
0.71
0.56
0.67
0.74
0.51
0.61
0.59
0.56
0.42
0.38
0.33
0.44
0.51
0.53
0.43
96
95
96
94
94
96
96
96
95
97
97
97
94
89
84
85
Flux Conductivity
(m3/m2-d) Rejection(%)
0.48
0.49
0.59
0.45
0.15
0.35
0.54
0.50
0.51
0.33
0.17
0.37
0.40
0.51
0.44
0.16
98
98
95
95
99
97
98
97
97
89
92
95
-
90
94
89
Color (%)
Rejection
99
-
99
99
99
99
99
99
99
99
99
99
-
99
96
99
PH=
6.8
8.5
6.6-7.8*
5.3
6.0
6.4
6.8
7.0*
6.8
4.0*
4.4
7.6
11.0
7.6
6.4*
5.2
Sodium chloride solution, 1000 mg/£.
Operating conditions: Pressure =2.76
recovery = 77%.
pH of raw feed adjusted prior to test
MPa (400 psig) ; T = 32°C; inlet
except as indicated by asterisk.
flow = 17 2
^ ^ *
,/min;
Plant #80 effluents: 1 - finishing basement, 2 - preparation basement, 3 - dyehouse,
4 - mercerizing, 5 - composite.
-------
TABLE A-3. PERFORMANCE OF WESTINGHOUSE CELLULOSE ACETATE MEMBRANES DURING SCREENING TESTS
en
Reference
Plant
#80d (5)
#42
#80d (4)
#70
#40S (2)
#80d (3)
#80d (2)
#80d (1)
#60
#41
Flux
(m3/m2-d)
0.84
1.24
0.94
1.09
0.86
0.86
0.94
1.22
1.27
1.01
Rejection
(%)
91.2
93.7
92.2
94.6
93.0
93.0
92.3
89.0
81.0
87.0
Performance with Wastewater
Flux
(m3/m2-d)
0.77
0.80
0.87
0.68
0.38
0.37
0.95
1.14
1.00
0.44
Conductivity
Re jection(%)
97.8
94.0
92.4
85.3
91.0
92.2
-
90.8
91.2
88.7
Color (%}
Rejection
91.8
99.0+
98.2
81.0
98.5
93.1
-
99.0+
98.0
97.0
PHC
6.8
7.0*
6.8
4.0*
4.4
7.6
11.0
7.6
6.4*
5.2
Sodium chloride solution, 1000 mg/SL.
Operating conditions: Pressure = 2.76 MPa (400 psig); T = 32°C; inlet flow = 11.3 A/min;
recovery = 77%.
pH of raw feed adjusted prior to test except as indicated by asterisk.
Plant #80 effluents: 1 - finishing basement, 2 - preparation basement, 3 - dyehouse,
4 - mercerizing, 5 - composite.
Plant #40 effluents: 1 - preparation, 2 - composite.
-------
TABLE A-4. PERFORMANCE OF AGED DYNAMIC HYPERFILTRATION MEMBRANES DURING SCREENING TESTS
en
00
-
Reference
Flux Rejection
Plant (m3/m2-d) (%)
#81
#80S (2)
#40
#806 (3)
#50
#60
#70
#44
#806 (5)
#41
-
2.5
2.5
4.2
-
4.0
4.2
3.7
3.4
3.7
-
85.4
86.0
84.0
-
77.5
79.0
79.0
78.0
78.0
c
Performance with Wastewater
Temp . Flux Temp .
(°C) (m3/m2-d) (°C)
4.0
32 4.0
38 4.0
47 4.3
4.7
50 4.0
55 3.6
53 3.3
53 2.6
55 2.1
65
66
60
62
61
61
61
61
61
64
Conductivity Color (%) ,
Reject ion (%) Rejection pH
83
76
91
84
88
89
84
82
87
85
99
99
99
98
99
99
95
99
99
99
11.0*
11.0*
6.6
8.2
6.4*
6.7
7.0
7.8*
6.8
8.2
Test module previously
employed
at La France.
Sodium chloride solution, 1000 r
Operating conditions: Pressure
, 3000 hours
d
*
i . t
in hyper filtration pilot
uy / A/ *
= 6.55 MPa (950 psig)
plant (EPA Gr
; recovery = 77%;
nt No. S800929)
membrane age =
pH of raw feed adjusted except as designated by asterisk.
Plant #80 effluents: 1 - finishing basement, 2 - preparation basement, 3 - dyehouse,
4 - mercerizing, 5 - composite.
-------
WATER REUSE SCREENING TEST CONDUCTED AT DEERING MILLIKEN LABORATORY
The potential for reuse of the product water and concentrated residue
was evaluated by laboratory dyeings conducted at Deering Milliken Research
Laboratory. All but one of the mills involved in the project process both
cotton and synthetic fibers. Samples of product water were evaluated with
basic and disperse dye systems. The dye formula and procedures are given
in Table A-5. The concentrates were evaluated by dyeing a fabric sample
in a blank dye bath with no dyes present in the bath. This was done to
determine the presence of recoverable dye. This dyeing procedure is given
in Table A-6.
The results of these tests indicate that no problems will be encounter-
ed with the reuse of product water in textile plant dyeings.
The concentrate water samples contained significant quantities of
dyestuff which stained the multifiber fabric and demonstrated the presence
of disperse and direct dyes in many samples. The value of dye in any waste
stream will depend on the plant production and the plant's ability to fit
its reuse into normal production. This must be determined by more tests
with each individual mill.
59
-------
TABLE A-5. EVALUATION OF PRODUCT WATER WITH
BASIC AND DISPERSE DYEING SYSTEMS
Basic Dye System
Migrasist AC
Sequesterant ST
Glaubers Salt
pH
Basic Dyes
Genacryl Yellow 4G
Genacryl Blue 3G
Astrazon Red 4G
3.00%
0.25%
5.00%
4.00
0.50%
0.30%
0.50%
on the weight of fabric
on the weight of fabric
on the weight of fabric
on the weight of fabric
on the weight of fabric
on the weight of fabric
Procedure
Add chemicals and dyes at room temperature. Add acrylic fabric
and raise to 230°F with agitation. Dye at 230°F for 45 minutes.
Cool bath to 200°F and rinse with water. Repeat with tap water
for comparison.
Disperse Dye System
Acetic Acid to give pH = 4.0
Carolid JAL 4.00%
Sequesterant ST 0.25%
Disperse Dyes
Palanil Yellow 3G 0.50%
Palanil Pink REL 0.50%
Resolin Blue FBL 0.50%
Procedure
on the weight of fabric
on the weight of fabric
on the weight of fabric
on the weight of fabric
on the weight of fabric
Add chemicals and dyes at room temperature. Add polyester fabric
and raise to 266°F with agitation. Dye at 266°F for 30 minutes.
Cool bath to 200°F and rinse with water. Repeat with tap water
for comparison.
60
-------
TABLE A-6. EVALUATION OF CONCENTRATE WATER WITH BLANK DYEBATHS
FOR BASIC, DISPERSE, AND DIRECT DYEING SYSTEMS
Basic Dye System
Acetic Acid 2.00% on the weight of fabric
Glaubers Salt 5.00% on the weight of fabric
No dyes used
Procedure
Add chemicals to concentrate water. Add multifiber fabric and
raise to 230°F with agitation. Dye at 230°F for 60 minutes.
Cool bath to 200°F and rinse with cold water.
Disperse Dye System
Acetic Acid 2.00% on the weight of fabric
Dye Carrier 4.00% on the weight of fabric
No dyes used
Procedure
Add chemicals to concentrate water. Add multifiber fabric and
raise to 266°F with agitation. Dye at 266°F for 60 minutes.
Cool bath to 200°F and rinse with cold water.
Direct Dye System
Tetrasodiumpyrophosphate 1.00% on the weight of fabric
Sodium Chloride 100% on the weight of fabric
No dyes used
Procedure
Add chemicals to concentrate water. .. Add multifiber fabric and
raise to 180°F with agitation. Dye at 180°F for 30 minutes.
Cool bath.
61-
-------
APPENDIX B
PLANT #50
The on-site tests conducted from December 10, 1974, to January 18,
1975, were to obtain the following information: (1) plant laboratory
evaluation of reuse, and (2) engineering performance data with membranes.
The samples taken for dye reuse evaluations were lost in transit to the
corporate central laboratory, and hence no reuse dyeings were conducted.
Plant #50 was not included in the concentrate treatability study because
this part of the project was not authorized until after January, 1975.
FIBERS AND CHEMICALS
The dyeing and finishing processes at Plant #50 involve several
different dyes and finishes. The dyeing is done in pressure jet and atmos-
pheric beck dyeing machines. The principal dyes employed are disperse,
acid, and direct dyes. The materials processed are polyester (65%) , rayon
(20%), and wool (15%).
Ninety percent of the 9091 m3/d (2,400,000 gallons/day) total water
usage is in the dyehouse. Allowing for evaporation in the dyehouse, the
composite waste stream is at least 80% by volume dyehouse wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based
on a monthly average for the winter of 1975, of plant wastewater discharge
parameters are: BODs = 629 mg/£j COD = 1919 mg/Jl; total suspended solids =
70 mg/Jl; total dissolved solids = 1511 mg/£; pH = 4.5; temperature = 140°F.
Tables B-l and B-2 present the results of analyses for four grab samples
obtained during the period of on-site testing. Plant #50 is classified
as Subcategory 5, knit fabric finishing.
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
62
-------
TABLE B-l. CHEMICAL ANALYSES OF PLANT #50 WASTEWATER8
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
500
1/6/75
608
30
103
36
34
490
458
196
400
70
360
0.41
6.6
0.01
0.15
4.42
0.84
0.06
0.39
0.45
0.1
3.28
526
1/10/75
2204
1150
-
0
-
790
730
-
-
168
360
0.796
4.2
-
-
-
3.70
0.15
0.11
3.680
0.74
™*
. Grab samples of combined plant effluent.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
63
-------
TABLE B-2. CHEMICAL ANALYSES OF PLANT #50 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conduc ti vi ty
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
, Grab samples of
D
532
1/13/75
2584
770
-
0
-
2768
2612
-
-
350
2300
0.093
3.5
-
-
-
0.48
0.11
0.11
5.595
0.31
-
combined plant effluent.
538
1/18/75
2280
565
-
0
-
2276
2244
-
-
350
2400
0.093
3.5
-
-
-
0.53
0.07
0.11
9.075
0.26
-
All results are in mg/&, except for color (Pt-Co units), turbidity
(NTU), conductivity (pmho/cm), and pH (unitless).
64
-------
SCHEDULE AND PROCEDURE
Schedule
The mobile hyperfiltration laboratory was started up at Plant #50,
the first plant participating in the on-site testing portion of the program,
on November 18, 1974. The system was checked out and shut down until
December 3, 1974, when formation of dynamic membranes was undertaken. On
December 10 testing with wastewater began.
The following is a list of events at Plant #50:
12/03 - Began dynamic membrane formation.
12/10 - Began parametric performance test; Selas module used. Product
recycled to feed tank.
12/23 - Began parametric performance test of UOP spiral module and
Westinghouse tubular module. Product water recycled to feed tank.
01/06 - Began parametric performance test of Selas modules, UOP spiral
module, and Westinghouse tubular module. Reuse samples were
generated.
01/10 - Began special tests.
01/13 - New Westinghouse tubular polysulfone ultrafilter installed.
01/15 - Moved to Plant #60.
01/18 - Special tests completed; last test run at Plant #60.
Procedure
The membranes for evaluation were selected based on availability and
the characteristics of wastewater. The wastewater was prefiltered through
25-micron cartridge filters prior to entering the mobile laboratory. The
pH was adjusted when necessary to meet membrane manufacturer specifications.
Figure B-l shows schematically the equipment arrangement. Three module
types were evaluated: the dual-layer dynamic membrane on Selas ceramic
tubes, the spiral-wound cellulose acetate manufactured by UOPb, and the
Westinghouse0 tubular cellulose acetate membrane.
REUSE
A sample of composite wastewater was drawn from the plant sewer, and
pumped through a 25-micron filter into the mobile laboratory. The
, Selas Corporation of America, Flotronics Division.
Universal Oil Products, ROGA Division.
Westinghouse Membrane Systems was sold to Union Carbide.
65
-------
WASTE FROM PLANTS I 8 2
TO LAGOON
CONCENTRATE
fTLING and
LEVELING BASIN
^^^ bNi
L
t
H
I^^^^H
I
/<
-) Y** FILTER
\
TA
i
TA
YR
PRODUCT
U .O .P
WESTING-
HOUSE
PRODUCT
SELAS
S
CONCENTRATE
HYPERFILTRATION LABORATORY
MAN
HOLE
WASTE
1 Figure B-l. Ficsw schematic for equipment set-up at Plant #50.
-------
hyperfiltration was conducted until 90% (by volume) of the water was
recovered as purified product water. Dyes, salts, etc., were concentrated
in the remaining 10% of the water. Samples of both the product water and
the concentrate were taken at 75% recovery and also at the 90% recovery
level.
Both the 75% and the 90% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course, repre-
sent the more severe test of reuse. Because membranes do not separate 100%
of the dissolved material, the 10% by volume residue is only about eight
times as concentrated as the plant composite wastewater (instead of the
volumetric factor of ten) .
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of
purified product water evaluated for reuse were obtained near the end of
the concentration (90%), and thus contain more chemicals than the average
product water would have. In fact, for these membranes the mixed product
water from a full-scale hyperfiltration plant would contain only about
one-third the contaminants shown by the analyses listed in Tables B-3 and
B-4.
The OOP and Westinghouse membranes were tested simultaneously and
therefore processed composite waste with exactly the same characteristics.
The dynamic membrane was tested separately. The collection of the samples
for reuse took less than three hours in the case of the cellulose acetate
membranes, and about twenty hours for the dynamic membranes. In both
instances, however, the concentrated residue had a high COD (5233 and 4800
mg/£), was highly colored, and contained about 0.3% dissolved solids.
REUSE EVALUATION
Since the samples taken for reuse evaluation were misplaced in transit
to the corporate dye laboratory, no reuse dyeings were conducted.
MEMBRANE PERFORMANCE
Three membrane performance tests were conducted. The first began on
December 10, 1974, utilizing Selas modules #4, #5, and #8, with #8 being
previously unexposed to a waste feed solution. During the run of approxi-
mately 200 hours, all product was recycled to the feed tank and tap water
was added to make up for evaporation losses.
On December 23, a 250-hour run was begun utilizing the UOP spiral-wound
cellulose acetate and a Westinghouse tubular cellulose acetate module, both
run from a common feed source. During the run all product was returned to
the feed tank maintaining a constant concentration. Both modules were
previously exposed to other wastewater.
The final run was 70 hours in length, utilizing Selas modules #4, #5,
and #1. Module #1 was previously unexposed to waste effluent. During this
67
-------
TABLE B-3. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #50
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
b
Selas
Product
505
1/7/75
84
15.6
20
10
<1
42
42
4
0
0
66
0.44
7.2
<0.01
0.01
0.68
0.40
<0.01
0.19
0.08
0.1
0.18
Selas
Concentrate
506
1/7/75
4880
170
1371
95
30
2352
2276
1328
2800
300
1250
7.9
6.7
<0.01
0.09
3.55
2.66
<0.01
0.20
1.44
0.20
1.78
Reuse tests conducted in Plant #50 dye laboratory.
Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
68
-------
TABLE B-4. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE3 AT PLANT #50
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
d
PARAMETER
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Westinghouse
Product
511
1/7/75
468
24
800
50
1
274
267
144
180
30
270
0.59
6.7
<0.01
0.04
0.82
0.25
<0.01
0.27
1.41
0.1
0.26
/* Reuse tests conducted in Plant #50 dye
Westinghouse module contained tubular
UOPC
Product
513
1/7/75
72
10
22
5
1
10
8
4
10
2
44
0.52
6.7
<0.01
<0.01
0.46
0.35
<0.01
<0.1
0.10
0.1
0.14
laboratory .
cellulose acetate
,,1 MMn. -»«rt^-^4-/^ VMy-imV
West/UOP
Concentrate
515
1/7/75
5233
285
1570
390
10
3250
3182
1764
2000
250
2500
0.65
7.1
<0.01
0.12
1.48
2.09
<0.01
0.11
0.88
0.12
0.70
membranes .
•v Vai^ AC!
., \J\JC 111OU.U-LC ^WliWCLXlICSVA ajfA J.O.J. wv^i-uiv-4 v-c; -L J-^AJ-^^V- w*v^- *-— *-*~ «^_.»~_ — — -
All results are in mg/&, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm) , and pH (unitless).
69
-------
run product and concentrate were constantly bled off in a set proportion
and makeup fresh feed was added as required to maintain a constant system
volume.
Three spent dye liquors were selected for consideration during the
special testing portion of this program: (1) a disperse dye, (2) a
basic dye, and (3) a disperse/basic dye.
The disperse dye liquor was run as received at a pH of 3.4 with the
Westinghouse tubular and UOP spiral modules to 87% volumetric recovery. The
waste was neutralized to ^1 with sodium hydroxide for the Selas modules and
concentrated to 86% volumetric recovery.
The basic dye was run as received at a pH of 3.8 with the UOP and
Westinghouse modules and neutralized to a pH of ^8 for the Selas modules to
recoveries of 71% and 87%, respectively.
The disperse/basic dye run utilizing the Selas modules was aborted
when excessive temperature of the system caused a module rupture. The
disperse/basic dye was concentrated to 85% volumetric recovery utilizing
the UOP and Westinghouse modules.
Samples of products and concentrates from each module and waste were
provided the mill for reuse evaluation and chemical analyses.
While at Plant #50, forty-two samples were collected for chemical
analyses. Of these, ten were subjected to chemical analyses by Plant #50,
six were subjected to chemical analyses by Clemson University, and twenty-
six were available for reuse potential tests and were analyzed by Plant #50.
Dynamic Membrane
Four modules of Selas ceramic tubes with dynamic Zr-PAA membranes were
evaluated in two tests. The performance is summarized in Figures B-2 and
B-3, plots of flux and rejection throughout the test periods. The
characteristic initially rapid flux decline is evident. Modules #8 and #1
were not exposed to a waste stream prior to testing. Module #4 was equipped
with a membrane exposed for 2000 hours operating time. This membrane
exhibited higher flux and lower rejection than the newer membranes tested.
Previous experience has shown that more reliable flux decline data are
obtained when the membranes are exposed to fresh feed. Therefore, the flux
that would be used for design cost projections is 1.0 m/d (25 GFD) and is
based on the 75-hour test when fresh feed was continuously added.
While the flux declined, the conductivity rejection increased. Both
phenomena would be the result of the formation of a self-rejecting layer
formed on the membrane surface from the constituents in the wastewater.
The conductivity rejection measures the separation or filtration of
electrolytes by the membrane. The filtration efficiency for larger organic
molecules is usually higher than for the electrolytes. Grab samples of the
70
-------
IOO.OH
z
o
o 80.0
UJ
UJ
o o oo
60.0
I20XX
NO. 5, V = 5.2"H
•N0.8,V=2.3m/8
0.0
40
80 120
TIME (hours)
5.0
4.0
3.0
2.0 ~
x
1.0
160
200
Figure B-2. Hyperfiltration of combined effluent at Plant #50 by
Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 60°C; pH = 6.4 - 7.8;
recovery = 60%.)
71
-------
100.0 -
I20.0
o.o
Q NO- I,V=2.7
1
3 15
i
30
- &
i
45
i
60
-A_
7!
0.0
5
TIME (hours)
4.0
3.0
•o
\
2.0
1.0
Figure B-3.
Hyperfiltration of combined effluent at Plant #50 by
Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 54°C; pH = 5.4 - 7.6;
recovery = 90%.)
72
-------
feed to the membrane and the product water passing through the membranes
were obtained during the 200-hour performance tests and analyzed to
indicate the filtration efficiency for several constituents. The results
of analyses for three pairs of samples are shown in Tables B-5, B-6, and
B-7.
The 95 - 99% rejection of organics, indicated by COD, BOD, and color
comparisons between the concentrate and product samples are greater than
the conductivity rejections. The phenol rejection is 85 - 99%. The
rejection of metals is very high, as indicated in cases where results are
significantly above the limits of detection.
Cellulose Acetate Membranes
The performance of spiral-wound and tubular cellulose acetate membrane
modules is summarized in Figure B-4, a plot of the flux and rejection
throughout the test period. The operating conditions were as specified by
the module manufacturer: 2.76 MPa (400 psig) , and feed rates of 17 dm3/min
(4.5 GPM) and 13 dm3/min (3.5 GPM) for the spiral and tubular modules,
respectively. Both modules had been previously used in testing.
The flux remained near constant throughout the 200-hour test period
during which time no washing procedures were attempted. All product water
was recycled to the feed tank maintaining a constant feed concentration.
The conductivity rejection was in the range of 90 - 95% throughout the test
period. The rejection of other wastewater constituents was also very high,
as indicated by the results of analyses of samples' taken during the 200-hour
test (see Tables B-8, B-9, and B-10). The tubular module exhibited higher
flux and lower rejection than the spiral module.
73
-------
TABLE B-5. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT .PLANT #50
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER13
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
516
Product
1/8/75
70
28
-
43
-
156
155
-
-
0.3
170
0.086
6.2
-
-
-
0.05
0.08
0.08
0.001
0.12
—
517
Concentrate
1/8/75
4633
820
-
263
-
2270
2217
-
-
120
1500
1.130
6.6
-
-
-
2.44
0.29
0.09
0.769
0.37
-
Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/fc, except for color (Pt-Co units), turbidity
(NTU), conductivity (pmho/cm), and pH (unitless).
74
-------
TABLE B-6. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #50
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
521
Product
1/9/75
0
24
-
63
-
176
176
-
-
0.3
220
0
6.6
-
-
-
0.03
0.02
0.08
0.004
0.10
—
522
Concentrate
1/9/75
5756
820
-
340
-
2640
2585
-
-
160
1700
1.255
6.6
-
-
-
3.50
0.25
0.10
.1.476
0.34
"
* Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/SL, except for color (Pt-Co units) , turbidity
(NTU), conductivity (ymho/cm), and pH (unitless).
75
-------
TABLE B-7. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #50
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER13
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
501
Product
1/17/75
76
21
-
4
-
253
251
-
-
0.7
90
0.008
6.0
-
-
-
0.03
0
0.07
0.08
0.07
—
502
Concentrate
1/17/75
912
150
-
90
-
756
664
-
-
22
6100
0.052
6.3
-
-
-
1.04
0.01
0.09
0.218
0.15
-
Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/&, except for color (Pt-Co units), turbidity
(NTU), conductivity (ymho/cm), and pH (unitless).
76
-------
100.0
o
LU
~3
UJ
a:
90-Qr^rr
80.0
A. A
A
45-OL A—SPIRAL,REJECT FLOW* I7dm?mjn (4.5GPM)
•o
? 30.0
V)
c
o
o
o»
* 15.0
u.
4
0.0
(
Q TUBULAR, REJECT FLOW = I3amymin (3-5GPM)
-
^ Q Q Q Q S_ jg a ^ ^
^^A>^_ A A A _.A A & A A
I 1 1 1 1
) 50 100 150 200 250
1.5
•o
•5
0.5 5
u_
0.0
TIME (hours)
Figure B-4.
Hyperfiltration of combined effluent at Plant #50 by
tubular Westinghouse and spiral-wound UOP cellulose
acetate membrane modules. (P = 2.8 MPa (400 paig);
T = 24°C; pH = 6.9 - 7.4; recovery = 50% and 75%
before and after 125 hours.)
77
-------
TABLE B-8. PERFORMANCE PARAMETERS OF WESTINGHOUSE AND UOP MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #50
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a
Westinghouse
Product
507
1/17/75
0
30
-
10
-
82
82
-
-
0.2
400
0.010
6.4
-
-
-
0
0
0.09
0.024
0.10
-
UOPb
Product
508
1/17/75
456
25
-
5
-
48
48
-
-
0.6
82
0.008
5.6
-
-
-
0
0.01
0.08
0.015
0.08
-
West/UOP
Concentrate
509
1/17/75
8664
300
-
94
-
1990
1990
-
-
0.5
2800
0.020
6.9
-
-
-
0.13
0.18
0.10
0.165
0.13
-
Westinghouse module
UOP module contained
c
contained tubular cellulose acetate membranes.
spiral-wound cellulose acetate membranes.
All results are in mg/Jl, except for color (Pt-Co units) , turbidity
(NTU), conductivity (pmho/cm), and pH (unitless).
78
-------
TABLE B-9. PERFORMANCE PARAMETERS OF UOP AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #50
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conducti vi ty
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zihc
Copper
Magnesium
, UOP module contained
uopa
Product
518
1/8/75
0
29
-
8
-
96
96
-
_
0.6
46
0.012
5.4
-
-
_
0.13
0.03
0.07
0.004
0.09
-
spiral-wound
Westinghouse
Product
519
1/8/75
281
58
-
57
-
400
393
'
-
11
250
0.005
6.0
-
-
-
0.10
0.12
0.08
0.019
0.10
—
UOP/West
Concentrate
520
1/8/75
2738
730
-
399
-
1760
1745
-
-
126
1600
0.540
6.8
-
-
-
0.93
0.26
0.12
0.255
0.25
—
cellulose acetate membranes.
«*i-.
-------
TABLE B-10. PERFORMANCE PARAMETERS OF WESTINGHOUSE AND UOP MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #50
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Ch romi um
i'Anc
Copper
Magnesium
Westinghouse module
UOP module contained
c
Westinghouse
Product
523
1/9/75
281
35
-
59
-
340
335
_ *
-
8
290
0.548
6.2
-
-
-
0.23
0.15
0.09
0.006
0.12
-
UOPb
Product
524
1/9/75
0
20
-
8
-
28
28
-
-
0.2
38
0.078
5.6
-
-
-
0.01
0
0.09
0.016
0.09
-
West/UOP
Concentrate
525
1/9/75
2457
275
-
495
-
1820
1808
-
-
40
1650
0.149
6.9
-
-
-
1
0.25
0.12
3.680
0.23
-
contained tubular cellulose acetate membranes.
spiral-wound cellulose acetate membranes.
All results are in mg/Ji, except for color (Pt-Co units), turbidity
(NTU) , conductivity (iamho/cm) , and pH (unitless) .
80
-------
APPENDIX C
PLANT #60
The on-site tests conducted from January 15, 1975, to February 26,
1975, were to obtain the following information: (1) plant laboratory
evaluation of reuse, and (2) engineering performance data with membranes.
Reuse of both the purified product and the concentrated residue was
evaluated in laboratory tests conducted by Plant #60 personnel. Samples
of wastewater, purifi|d product water, and concentrated residue were analyzed
by Nardin Laboratory. In addition, the treatability of the concentrated
residue was evaluated in bench-scale tests, Appendix J.
FIBERS AND CHEMICALS
^
The dyeing and finishing processes at Plant #60 involve several
different dyes and finishes. The dyeing is done in atmospheric becks. The
principal dyes employed, comprising 95% of the total usage, are acid, pre-
metallized, and disperse dyes. The materials processed are acrylic (10%),
nylon (80%), and polyester (10%).
Ninety percent of the 2724 m3/d (720,000 gallons/day) total water usage
was in the dyehouse. Allowing for evaporation in the dyehouse, the composite
waste stream was about 95% by volume dyehouse wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based
on a monthly;average for the summer of 1974, of plant wastewater discharge
parameters are: BODs = 125 mg/&; COD = 1070 mg/&; total suspended solids =
46 mg/Jl; total dissolved solids = 552 mg/fc; pH = 6.1; temperature = 100°F.
Tables C-l, C-2, C-3, and C-4 present the results of analyses for twelve
grab samples obtained during the period of on-site testing. Plant #60 is
classified as Subcategory 6, carpet
Division of Commonwealth Laboratory, Inc., Greenville, SC.
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
81
-------
TABLE C-l. CHEMICAL ANALYSES OF PLANT #60 WASTEWATER3
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
544
1/20/75
837
64
172
48
2
442
426
282
30
65
245
0.07
6.7
0.001
0.17
2.63
0.67
0.1
0.1
0.31
0.1
1.6
545
1/20/75
680
50
121
37
2
396
365
258
60
35
210
o.'oe
6.2
0.001
0.07
2.76
0.98
0.16
0.1
0.46
0.11
1.87
551
1/27/75
760
64
122
45
0.3
414
366
258
50
40
219
0.04
6.4
0.001
0.01
0.76
1.08
0.18
0.1
0.51
0.1
1.82
a
Grab samples of total plant effluent.
All results are in mg/St,, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
82
-------
TABLE C-2. CHEMICAL ANALYSES OF PLANT #60 WASTEWATER*
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
552
1/27/75
845
136
137
20
5
394
328
316
110
60
95
0.02
5.9
0.001
0.13
0.87
3.42
0.1
0.1
0.23
0.15
2.03
553
1/22/75
653
24
142
42
2
416
396
288
80
30
217
0.01
6.7
0.001
0*13
0.63
2.04
0.1
0.1
0.33
0.11
2.85
554
1/28/75
447
76
100
30
3
318
274
224
190
60
140
0.10
6.3
0.001
0.08
0.71
1.56
0.1
0.1
0.23
0.35
2.45
Grab samples of total plant effluent.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU) , conductivity (ymho/cin) , and pH (unitless).
83
-------
TABLE C-3. CHEMICAL ANALYSES OF PLANT #60 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
PARAMETER13
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a
Grab samples of
j^f -• ~ ^
555
1/29/75
1140
220
235
-33
6
804
759
420
180
90
850
0.05
4.2
0.001
0.33
0.42
2.75
0.1
0.1
0.79
0.58
3.92
total plant effluent.
566
2/10/75
1270
92
287
61
4
710
680
364
100
60
460
0.05
6.6
0.001
0.14
0.44
1.79
0.1
0.1
1.22
0.22
2.73
572
2/11/75
1455
240
355
20
4
860
784
622
400
90
400
0.02
6.0
0.001
0.15
4.09
1.73
0.1
0.1
0.19
0.20
3.58
All results are in mg/SL, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
84
-------
TABLE C-4. CHEMICAL ANALYSES OF PLANT #60 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
, Grab samples of
573
2/12/75
950
160
177
28
9
802
757
368
210
50
595
0.05
5.8
0.001
0.15
4.09
1.79
0.1
0.1
0.77
0.13
2.84
total plant effluent.
580
2/13/75
943
100
180
15
3
430
386
306
100
110
160
0.06
6.2
0.001
0.11
3.16
0.85
0.1
0.1
0.12
0.1
1.92
*^ m^ / l^-k*__ ^^**V t % V% *1 ^ ft 1
593
2/17/75
2870
275
620
40
2
1154
1108
1046
1150
110
140
0.17
6.6
0.001
0.15
2.69
0.62
0.1
0.1
0.17
0.16
2.54
+- 1 1 v"V\ -i /^ •! +• * r
(FTU), conductivity (ymho/cm), and pH (unitless).
85
-------
SCHEDULE AND PROCEDURE
Schedule
The mobile laboratory arrived at Plant #60 on January 15, 1975. The
utilities were connected and the system was placed in operation on
January 20.
Initially, one-gallon (3.8&) samples of purified product and concentrate
were collected for reuse evaluation in the plant laboratory- A 38A sample
of concentrate was later collected for the biological treatability study.
The following is a list of events at Plant #60:
01/15 - Arrived from Plant #50.
01/20 - Checked OOP spiral, Westinghouse tubular, and Selas bundles.
01/21 - Began parametric performance test with daily addition of fresh feed.
Selas, UOP, and Westinghouse cellulose acetate modules were used.
01/23 - Samples for reuse evaluation at 75% recovery were generated.
01/29 - Samples for reuse evaluation at 92% recovery were generated.
02/10 - Began parametric performance test with continuous addition of fresh
feed.
02/17 - Began special tests of selected spent dye liquors taken from the
becks. Selas and UOP modules used.
02/18 - Cleaned system and formed Zr-PAA membranes on Selas modules.
02/24 - Ended membrane formation.
02/26 - Moved to Plant #70.
Procedure
The membranes for evaluation were selected based on availability and
the characteristics of wastewater. The wastewater was prefiltered through
25-micron cartridge filters prior to entering the mobile laboratory. The
pH was adjusted when necessary to meet membrane manufacturer specification.
Figure C-l shows schematically the equipment arrangement. Three module
types were evaluated: the dual-layer dynamic membrane on Selas ceramic
tubes, the spiral-wound cellulose acetate manufactured by UOP*5, and the
tubular cellulose acetate module by Westinghouse.0
Selas Corporation of America, Flotronics Division.
Universal Oil Products, ROGA Division.
Westinghouse Membrane Systems was sold to Union Carbide.
86
-------
RETURN LINE
00
f\f sooA FILTER
WASTE
SUMP
r
-04-
^f , ^
CONCENTRATE
PRODUCT
TANK
U.O.R
WEST.
PRODUCT ->_J
SELAS
TANK
CONCENTRATE
HYPERFILTRATION
LABORATORY
FILTER
Figure C-l. Flow schematic for equipment set-up at Plant #60.
-------
REUSE
All three types of membranes were used to generate samples for reuse
evaluation. A sample of composite wastewater was drawn from the plant sewer
through a 25-micron cartridge filter into the mobile laboratory. Hyper-
filtration of wastewater was conducted until 92% (by volume) of the water
was recovered as purified product water. Dyes, salts, etc., were concen-
trated in the remaining 8% of the water. Samples of both the product water
and the concentrate were taken at 75% recovery as well as at the 92%
recovery level.
Both the 75% and the 92% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 92% recovery samples were subjected
to detailed chemical analyses. The 92% recovery samples, of course,
represent the more severe test of reuse. Because membranes do not reject
100% of the dissolved material, the 8% by volume residue is only about ten
times as concentrated as the plant composite wastewater (instead of the
volumetric factor of twelve).
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of
purified product water evaluated for reuse were obtained just at the end
of the concentration (92%) , and thus contain higher concentrations of
chemicals than would be in the average product water. In fact, for these
membranes the mixed product water from a full-scale hyperfiltration plant
would contain only about 33% of the contaminants shown by the analyses
listed in Tables C-5 and C-6.
The three types of membranes were not operated simultaneously and
therefore did not process composite wastewater samples of exactly the same
characteristics. The collection of the samples for reuse took less than
five hours in the case of the cellulose acetate membranes, and about ten
hours for the dynamic membrane. In all instances, however, the concentrated
residue had a high COD (4560 and 7650 mg/Jl) , was highly colored, and con-
tained about 0.5% dissolved solids.
Since it may not always be desirable to attempt direct reuse or re-
clamation of the concentrate, the 92% recovery concentrate was used in the
treatability tests.
REUSE EVALUATION
Since the majority of the fibers processed by Plant #60 are nylon (80%),
the dyes, as well as the leveling agents, can be reused after hyperfiltra-
tion. since over 95% of the dyestuff is exhausted from the bath onto the
fibers, less than 5% of the dye is discharged to the waste stream. The
auxiliary chemicals, which are not consumed in the process, are all
discharged with the wastewater.
Reuse of Product Water
As a stringent test of the reuse of the product water, the 92% recovery
88
-------
TABLE 05. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #60
(92% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
b
Selas
Product
561
1/29/75
120
2.1
28
19
<1
62
62
18
10
0
55
0.03
6.8
<0.01
0.03
0.55
0.47
<0.01
-
-
<0.1
0.15
Selas
Concentrate
562
1/29/75
4560
66
1457
70
14
3148
3109
2138
1800
100
1000
0.02
6.4
<0.01
0.30
1.42
0.94
0.06
-
-
0.11
1.03
Reuse tests conducted in Plant #60 dye laboratory.
Selas module contained ceramic tubes with dynamic membranes.
° All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
89
-------
TABLE C-6. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #60
(92% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
i
UOPb
Product
563
1/29/75
64
5
13
10
<1
10
10
4
8
2
37
0
6.5
<0.01
0.01
0.38
0.27
<0.01
-
-
<0.1
0.11
/-«
Westinghouse
Product
564
1/29/75
284
14
63
5
3
186
181
80
40
10
140
0.03
5.6
<0.01
<0.01
0.66
0.30
<0.01
-
-
0.1
0.11
UOP/West
Concentrate
565
1/29/75
7650
1800
1800
160
50
6314
6303
3504
1500
60
2700
0
5.8
<0.01
1.32
3.77
8.48
<0.01
-
-
0.50
1.30
a
Reuse tests conducted in Plant #60 dye laboratory.
UOP module contained spiral-wound cellulose acetate membranes.
Westinghouse module contained tubular cellulose acetate membranes.
All results are in mg/Jl, except for color (Pt-Co units), turbidity
(FTU) , conductivity (ymho/cm) , and pH (unitless) .
90
-------
samples were evaluated. The analyses of the product water indicates that,
in general, the COD and dissolved solids are more than expected for tap
water, but the concentration of metals is less.
All of the purified product water generated by the mobile laboratory
at Plant #60 was suitable for reuse. Two dyeings, including tricolor carpet
shades, were conducted by the plant laboratory using the product water.
The first was Amber Red on polyester fabric using the dyes: Disperse
yellow Three, Cerise Y, Disperse Blue 87, Pat-Level-40, Kelate 100, and
Antifoam J-S. The second was Golden Touch Tricolor on polyester/nylon blend
fabric using the dyes: Basic Yellow 53, Basic Red 17, Basic Blue 22,
Disperse Blue 87, Acid Yellow 135, Acid Red 266, Pat-Level-40, Antifoam,
and metasodium phosphate.
The dyeing procedure for these tests was:
(1) Add dyes and leveling agents to bath.
(2) Add carpet swatch and bring to boil over thirty minutes.
(3) Boil for thirty minutes to one hour.
(4) Rinse in cold water and dry.
Reuse ofConcentrate
The attempts by the laboratory to use the concentrate in standard
production procedures had limited success. The composite waste contained a
complex mixture of dyes which could only be reused to dye a dull or dark
shade.
It may be possible, when the wastewater and chemicals are recycled,
to change the process to (1) achieve faster dyeing cycles, and/or (2)
to eliminate the need for some auxiliary chemicals. For example, with
direct dyeing of cellulose, salt can be eliminated by using higher concen-
trations of dye in the dyebath. Excess dyestuffs can be recovered by the
membranes for reuse in the next cycle. Depending on the amount of fiber
dyed and range of colors, this modification may or may not be practical.
Water, chemicals, and energy requirements will play a major role in the
selection of dyeing processes used in the future.
MEMBRANE PERFORMANCE
Universal Oil Product and Westinghouse cellulose acetate modules, and
Selas dynamic Zr-PAA membrane modules, were operated on prefiltered (no pH
adjustment was necessary) composite wastewater in two tests of 110 and 340
hours. During the 340-hour test, fresh feed was added on a daily basis
after which sufficient quantities of product and concentrate were discarded
to maintain a prescribed recovery. During the 110-hour test, fresh feed
was added and product and concentrate were discarded on a continuous basis.
The performance of the membranes was monitored by periodic measurements of
the product water flow rate through the membranes and the percentage
conductivity rejection.
91
-------
The two cellulose acetate modules and the Zr-PAA modules were fed
from separate feed tanks so that high-temperature operation of the Zr-PAA
membranes would be possible.
Dynamic Membrane
Two modules of Selas ceramic tubes with dynamic Zr-PAA membranes were
evaluated. The performance is summarized in Figures C-2 and C-3, graphs
of flux and rejection throughout the test periods. The characteristic
initially rapid flux decline is evident. One of the modules, #6, was
equipped with new membranes and therefore had a higher initial flux. Module
#5 was equipped with membranes that had already been used at Plant #50. This
older membrane exhibited a lower initial flux.
The effect of fluid velocity on the flux decline was the subject of
parametric testing. The lowering of the velocity of #5 and raising the
velocity of #6 at the 240-hour point (see Figure C-2) showed little effect
on the flux decline rate. The flux that would be used for design cost
projections is 0.8 m/d (20 gallons/ft2/d) at 50°C and 6.8 MPa (1000 psig),
a value of only about 30% of the initial flux.
The conductivity rejection allows measurement of the electrolyte
filtration by the membrane. The filtration efficiency for larger organic
molecules is usually higher than for the electrolytes. Grab samples of
the feed to the membrane and the product water passing through the membranes
were obtained during the performance tests and analyzed to indicate the
filtration efficiency for several constituents. The results of analyses
for four pairs of samples are shown in Tables C-7 through C-10.
The 95 - 99% rejection of organics, indicated by COD, BOD, and color
comparisons between the concentrate and product samples are greater than
the conductivity rejections. The rejection of metals is very high/ as
indicated in cases where results are significantly above the limit of
detection.
Cellulose Acetate Membranes
The performance of spiral-wound and tubular cellulose acetate membrane
modules is summarized in Figures C-4 and C-5, graphs of the flux and re-
jection throughout the test periods. The operating conditions were as
specified by the module manufacturers: 2.76 MPa (400 psig), and feed rates
of 14 - 15 dmVmin (3.5 - 4 GPM) , and 12 dm3/ndn (3.2 GPM) for the spiral
and tubular, respectively.
The flux declined throughout the test periods during which time no
washing procedures were attempted. The conductivity rejection was in the
range of 90 - 95% for the spiral and 60 - 90% for the tubular. The re-
jection of other wastewater constituents was also very high, as indicated
by the results of analyses of samples taken during the two tests (see
Tables C-ll through C-14).
92
-------
100.0
2 80.0
o
to
-3
UJ
(T
60.0
—B- a
a
a a .a
A NO. 5, V =4.9 "H and 2.6 m/s,BEFORE AND AFTER 240 HR
O N0.6,V*3.I "H and 4.9 "H,BEFORE AND AFTER 240 HR
4.0
-80.0
•o
*S»
CM
V.
V)
c.
o
= 40.0
o _
o» G
*•" •
X
u.
00
_
X
_CT
Or ^**""ts— ^ Q^ _
\^ A. A A A ^^ ^^ *3
1 1 1 1 1
3.0 ^
\
CM
^E
2.0 1
-^_r-
X
3
1.0 ^
0
0 72 144 216 288 360
TIME (hours)
Figure C-2.
Hyperfiltration of combined effluent at Plant #60 by
Zr(IV)-PAA membranes on Selas ceramic supports. (P =
6.9 MPa (1000 psig); T = 50°C; pH = 6.6 - 7.2; recovery
75%; maintained by daily addition of fresh feed and
recycled product.)
93
-------
100.0
60.0
A fcn&r A:
.IT
120.0
A NO. 5, V= 1.6
Q N0.6tV=3.3m/8
-— AA
^^
24
48 72
TIME (hours)
96
5.0
4.0
3.0
2.0
1.0
0.0
•D
CM
120
Figure C-3.
Hyperfiltration of coiribined effluent at Plant #60 by
Zr(IV)-PAA mentoranes on Selas ceramic supports. (P =
6.9 MPa (1000 psig); T = 61°C; pH = 6.1 - 6.9; recovery
75%.)
94
-------
TABLE C-7. PERFORMANCE PARAMETERS OF SELAS MODULES3 IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
567
Concentrate
2/10/75
1330
96
225
62
3
722
679
370
120
40
450
0
6.6
0.001
0.15
3.06
1.60
0.1
0.1
1.28
0.18
2.36
568
Product
2/10/75
69
6
42
8
0.5
30
28
22
0
0
30
0
6.4
0.001
0.27
2.76
1.40
0.1
0.1
0.09
0.1
1.25
k Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/Jl, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
95
-------
TABLE C-8. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
574
Product
2/12/75
77
7
60
14
0.5
84
83
26
5
3
70
0.01
6.8
0.001
0.02
0.53
0.50
0.1
0.1
0.1
0.1
1.04
575
Concentrate
2/12/75
5270
380
1080
58
25
3244
3205
2140
1200
160
1400
0.13
6.1
0.001
0.65
4.57
2.63
1.4
0.1
3.04
0.28
7.7
Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
96
-------
TABLE C-9. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids -
Dissolved' Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
582
Product
2/13/75
73
6
62
15
0.5
78
76
14
5
0
80
0.05
7.0
0.001
0.01
0.72
0.75
0.1
0.1
0.15
0.1
1.07
583
Concentrate
2/13/75
6374
190
1100
47
30
1782
1734
1112
400
300
1550
0.16
6.1
0.001
0.94
3.97
4.85
0.28
0.24
3.73
0.46
8.74
* Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/S., except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
97
-------
TABLE C-10. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
SAMPLE NUMBER
TYPE
DATE TAKEN '
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
587
Product
2/14/75
134
24
37
15
0.5
184
171
98
30
15
110
0.06
6.1
. 0.001
0.1
0.76
0.44
0.11
0.1
0.19
0.1
1.31
588
Concentrate
2/14/75
7100
800
1380
38
22
3668
3639
2270
2000
300
1600
0.12
5.8
0.001
1.02
0:84
4.79
3.87
0.21
3.50
0.59
9.22
, Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
98
-------
100.0
3?
Z
2 80.0
h-
o
UJ
UJ
* 15-0
_^
u.
0.0
- A SPIRAL, REJECT FLOW = 17 (4.5) ond I4(3.7)dm?inin
BEFORE AND AFTER 192 HR
Q TUBULAR, REJECT FLOW = 1 1- 15 dmymjn (3-4GPM)
••
-
\Q Q
] e ^"^^-^ a Q
^^-A-^-^ A A A Er~~S— g -^Q t^^.
A A ^ — A — A—
l 1 1 I
(6PM)
1.5
—
1.0 c^
*L
X
0.53
u.
0.0
72
144 215
TIME (hours)
288
360
Figure C-4.
Hyperfiltration of combined effluent at Plant #60 by
Westinghouse tubular and UOP spiral-wound cellulose
acetate membrane modules. (P = 2.8 MPa (400 psig);
T = 20°C; pH = 6.4 - 7.0; recovery = 75% and 90% before
and after 160 hours.)
99
-------
100.0,
z
o
o
LU
80.0
60.0
45.0
30.0
o
o>
15.0
A SPIRAL, REJECT FLOW*l4and 15 dmVmin (3-8 and 4.06PM)
BEFORE AND AFTER 72 HR 3
O TUBULAR, REJECT FLOW = 12 dmXmjn (3.26PM)
48 72
TIME (hours)
120
1.5
\
CJ
0.5
0.0
Figure C-5.
Hyperfiltration of coiribined effluent at Plant #60 by
Westinghouse tubular and UOP spiral-wound cellulose
acetate membrane modules. (P = 2.8 MPa (400 psig);
T = 22°C; pH = 6.4 - 6.9; recovery - 75%.)
100
-------
TABLE Oil. PERFORMANCE PARAMETERS OF UOP AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
UOP/West
Concentrate
569
2/10/75
1765
128
345
14
4
710
670
630
220
40
92
0.05
6,1
0.001
0.02
0.81
2.29
0.11
0.1
0.21
0.14
3.56
uopa
Product
570
2/10/75
41
9
6
4
0
20
19
16
0
0
6.9
0
5.7
0.001
0.07
0.57
1.77
0.11
0.1
0.07
0.11
2.24
b
Westinghouse
Product
571
2/10/75
126
10
31
4
1
72
65
62
5
15
19
0.02
5.6
0.001
0.17
0.57
1.67
0.11
0.1
0.1
0.1
1.4
f UOP module contained spiral-wound cellulose acetate membranes.
Westinghouse module contained tubular cellulose acetate membranes.
° All results are in mg/H, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
101
-------
TABLE C-12. PERFORMANCE PARAMETERS OF WESTINGHOUSE AND UOP MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
, Westinghouse module
UOP module contained
c
Westinghouse
Product
576
2/12/75
837
124
155
12
5
558
540
390
70
20
190
0.01
5.6
0.001
0.14
0.39
1.21
0.1
0.1
0.45
0.57
2.94
uopb
Product
577
2/12/75
36
5
6
4
1
12
12
10
0
2
16
0.02
6.0
0.001
0.01
0.46
0.52
0.1
0.1
0.07
0.1
1.09
West/UOP
Concentrate
578
2/12/75
3525
250
840
36
28
2136
2097
1638
380
40
620
0.02
6.2
• o.ooi
0.47
0.43
3.21
0.22
0.1
1.07
0.16
6.76
contained tubular cellulose acetate membranes.
spiral-wound cellulose acetate membranes.
All results are in mg/£, except for color (Pt-Co units) , turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
102
-------
TABLE C-13. PERFORMANCE PARAMETERS OF WESTINGHOUSE AND UOP MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Westinghouse
Product
584
2/13/75
337
8
80
16
1
188
176
118
40
30
110
0.02
5.8
0.001
0.11
0.37
2.73
0.1
0.28
0.24
0.15
3.44
UOP
Product
585
2/13/75
45
6
94
17
0.3
12
10
10
5
5
39
0.04
6.4
0.001
0.01
0.35
0.71
0.1
0.1
0.08
0.1
1.59
West/UOP
Concentrate
586
2/13/75
4660
290
870
77
10
2840
2804
1976
1200
40
1100
0.11
6.1
0.001
0.61
0.69
3.21
0.11
0.1
0.99
0.18
6.98
k Westinghouse module contained tubular cellulose acetate membranes.
UOP module contained spiral-wound cellulose acetate membranes.
C All results are in mg/fc, except for color (Pt-Co units), turbidity
(FTU), conductivity (vimho/cm) , and pH (unitless).
103
-------
TABLE C-14. PERFORMANCE PARAMETERS OF UOP AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #60
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
uopa
Product
589
2/14/75
36
5
8
3
0.5
10
9
2
15
0
16
0.01
6.4
0.001
0.01
0.63
0.69
0.1
0.1
0.1
0.1
3.92
Westinghouse
Product
590
2/14/75
219
16
54
12
1
190
182
118
70
10
91
0
6.2
0.001
0.06
0.70
1.02
0.22
0.1
0.29
0.1
2.48
UOP /West
Concentrate
591
2/14/75
3550
150
620
48
19
2060
2038
1412
750
90
840
0.04
6.2
0.001
0.52
0.69
2.38
0.13
0.1
0.91
0.1
5.77
UOP module contained spiral-wound cellulose acetate membranes.
Westinghouse module contained tubular cellulose acetate membranes.
All results are in mg/Jl, except for color (Pt-Co units) , turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
104
-------
APPENDIX D
PLANT #70
The on-site tests conducted from February 26, 1975, to March 26, 1975,
were to obtain the following information: (1) plant laboratory evaluation
of reuse, and (2) engineering performance data with membranes. Reuse of
both the purified product water and the concentrated residue was evaluated
in laboratory tests conducted by Plant #70 personnel. Samples of waste-
water, purified product water, and the concentrated residue were analyzed by
Nardin Laboratory.3 In addition, the treatability of the concentrated
residue was evaluated in bench-scale tests, Appendix J.
The production parameters of Plant #70, given in Table D-l, provide a
basis for evaluation of the results of the project. The factors are
important in the evaluation of the practicality of scale-up from the pilot
plant.
FIBERS AND CHEMICALS
The dyeing and finishing processes at Plant #70 involve several
different dyes and finishes. The dyeing is done in high-temperature package-
dyeing machines and atmospheric skein-dyeing equipment. The principal dyes
employed, comprising 95% of the total usage, are basic dyes. The materials
processed are acrylic (98%), nylon (1%), and wool and mohair (1%).
Ninety percent of the 1892 m3/d (500,000 gallons/day) total water
usage is in the dyehouse. Allowing for evaporation in the dyehouse, the
composite waste stream is at least 85% by volume dyehouse wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based
on a monthly average for the summer of 1974, of plant wastewater discharge
parameters are: BOD5 = 375 mg/A; COD - 700 mg/A; total suspended solids =
140 mg/SL; total dissolved solids = 800 mg/Jl; pH » 4.0; temperature = 160°F.
Table D-2 presents the results of analyses for two grab samples obtained
, Division of Commonwealth Laboratory, Inc., Greenville, SC.
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
022-a, US Environmental Protection Agency, Washington, DC, 1974.
105
-------
TABLE D-l. PLANT #70 PRODUCTION CAPACITY PARAMETERS
QUANTITIES USED
Materials: acrylic, nylon, wool, mohair
Water (total to plant), m3/day 1,892
(gallons/day) (500,000)
Water (to dyehouse), ra3/day 1,649
(gallons/day) (435,335)
Dyes, kg/day 250
(pounds/day) (550)
Auxiliary Chemicals, kg/day 1,140
(pounds/day) (2,514)
Q
Energy (for process steam), joules/day 292 x 10
(Btu/day) (278 x 106)
UNIT COSTS
Water,
-------
TABLE D-2. CHEMICAL ANALYSES OF PLANT #70 WASTEWATER3
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BQD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conduct i vi ty
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
600
2/28/75
226
135
-
34
8
371
329
-
20
2.1
430
0.011
7.25
-
-
0.120
0.020
0.067
0.020
0.125
0.018
—
617
3/10/75
973
510
-
38
55
723
657
-
500
6.3
540
0.009
7.50
-
-
0.360
0.475
0.100
0.020
4.792
3.357
^
, Grab samples of total plant effluent.
All results are in mg/£, except for color (APHA units), turbidity
(NTU), conductivity (umho/cm), and pH (unitless).
107
-------
during the period of on-site testing. Plant #70 is classified as Sub-
category 7, stock and yarn dyeing and finishing.a
SCHEDULE AND PROCEDURE
Schedule
The mobile laboratory arrived at Plant #70 on February 26, 1975. The
utilities were connected and the system was placed in operation on
February 28.
Initially, one-gallon (3.8£) samples of purified product and concentrate
were collected for reuse evaluation in the plant laboratory. A 38£ sample
of concentrate was later collected for the biological treatability study.
The following is a list of events at Plant #70:
02/26 - Arrived from Plant #60; utilities connected.
02/27 - Operated UOP module with standard salt solution (1000 mg/£).
02/28 - Operated Selas modules #9, #4, and #12 with standard salt solution.
03/03 - Plant personnel replaced 5 kva transformer in mobile lab.
03/04 - Began reuse tests; feed neutralized from 4.3 to 7.1 for Selas
modules. Not neutralized for UOP module.
03/07 - Began engineering performance tests? waste neutralized to ^-7 for
all modules.
03/15 - Ended engineering performance tests.
03/19 - Operated Selas #9, #4 with salt solution. Began special tests with
spent dye liquor.
03/21 - Ended special tests.
03/25 - Prepared for departure.
03/26 - Moved to Plant #40.
Procedure
The membranes for evaluation were selected based on availability and
the characteristics of the wastewater. The wastewater was prefiltered
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
108
-------
through 25-micron cartridge filters prior to entering the mobile laboratory.
The pH was adjusted when necessary to meet membrane manufacturer specifi-
cations. Figure D-l shows schematically the equipment arrangement. Two
module types were evaluated: the dual-layer dynamic membrane on Selasa
ceramic tubes, and the spiral-wound cellulose acetate manufactured by OOP*3.
REUSE
Both types of membranes were used to generate samples for reuse
evaluation. A sample of composite wastewater was drawn from the plant sewer,
and pumped through a 25-micron filter into the mobile laboratory. The
hyperfiltration was conducted until 90% (by volume) of the water was recover-
ed as purified product water. Dyes, salts, etc., were concentrated in the
remaining 10% of the water. Samples of both the product water and the
concentrate were taken at 75% recovery, and also at the 90% recovery level.
Both the 75% and the 90% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course,
represent the more severe test of reuse. Because membranes do not separate
100% of the dissolved material, the 10% by volume residue is only about
eight times as concentrated as the plant composite wastewater (instead of
the volumetric factor of ten).
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of
purified product water evaluated for reuse were obtained near the end of
the concentration (90%), and thus contain more chemicals than the average
product water would have. In fact, for these membranes the mixed product
water from a full-scale hyperfiltration plant would contain only about
one-third the contaminants shown by the analyses listed in Tables D-3 and
D-4.
The two types of membranes were not tested simultaneously and therefore
did not process composite waste with exactly the same characteristics. The
collection of the samples for reuse took less than five hours in the case
of the cellulose acetate membrane, and about ten hours for the dynamic
membrane. In both instances, however, the concentrated residue had a high
COD (3300 and 4850 mg/A), was highly colored (Table D-3), and contained
about 0.5% dissolved solids.
Since it may not always be desirable to attempt direct reuse or
reclamation of the concentrate, the 90% recovery concentrate was used in
the treatability tests.
Selas Corporation of America, Flotronics Division.
Universal Oil Products, ROGA Division.
109
-------
TABLE D-3. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #70
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
UOPb
Product
611
3/4/75
368
80
84
-50
<0.3
144
144
80
10
0
135
0.05
4.6
0.002
<0.01
<0.01
0.57
<0.1
<0.01
0.01
0.17
2.56
UOP
Concentrate
613
3/4/75
3300
260
750
-70
70
3620
3608
1680
450
50
2500
0.08
4.9
0.003
0.56
2.25
1.37
0.21
0.21
9.22
0.73
1.19
Reuse tests conducted in Plant #70 dye laboratory.
UOP module contained spiral-wound cellulose acetate membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
110
-------
TABLE D-4. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #70
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
607
3/4/75
226
56
88
35
<0.3
272
272
126
0
0
250
0.06
8.5
<0.001
<0.01
0.01
0.79
<0.1
-------
IOM
SUMP
OVERFLOW
TO
SUMP
TANK
r
~l
>
f
>_...
i
T
i \
'AN
t
K
UTRAUZJNG
NK
t
\
PRODUCT
CONCENTRATE
— U.OP.
SELAS
HYPERFILTRATION LABORATORY
CONCENTRATE
FILTER
TOTALIZING
FLOW
METER
J
TO SUMP
WASTE
PRODUCT
Figure D-l. Plow schematic for equipment set-up at Plant #70.
-------
REUSE EVALUATION
Since most fibers processed by Plant #70 are acrylic (>98%), the waste
stream contains mostly basic dyes. All these dyes, as well as the leveling
agents and carriers used as auxilaries with them, can be recovered by
hyperfiltration. Over 95% of the dyestuff is exhausted from the bath onto
the fibers. Therefore, less than 5% of the dye is discharged to' the waste
stream. The auxiliary chemicals, which are not consumed in the process,
are discharged with the wastewater and could be recovered. The analytical
results for purified product and the concentrated residue, at the 90%
recovery level by the cellulose acetate and dynamic membranes, are presented
in Tables D-3 and D-4, respectively.
Reuse of Product Water
As a stringent test of the reuse of the product water, the 90% recovery
samples were evaluated. The analyses of the product water (Table D-3)
indicates that, in general, the COD and dissolved solids are more than
expected for tap water, but the concentration of metals is less.
The product water was evaluated in the plant laboratory and found to
be equivalent to normal process water. One of the two membrane units
evaluated produced a slightly colored product water. The cause was traced
to a mechanical breakdown rather than poor membrane rejection.
The specific procedure used by the Plant #70 dye laboratory for
evaluation of the reuse of product water was as follows:
(1) Raise dyebath to 66°C (150°F).
(2) Add the following chemicals:
Sequesterene ST 0.10% of the weight of fabric
Sodium Acetate 1.00% of the weight of fabric
Chemogen RC-90 2.00% of the weight of fabric
Migrassist AC 2.00% of the weight of fabric
Glaubers Salt 5.00% of the weight of fabric
Basic Yellow 13 0.0095% of the weight of fabric
Basic Red 18 0.0410% of the weight of fabric
Basic Blue 3 0.0300% of the weight of fabric
Basic Blue 71 0.0970% of the weight of fabric
(3) Raise temperature at l°/min to 43°C (110°F) and hold for 45
minutes.
(4) Cool.
(5) Rinse until clear.
Reuse of Concentrate
The attempts by the laboratory to use the concentrate in standard
production procedures were not successful. The composite waste contained
only small quantities of dye. No attempts were made to determine special
formulations and to evaluate corresponding dye savings.
It is possible, when the wastewater and chemicals are recovered by
113
-------
hyperfiltration, to change the process to (1) achieve faster dyeing
cycles, and/or (2) to eliminate the need for some auxiliary chemicals.
For example, with direct dyeing of cellulose, salt can be eliminated by
using higher concentrations of dye in the dyebath. Excess dyestuffs will
be recovered by the membranes for reuse in the next cycle. Depending on
the amount of fiber dyed and range of colors, this modification may or may
not be practical. Water, chemicals, and energy requirements will play a
major role in the selection of dyeing processes used in the future.
MEMBRANE PERFORMANCE
Both the cellulose acetate membrane and the dynamic membrane were
operated on pretreated composite wastewater (Table D-5) for 200 hours
beginning on March 7, 1975. The performance of the membranes was monitored
by periodic measurements of the product water flow rate through the
membranes and the conductivity rejection.
The wastewater feed to the UOP cellulose acetate and the dynamic Zr-PAA
membranes was from a common tank. The incoming feed was neutralized and
controlled at about pH - 7 with sodium hydroxide. The volumetric recovery
was allowed to rise to ^80% by the withdrawal of product water and was
maintained at 80% throughout the 200-hour test. The circulation velocities
through the Selas module were changed at the 77-hour point in the test as
shown in Figure D-2. The temperature was maintained at near 30°C because
of temperature limitations of the cellulose acetate membrane.
Dynamic Membrane
Three different modules of Selas ceramic tubes with dynamic Zr-PAA
membranes were evaluated. The performance is summarized in Figure D-2, a
plot of flux and rejection throughout the test period. The characteristic
initially rapid flux decline is evident. One of the modules, #9, was
equipped with new membranes and therefore had a higher initial flux.
Module #4 was equipped with ten-month old membranes that had already been
used at several other plants. This older membrane exhibited a lower
initial flux.
The effect of fluid velocity on the flux decline is illustrated in the
figure. The operation of module #12 at 4.25 m/s (14 fps) may have permitted
it to achieve a higher, more stable flux in the period from 77 to 200 hours.
The lowering of the velocity in the other two modules at 77 hours caused
a gradual decrease in flux.
The flux that would be used for design cost projections is 0.7 m/d
}allons/ft2/d) at 26
45% of the initial flux.
(18 gallons/ft2/d) at 28°C and 6.8 MPa (1000 psig), a value of only about
While the flux declined, the conductivity rejection increased. Both
phenomena would be the result of the formation of a self-rejecting layer
formed on the membrane surface from the constituents in the wastewater.
The conductivity rejection is a measure of the separation or filtration
114
-------
TABLE D-5. CHEMICAL ANALYSES OF WASTEWATER TREATED*1 FOR
MEMBRANE PERFORMANCE TESTS AT PLANT #70
SAMPLE NUMBER
DATE TAKEN
PARAMETER13
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conducti vi ty
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
618
3/13/75
708
390
-
43
60
1216
1164
-
500
4.6
850
0.012
7.65
-
-
0.400
0.025
0.030
0.020
1.875
1.161
""
623
3/14/75
622
355
-
41
16
1115
1065
-
200
2.2
880
0.008
7.50
-
-
0.320
0.050
0.033
0.020
1.750
0.750
a Grab sample of combined effluent with 25-micron prefiltration,
followed by neutralization to pH ^ 7.
All results are in mg/£, except for color (APHA units), turbidity
(NTU), conductivity (ymho/cm), and pH (unitless).
115
-------
100.0
* 9
o
p 85-Qli.
u
UJ
UJ
70.0
SB
o o
o
A"
O
Q
0©
A
00
J A "
60.0
•o
£ 40.0
c
o
o> <
x20.0
u_
0.0
- 0 NO. 4, V= 4.3 and 2.4 m/i BEFORE AND AFTER 77 HR
A N0.9,V=4.9and 2.6 m/fc BEFORE AND AFTER 77 HR
Q NO.I2,V=2.8 and 4.6 m/t BEFORE AND AFTER 77 HR
-
> tf^ ,A
—o— -^2s--& _2A. 0=8=^^^. ^^
0
1 1 1 1 1
2.0
•a
\
CM
\
=3
U.
40
80 120
TIME (hours)
160
200
Figure D-2.
Hyperfiltration of combined effluent at Plant #70 by
Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 28°C; pH = 5.5 - 7.6;
recovery = 90%.)
116
-------
of electrolytes by the membrane. The filtration efficiency for larger
organic molecules is usually higher than for the electrolytes. Grab samples
of the feed to the membrane and the product water passing through the
membranes were obtained during the 200-hour performance tests and analyzed
to indicate the filtration efficiency for several constituents. The
results of analyses for three pairs of samples are shown in Tables D-6,
D-7, and D-8.
The 95 - 99% rejections of organics, indicated by COD, BOD, and color
comparisons between the concentrate and product samples are greater than
the conductivity rejections. The phenol rejection is about 88%. The
rejection of metals is very high, as indicated in cases where results are
significantly above the limits of detection.
Cellulose Acetate Membrane
The performance of spiral-wound cellulose acetate membrane modules is
illustrated in Figure D-3, a plot of the membrane flux and rejection
throughout the test period. The operating conditions were as specified
by the UOP module manufacturer: 2.76 MPa (400 psig) , and a feed rate of
0.8 - 0.9 m3/hr (3.5 - 4 GPM) . This module had been used at two previous
sites (Plant #50 and Plant #60).
The flux declined throughout the 200-hour test period during which
time no washing procedures were attempted. The conductivity rejection was
in the range of 90 - 95% throughout the test period. The rejection of
other wastewater constituents was also very high, as indicated by the results
of analyses of samples taken during the 200-hour test (see Tables D-9, D-10,
and D-ll).
117
-------
TABLE D-6. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #70
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
614
Concentrate
3/10/75
2661
2000
-
38
90
5600
5480
-
500
7.9
4100
0.042
7.15
-
-
1.280
0.075
0.567
0.020
3.125
2.464
-
615
Product
3/10/75
94
39
-
9
1
183
177
-
10
0.15
190
0.005
7.60
-
-
0.040
0.020
0.030
0.020
0.005
0.018
-
Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/£, except for color (APHA units), turbidity
(NTU), conductivity (pmho/cm), and pH (unitless).
118
-------
TABLE D-7. PERFORMANCE PARAMETERS OF SELAS MODULESa IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #70
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
622
Product
3/13/75
51
45
-
8
2
159
159
-
5
0.10
170
0.005
7.40
-
-
0.040
0.020
0.030
0.020
0.005
0.018
—
621
Concentrate
3/13/75
2303
2200
-
83
110
5448
5412
-
500
4.1
4400
0.661
7.55
—
-
0.330
0.025
0.500
0.020
3.042
2.946
a Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/£, except for color (APHA units), turbidity
(NTU), conductivity (ymho/cm), and pH (unitless).
119
-------
TABLE D-8. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #70
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER13
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
624
Concentrate
3/14/75
2280
1450
-
72
90
5585
5535
-
500
1.9
3700
0.055
8.00
-
-
0.800
0.020
0.030
0.020
0.005
0.010
-
625
Product
3/14/75
51
48
-
11
1
233
227
-
5
0.20
190
0.005
7.25
-
-
0.040
0.020
0.030
0.020
0.005
0.018
-
a
Selas module contained
ceramic tubes with
i . i ^ _ _ _ _._•»_._
dynamic membranes.
All results are in mg/&, except for color (APHA units), turbidity
(NTU), conductivity (pmho/cm), and pH (unitless).
120
-------
100.0
z
o
£ 80.0
o
UJ
-3
UJ
oc.
60.0
A A
A A
A
A
A
A A
A
15.0
A SPIRAL, REJECT FLOW* 13-13
x 5.
A
A
0.0
«ar—
1
0 40
v* — —
,
80
JB, „
i
120
A A^_A
1
160
^T^
A
,
200
0.6
0.4~
\
CVI
£
0.2 x
=3
_l
U.
0.0
TIME (hours)
Figure D-3.
Hyperfiltration of combined effluent at Plant #70 by a
UOP spiral-wound module with cellulose acetate membranes.
(P = 2.8 MPa (400 psig); T = 26°C; pH = 4.1 - 7.7;
recovery = 90%.)
121
-------
TABLE D-9. PERFORMANCE PARAMETERS OF UOP MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #70
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
614
Concentrate
3/10/75
2661
2000
-
38
90
5600
5480
-
500
7.9
4100
0.042
7.15
-
-
1.280
0.075
0.567
0.020
3.125
2.464
-
616
Product
3/10/75
140
80
-
11
1
143
137
-
5
2.1
52
0.005
6.70
-
-
0.080
0.020
0.030
0.020
0.005
0.010
-
UOP module contained spiral-wound cellulose acetate membranes.
All results are in rng/A, except for color (APHA units), turbidity
(NTU), conductivity (pmho/cm), and pH (unitless).
122
-------
TABLE D-10. PERFORMANCE PARAMETERS OF UOP MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #70
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
- - i j - • ••• ' • —
a UOP module contained
*J -»«11 ^ 1 .!_ _ •»»,•,«. £ « «**
621
Concentrate
3/13/75
2303
2200
-
83
110
5448
5412
-
500
4.1
4400
0.661
7.55
-
-
0.330
0.025
0.500
0.020
3.042
2.946
-
_•___——————•—••—•——
spiral-wound cellulose
v /n AW4*vt4- fr\v /ii-il rkv (I
620
Product
3/13/75
148
36
-
9
1
76
64
-
5
0.35
66
0.005
6.85
—
—
0.040
0.020
0.030
0.020
0.005
0.010
~
acetate membranes.
IVPHA units ) . turbiditv
n.t J- i. V*fc* Wtd. \~+~r «AA. -M —.-- -..^y^ "~ W ~— — — ^___
(NTU), conductivity (ymho/cm), and pH (unitless).
123
-------
TABLE D-ll. PERFORMANCE PARAMETERS OF UOP MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #70
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
624
Concentrate
3/14/75
2280
1450
-
72
90
5585
5535
-
500
1.9
3700
0.055
8.00
-
-
0.800
0.020
0.030
0.020
0.005
0.010
-
626
Product
3/14/75
156
32
-
10
1
83
77
-
5
0.45
120
0.005
7.30
-
-
0.040
0.020
0.033
0.020
0.005
0.005
-
UOP module contained spiral-wound cellulose acetate membranes.
All results are in mg/Jl, except for color (APHA units) , turbidity
(NTU) , conductivity (iamho/cm) , and pH (unitless) .
124
-------
APPENDIX E
PLANT #40
The on-site tests conducted from March 26, 1975, to April 23, 1975,
were to obtain the following information: (1) plant laboratory evaluation
of reuse, and (2) engineering performance data with membranes. Reuse of
both the purified product water and the concentrated residue was evaluated
in laboratory tests conducted by Plant #40 personnel. Samples of waste-
water, purified product water, and concentrated residue were analyzed by
Nardin Laboratory.3 In addition, the treatability of the concentrated
residue was evaluated in bench-scale tests, Appendix J.
The production parameters of Plant #40, Table E-l, provide a basis for
evaluation of the results of the project. The factors are important in the
evaluation of the practicality of scale-up from the pilot plant.
FIBERS AND CHEMICALS
Plant #40 is presently operated to scour, bleach, dye, and finish
cotton and cotton/polyester blended fabrics on continuous ranges. The
chemicals and dyes used by the plant are those which are common to the
finishing of cotton and polyester fibers: sulfur, vat, fiber reactive,
disperse, and napthol dyes.
Ninety percent of the 20,833 m3/d (5,500,000 gallons/day) total water
usage is in the plant. Allowing for evaporation in drying, the composite
waste stream is at least 85% by volume plant wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based
on a monthly average for the summer of 1974, of plant wastewater discharge
parameters are: BODs = 350 mg/Jl; COD 1290 mg/£; total suspended solids =
346 mg/£; total dissolved solids = 3310 mgA; pH « 11.6; temperature = 100°F.
Tables E-2, E-3, and E-4 present the results of analyses for eight grab
Division of Commonwealth Laboratory, Inc., Greenville, SC.
125
-------
TABLE E-l. PLANT #40 PRODUCTION CAPACITY PARAMETERS
QUANTITIES USED
Materials: cotton, cotton/polyester
Water (total to plant), m3/day
\ (gallons/day)
Water (wet finishing), m3/day
(galIons/day)
Dyes, kg/day
(pounds/day)
Auxiliary Chemicals, kg/day
(pounds/day)
Energy (for process steam), joules/day
(Btu/day)
20,833
(5,500,000)
20,545
(5,400,000)
8,353
(18,565)
39,342
(86,750)
7358 x 109
(7008 x 106)
UNIT COSTS
Water, £/m3
($/1000 gallons)
Fuel, C/107 joules
($/106 Btu)
2
(0.06)
2.0
(2.20)
126
-------
TABLE E-2. CHEMICAL ANALYSES OF PLANT #40 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
633
4/2/75
1360
270
534
1549
13
4000
2920
768
350
6.0
6400
0.004
11.7
<0.1
<0.04
2.0
0.2
0.1
13
2.2
0.4
1.9
648
4/3/75
1520
330
620
1424
15
3140
2888
910
250
10
5800
0.097
11.7
<0.1
<0.04
2.5
0.2
0.1
0.15
1.3
0.2
2.0
654
4/7/75
1860
380
563
1158
13
3812
3634
1020
300
5.5
4500
0.053
11.5
<0.1
<0.04
1.5
0.2
0.1
31
3.2
0.4
1.8
Grab samples of total plant effluent.
All results are in rng/S,, except for color (APHA units) , turbidity
(mg/fc SIO2) , conductivity (yiriho/cm) , pH (unit less), and mercury (yg/K.)
127
-------
TABLE E-3. CHEMICAL ANALYSES OF PLANT #40 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
655
4/7/75
1340
360
615
1408
14
2784
2568
576
200
6.5
6700
0.097
11.8
<0.1
0.04
1.2
0.2
0.1
61
4.3
1.6
2.1
661
4/8/75
1420
340
558
1483
38
2990
2840
620
250
13
6500
0.159
11.8
<0.1
0.04
2.2
0.2
0.1
8
5.6
1.0
10.8
667
4/9/75
1460
420
547
1599
12
3344
3226
912
150
14
7100
0.060
11.8
<0.1
0.04
1.8
0.2
0.1
13
1.1
1.0
1.7
Grab samples of
total plant effluent.
All results are in mg/Jl, except for color (APHA units) / turbidity
(mg/H SIO2), conductivity (ymho/cm), pH (unitless), and mercury (yg/A)
128
-------
TABLE E-4. CHEMICAL ANALYSES OF PLANT #40 WASTEWATER^
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
668
4/9/75
1424
585
372
1650
10
3750
3670
1900
720
170
8200
0.10
11.9
1.0
<0.01
0.96
2.25
0.47
5.13
2.20
1.52
2.06
677
4/10/75
1160
350
666
1674
14
3388
3190
1082
100
7.0
6500
0.080
11.8
<0.1
0.08
1.5
2
0.1
3
1.5
9.0
2.2
* Grab samples of total plant effluent.
All results are in mg/A, except for color (APHA units), turbidity
(mg/Si SI02) , conductivity (umho/cm) , pH (unitless) , and mercury
129
-------
samples obtained during the period of on-site testing. Plant #40 is
classified as Subcategory 4, woven fabric dyeing and finishing.a
SCHEDULE AND PROCEDURE
Schedule
Testing was begun on April 1, 1975. Initially, one-gallon (3.8£)
samples of purified product and concentrate were collected for reuse evalu-
ation in the plant laboratory, The UOP module was then taken out of
operation for the remainder of Plant #40's testing program. A 38£ sample of
concentrate was later collected for the biological treatability study.
The following is a summary of events at Plant #40:
03/26 - Arrived from Plant #70; utilities connected.
04/01 - Began parametric performance test with Westinghouse polysulfone
ultrafilter and Selas modules.
04/02 - Reuse test samples generated.
04/11 - Parametric performance test completed.
04/15 - Began special tests.
04/22 - Special tests completed.
04/23 - Departed to Plant #80.
Procedure
The membranes for evaluation were selected based on availability and
the characteristics of the wastewater. The wastewater was prefiltered
through 25-micron cartridge filters prior to entering the mobile laboratory.
The pH was adjusted when necessary to meet membrane manufacturer specifi-
cations. Figure E-l shows schematically the equipment arrangement. Three
types of membranes were employed in these tests: the UOP33 spiral-wound
cellulose acetate membrane, the dual-layer dynamic membrane on the Selasc
ceramic tubes, and the Westinghoused tubular polysulfone ultrafilter.
REUSE
All types of membranes were used to generate samples for reuse
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
Universal Oil Products, ROGA Division.
c
Selas Corporation of America, Flotronics Division.
Westinghouse Membrane Systems was sold to Union Carbide.
130
-------
OVERFLOW
SUMP
TANK
FILTER
TANK
PRODUCT
CONCENTRATE
SPARSE
pH ADJUST
SELAS
WESTINGHOUSE
HYPERFILTRATION
LABORATORY
TOTALIZING
FLOW METER
TO SUMP
.WAS
(T
Figure E-l. Flow schematic for equipment set-up at Plant #40.
-------
evaluation. A sample of composite wastewater was drawn from the plant sewer,
and pumped through a 25-micron filter into the mobile laboratory. The
hyperfiltration was conducted until 90% (by volume) of the water was recover-
ed as purified product water. Dyes, salts, etc., were concentrated in the
remaining 10% of the water. Samples of both the product water and the
concentrate were taken at 75% recovery, and also at the 90% recovery level.
Both the 75% and the 90% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course,
represent the more severe test of reuse. Because membranes do not separate
100% of the dissolved material, the 10% by volume residue is only about eight
times as concentrated as the plant composite wastewater (instead of the
volumetric factor of ten).
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of
purified product water evaluated for reuse were obtained near the end of
the concentration (90%), and thus contain more chemicals than the average
product water would have. In fact, for these membranes the mixed product
water from a full-scale hyperfiltration plant would contain only about one-
third the contaminants shown by the analyses listed in Table E-5.
The three types of membranes were tested simultaneously and therefore
processed composite waste with exactly the same characteristics. The
collection of samples for reuse took about twenty-four hours. The concen-
tration was accomplished by withdrawing Selas and UOP products while
recycling the Westinghouse product to the concentrate tank.
The product water contained high concentrations of solids (1440 and
1222 mg/£) and COD (218 and 178 mg/A). This was expected because of the
high concentrations in the waste stream and was not indicative of poor
membrane performance.
The concentrate water was very strong, containing 12210 mg/& total
solids, and 5020 mg/£ of COD. The total solids are mostly salts as
indicated by the high (78%) percentage of non-volatile substances in the
concentrate. This data agrees with the percentage of non-volatile salt
found in the plant effluent (77%).
Since it may not always be desirable to attempt direct reuse or
reclamation of the concentrate, the 90% recovery concentrate was used in
the treatability tests.
REUSE EVALUATION
Since the fibers processed by Plant #40 are cotton and polyester, the
waste stream contains the many chemicals associated with the scouring,
desizing, and dyeing of these fibers and their blends. Because of this
there was little likelyhood that chemicals could be recovered from the
concentrated residue. There is the possibility of recovering chemicals
from isolated process waste streams. Because of this possibility, rinse
132
-------
TABLE E-5. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSEa AT PLANT #40
(90% Water Recovery)
TYPE
Selas
Product
UOP
Product
West
Product
S/DOP/W
Concentrate
SAMPLE NUMBER
643
644
645
646
DATE TAKEN
4/2/75
4/2/75
4/2/75
4/2/75
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
218
58
27.5
73
3
1440
1432
140
20
10
2200
0.01
7.0
<0.001
0.27
178
40
25.5
32
1222
1222
122
30
20
1650
0.22
6.4
<0.001
1780
795
480
290
70
9356
9337
830
300
60
12000
0.16
7.1
<0.001
5020
1800
1200
270
105
12210
12120
2698
2500
400
13600
0.21
6.4
<0.001
0.25
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
0.36
1.76
<0.1
<0.1
0.30
0.112
1.97
<0.01
1.79
<0.1
<0.1
0.133
<0.1
1.77
<0.01
0.87
0.26
0.64
2.88
1.16
1.07
0.74
3.80
Q.I
3.60
9.30
5.51
2.17
a Reuse tests conducted in Plant #40 dye laboratory.
Selas module contained ceramic tubes with dynamic membranes.
d
e
UOP module contained spiral-wound cellulose acetate membranes.
Westinghouse module contained tubular polysulfone ultrafilter membranes.
All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymhp/cm), and pH (unitless).
133
-------
water from the indigo range was subjected to hyperfiltration concentration.
The analyses results for the purified product water and the concentrated
residue from both the cellulose acetate and the dynamic membranes are
presented in Table E-5.
Reuse of Product Water
As a stringent test of the reuse of the product water, the 90%
recovery samples were evaluated. The analyses of the product water indicates
that, in general, the COD and dissolved solids are much more than expected
for tap water.
All of the purified product water generated by the mobile laboratory
at Plant #40 was evaluated in the plant laboratory and found suitable for
reuse in the plant.
The product water was used in the laboratory to dye a bottle green
reactive dye formulation on a 100% cotton sateen fabric. It was also used
in a padding formulation containing no dye to determine if any background
color would interfere with continuous pad-dry-thermosol-steam operation.
Laboratory pad evaluation was conducted to identify color impurities
in the product water which would interfere with continuous dyeing. No
stains or colorations were detected which would interfere with continuous
dyeing.
The product water was padded onto the trial fabric as would normally
be run in laboratory dyeings. No additives or dyestuffs were added to the
sample water. The fabrics used were Super Twill (100% cotton), and
Equestrian Twill (65% polyester/35% cotton).
Both fabrics were run simultaneously with regular plant water used as
the control. For the 100% cotton fabric, fabric samples were retained
after the pad-drying process and again after the final treatment which is
steaming, rinsing, oxidizing, and drying. For the polyester/cotton fabric,
fabric samples were retained after the pad-drying process, again after
thermosoling, and after the final treatment, which is steaming, rinsing,
oxidizing, and drying. These fabric samples are available for further
testing and evaluation.
The procedures employed in the test dyeing of Super Twill, 100% cotton,
were standard for continuous running.
For the trial fabric Equestrian Twill, 65% polyester/35% cotton, all
procedures were the same as those for the Super Twill fabric with the
exception that after drying through the Fosteria unit the fabric was
thermosoled for ninety seconds at 410°F.
No problems were encountered with the use of the product water for
laboratory test dyeings and the fastness properties of the dyed fabric were
the same as those obtained with normal plant water.
134
-------
Reuse of Concentrate
The concentrates resulting from 70% and 95% recoveries were evaluated
in the laboratory for a pad-dry-thermosol-steam procedure. Minimal dye
concentration was obtained on the treated fabric giving evidence of small
concentrations of a mixture of dyes and chemicals in the concentrate. No
value could be observed from reuse of the concentrate obtained from the
composite waste stream.
A sample of indigo rinse water was concentrated by the hyperfiltration
membranes to evaluate the recovery of indigo dye. The concentrate obtained
was then evaluated by plant laboratory personnel. The results indicated
that the concentrated indigo rinse water could be used to formulate a dyeing
solution for reuse with equivalent fastness properties to the original dye.
A significant savings of indigo was indicated by the laboratory results.
It is possible, when the wastewater and chemicals are recovered by
hyperfiltration, to change the process to (1) achieve faster dyeing cycles,
and/or (2) to eliminate the need for some auxiliary chemicals. For
example, with direct dyeing of cellulose, salt can be eliminated by using
higher concentrations of dye in the dyebath. Excess dyestuffs will be
recovered by the membranes for reuse in the next cycle. Depending on the
amount of fiber dyed and range of colors, this modification may or may not
be practical. Water, chemicals, and energy requirements will play a major
role in the selection of dyeing processes used in the future.
MEMBRANE PERFORMANCE
The polysulfone ultrafilter and the dynamic membrane were operated on
pretreated composite wastewater (Table E-2) for 200 hours beginning on
April 1, 1975. The performance of the membranes was monitored by periodic
measurements of the product water flow rate through the membranes and the
conductivity rejection.
The Westinghouse polysulfone and the dynamic Zr-PAA membranes were fed
from a common tank. The incoming feed was neutralized to pH - 7 - 9.5 with
sulfuric acid and controlled in that range. Tables E-6 and E-7 show
analyses performed on feed water after neutralization and 25-micron filtra-
tion. The volumetric recovery was allowed to rise to ^90%, to obtain
samples for reuse evaluation, but was then lowered to 80% and maintained
there throughout the remainder of the 200-hour test. The temperature was
maintained at near 45°C, the average temperature of the plant outfall. At
about midway in the test a cooling water stoppage occurred causing excessive
loop temperature and the rupture of modules #4 and #12. Module #9, a
previously used module, was substituted for #12, the position of #4 was
plugged, and the test continued.
Dynamic Membrane
Four modules of Selas ceramic tubes with dynamic Zr-PAA membranes were
evaluated. The performance is summarized in Figure E-2, a plot of flux and
rejection throughout the test period. One of the modules, #11, was equipped
135
-------
TABLE E-6. CHEMICAL ANALYSES OF WASTEWATER TREATED FOR
MEMBRANE PERFORMANCE TESTS AT PLANT #40
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pli
Mercury
Manganese
Calcium
I L on
Nickel
Chromium
Zinc
Copper
Magnesium
649
4/3/75
1300
250
399
0
12
3516
3362
598
50
9.5
3600
0.077
6.3
<0.1
0.04
0.6
1.0
0.1
2.5
2
0.5
1.5
656
4/7/75
1280
280
408
83
17
4832
3432
618
100
5.5
3700
0.153
6.8
-
0.12
0.87
0.2
0.1
5
3.5
1.4
3.0
662
4/8/75
1280
310
499
124
25
5038
4864
76
100
3.0
3400
0.045
6.0
-
0.08
0.80
3
0.1
3
4.0
1.6
6.6
Grab samples of combined effluent with 25-micron prefiltration,
followed by neutralization to pH *\» 6.5.
All results are in mg/£, except for color (APHA units), turbidity
(mg/A SIO2), conductivity (ymho/cm), pH (unitless), and mercury
136
-------
TABLE E-7. CHEMICAL ANALYSES OF WASTEWATER TREATED3 FOR
MEMBRANE PERFORMANCE TESTS AT PLANT #40
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
669
4/9/75
1600
400
723
174
27
6030
5726
958
350
7.0
5800
0.103
6.3
-
0.2
1.4
2.8
0.3
13
3.7
2.2
4.8
678
4/10/75
1080
300
361
1424
11
4516
3076
528
100
0
3200
0.020
5.9
-
0.08
0.93
1
0.1
8
1.7
1.3
1.6
a Grab samples of combined plant effluent with 25-micron prefiltration,
followed by neutralization to pH ^ 6.0.
All results are in mg/£, except for color (APHA units), turbidity
(mg/£ SIO2)/ conductivity (umho/cm), and pH (unitless).
137
-------
100.0,
*?%
2 80.0
O
ui
-»
ui
ce
60.0
'*&e
r?° °°
1 ©
0
till
13 a
i i
I20.0U © N0.4,Vs4.3"H
D NO. II,V=4.9
"O
CJ
a)
c
—
"o
o>
80.0
4Q°
0.01
43
a a
O ---
NO. 9,V*2.5m/8
NO. I2,V»2.5 m/
X
86 129
TIME (hours)
172
215
M
5.0
4.0 _
3.
2.0
1.0
0.0
Figure E-2.
Hyperfiltration of combined effluent at Plant #40 by
Zr(lV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 45°C; pH - 7.0 - 9.5;
recovery = 75%.)
138
-------
with new membranes and therefore had a somewhat higher initial flux.
Module #4 was equipped with ten-month old membranes that had already been
used at several other plants. This older membrane exhibited a lower
initial flux. Table E-8 shows the analyses of product water from module #4,
and the corresponding concentrate.
The effect of fluid velocity on flux decline was the subject of para-
metric testing. But the rupture of modules #4 and #12 near the midpoint of
the tests prevented an adequate comparison between low velocity (2.5 m/s)
and high velocity (4.9 m/s) flux decline rates. Module #11 operating at
4.9 m/s did achieve a stable flux of 1.0 m/d (25 gallons/ft2/d) at 45°C and
6.9 MPa (1000 psig) . This flux is used in design cost projections.
The somewhat erratic conductivity rejections are the result of the
widely varying pH (7 - 9.5) throughout the test.
The conductivity rejection allows measurement of the electrolyte
filtration by the membrane. The filtration efficiency for larger organic
molecules is usually higher than for the electrolytes. Grab samples of
the concentrate and product waters passing through the membranes were
obtained during the 200-hour performance tests and analyzed to indicate the
filtration efficiency for several constituents. The results of analyses
for three pairs of samples are shown in Tables E-8 through E-13.
The high rejections of organics, indicated by COD, BOD, and color
comparisons between the concentrate and product samples are greater than the
conductivity rejections. The phenol rejection is about 88%. The rejection
of metals is very high, as indicated in cases where results are significantly
above the limit of detection.
Indigo dye waste was selected as the feed of interest for the special
tests. Figure E-3 shows data taken during two runs. During the first 50
hours a composite wash water from the total dye range was processed to 90%
volumetric recovery. The waste was processed as received at a pH of 8.5.
The loop was then drained and indigo waste taken from the first hot rinse
box on the range was introduced without pH adjustment at a pH of 11.2. A
cluster of porous ceramic tubes normally used on a membrane support was
installed in the loop.
Polysulfone Ultrafilter
The performance of the tubular polysulfone ultrafiltration module is
summarized in Figure E-4, a plot of the flux and rejection throughout the
test period. The operating conditions were as specified by the manufacturer:
2.1 MPa (300 psig), a feed rate of 8.3 - 13.6 dnr/min (2.3 - 3.6 GPM), and
a temperature of 40°C. This module was first used at this site.
The flux showed a rapid decline to 0.1 m/d (2.5 gallons/ft2/d) while
the rejection rose to near 60%, presumably due to the formation of a
self-rejecting fouling layer formed from feed constituents. No washing
procedures were attempted.
139
-------
TABLE E-8. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #40
SAMPLE NUMBER
TYPE
DATE TAKEN
d
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
650b
Product
4/3/75
142
20
223
74
0.10
464
460
52
0
5.0
890
0.02
7.4
-
0.04
0.74
-
-
0.15
0.07
0.04
0.08
»-•!.. !!••• .. • [^'•••— •.••••••.I • ,p III
' 651°
Product
4/3/75
80
120
30
49
0.22
698
698
68
0
8
1200
0.0415
7.0
-
0.04
0.06
-
o.i
0-.15
0.1
0.08
0.08
653
Concentrate
4/3/75
1100
580
1256
33
43
9250
8854
2142
200
13.0
8300
0.065
5.9
0.043
0.08
1.7
8
0.7
15
5.8
3.3
9.2
•"-•••""•"•"•— "•••WH^*— I—M^BM-WHMHW
Selas module contained ceramic tubes with dynamic membranes.
Combined product from modules #4, #11, and #12.
Product from module #4.
All results are in mg/A, except for color (APHA units), turbidity
(mg/fc SIO2) , conductivity (ymho/cm) , pH (unitless) , and mercury (yg/£)
140
-------
TABLE E-9. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #40
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER13
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
657
Product
4/7/75
320
95
26
0
0.7
500
488
90
5
11
690
0.030
6.8
-
0.04
0.07
-
-
0.15
0.05
0.04
0.02
660
Concentrate
4/7/75
1650
360
1392
266
52
11976
11566
2180
800
11
10000
0.161
6.3.
<0.057
0.4
2.3
10.6
1.7
13
5.8
2.4
11.4
a Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/t, except for color (APHA units), turbidity
(mg/SL SI02) , conductivity (ymho/cxn) , pH (unitless), and mercury (yg/A)
141
-------
TABLE E-10. PERFORMANCE PARAMETERS OF SELAS AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #40
TYPE
SAMPLE NUMBER
DATE TAKEN
c
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a
Selas
Product
663
4/8/75
180
80
23
66
0.73
356
356
72
20
4
470
0.040
6.4
-
0.04
0.07
-
0.1
0.15
0.05
0.1
0.04
Westinghouse
Product
665
4/8/75
1500
350
548
124
21
6266
6084
932
150
5.5
6400
0.1435
6,6
-
0.12
-
-
-
-
0.2
-
-
Selas /West
Concentrate
666
4/8/75
1400
680
1271
349
51
1400
10062
2278
400
7.0
9700
0.109
6.2
<0.057
0.4
2.4
14
1.9
13
5.8
3.2
12.4
Selas module contained ceramic tubes with dynamic membranes.
Westinghouse module contained tubular polysulfone ultrafliter membranes.
All results are in mg/Jl, except for color (APHA units) , turbidity
(mg/H SIO?) , conductivity (vimho/cm), pH (unitless), and mercury (ug/Jl.).
142
-------
TABLE E-ll. PERFORMANCE PARAMETERS OF SELAS AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #40
TYPE
SAMPLE NUMBER
DATE TAKEN
c
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
670
4/9/75
200
30
20
99
0.05
100
0
0
5
11
880
0.025
6.4
-
0.04
0.007
-
-
0.15
0.06
0.04
0.02
Westinghouse
Product
672
4/9/75
1160
170
489
316
25
5890
5764
682
100
12
5800
0.153
6.8
-
0.08
1.2
-
-
0.88
0.02
0.1
5.0
Selas /West
Concentrate
673
4/9/75
1400
590
960
408
44
9184
8852
1528
500
15
8200
0.1355
6.8
<0.057
0.32
2.1
15
1.4
10
4.5
3.0
11
* Selas module contained ceramic tubes with dynamic membranes.
Westinghouse module contained tubular polysulfone ultrafilter membranes.
C All results are in mg/A, except for color (APHA units), turbidity
(mg/i SI02) , conductivity (Mmho/cm), pH (unit less), and mercury (yg/8.).
143
-------
TABLE E-12. PERFORMANCE PARAMETERS OF SELAS AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #40
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a
Selas
Product
674
4/10/75
200
100
44
749
0.01
486
486
144
0
0
730
0.033
6.6
-
0.04
0.07
-
-
0.15
0.02
0.1
0.02
Westinghouse Selas/West
Product Concentrate
675
4/10/75
1220
200
569
3833
16
6884
6692
864
200
12.0
6800
0.1245
6.6
-
0.12
1.5
-
-
1.8
0.03
0.1
6.8
676
4/10/75
1500
450
1192
316
46
10728
10366
1710
300
14.0
9600
0.140
7.0
<0.057
0.32
2.6
14
1.1
23
3.6
2.9
9.2
a
Selas module
Westinghouse
contained ceramic tubes with dynamic
module contained tubular polysulfone
membranes.
ultraf liter membrane
All results are in mg/£, except for color (APHA units), turbidity
(mg/£ SIO2), conductivity (ymho/cm), pH (unitless), and mercury (yg/fc) .
144
-------
TABLE E-13. PERFORMANCE PARAMETERS OF WESTINGHOUSE MODULES3 IN
THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #40
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER13
COD
BOD
T6c
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
652
Product
4/3/75
800
290
223
324
19
5322
5220
594
150
13.0
6500
0.111
7.0
<0.086
0.04
1.1
-
-
1.0
0.38
0.24
4.6
653
Concentrate
4/3/75
1100
580
1256
33
43
9250
8854
2142
200
13,0
8300
0.065
5.9
<0.043
0.08
1.7
8
0.7
15
5.8
3.3
9.2
a Westinghouse module contained tubular polysulfone ultrafliter membranes.
b All results are in mg/S,, except for color (APHA units), turbidity
(mg/£ SI02), conductivity (ymho/cm), PH (unitless), and mercury (yg/A).
145
-------
loo.
O
111
-D
UJ
cc
60.0
A
r
-Q0
20.0
J—±.
120.01
A NO. 9, V = 4.
0 NO.II,V = 2.
0
36
72 108
TIME (hours)
144
-5.0
_4.0
x»,
M
^ 80.0
1
f
X,
=> 40.0
""
T IVW- IW| » — T»\J X^J —
t-
^^ "4v»
*M
STOP ^
b~~^^^,^ ~^^ -
Q— ~TJ
^^
onf^ i i i i i
•o
*o J
ION
^,
2.0 5
_i
u.
1.0
0.0
180
Figure E-3.
Hyperfiltration of indigo waste at Plant #40 by
Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 40°C; pH = 8.6 - 11.0.)
146
-------
64.0
z
£32.0
o
yj
"9
til
o:
0.0
Q
Q
Q
Q
Qg^
-------
APPENDIX F
PLANT #80
The on-site tests conducted from April 23, 1975, to May 21, 1975, were
to obtain the following information: (1) plant laboratory evaluation of
reuse, and (2) engineering performance data with membranes. Reuse of both
the purified product water and the concentrated residue was evaluated in
laboratory tests conducted by Plant #80 personnel. Samples of wastewater,
purified product water, and concentrated residue were analyzed by Nardin
Laboratory.3 in addition, the treatability of the concentrated residue was
evaluated in bench-scale tests, Appendix J.
The production parameters of Plant #80, Table F-l, provide a basis
for evaluation of the results of the project. The factors are important in
the evaluation of the practicality of scale-up from the pilot plant.
FIBERS AND CHEMICALS
The primary processes at Plant #80 are scouring, bleaching, dyeing,
and finishing of cotton and cotton/polyester blended fabrics on continuous
ranges. The dyes used in the plant are those common to the finishing of
cotton and polyester fibers: sulfur, vat, fiber reactive, disperse, and
napthol dyes.
Thirty percent of the 11,364 m3/d (3,000,000 gallons/day) total water
usage is in the dyehouse. Allowing for evaporation in the dyehouse, the
composite waste stream is at least 30% by volume dyehouse wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based on
a monthly average for the summer of 1975, of plant wastewater discharge
parameters are: BODs = 349 mg/£; COD = 645 mg/fc; total suspended solids =
193 mg/Jl; total dissolved solids = 2473 mg/fc; pH = 11.8; temperature = 110°F.
Tables F-2 and F-3 present the results of analyses for five grab samples
a
Division of Commonwealth Laboratory, Inc., Greenville, SC.
148
-------
TABLE F-l. PLANT #80 PRODUCTION CAPACITY PARAMETERS
QUANTITIES USED
Materials: cotton, cotton/polyester
Water (total to plant), m3/day
(gal Ions /day)
Water (to dyehouse) ,
Dyes , kg/day
(pounds /day)
(gal Ions /day)
Auxiliary Chemicals, kg/day
(pounds/day)
Energy (for process steam) , joules/day
(Btu/day)
13,257
(3,500,000)
4,545
(1,200,000)
3,162
(6,973)
29,035
(64,023)
4630 x 109
(4410 x 106)
UNIT COSTS
Water, <=/m3
($/1000 gallons)
Fuel, C/107 joules
($/106 Btu)
4
(0.15)
1.0
(1.10)
149
-------
obtained during the period of on-site testing. Plant #80 is classified as
Subcategory 8, commission finishing.3
SCHEDULE AND PROCEDURE
Schedule
The mobile laboratory arrived at Plant #80 on April 23, 1975. The
utilities were connected and the system was placed in operation on April 29.
Initially, one-gallon (3.8£) samples of purified product and concentrate
were collected for reuse evaluation in the plant laboratory. The reuse
samples were generated from the dyehouse wastewater and not from total plant
composite wastewater. The ten-gallon (38A) sample of concentrate for the
treatability study was collected later from total plant composite wastewater.
The following is a list of events at Plant #80:
04/23 - Arrived from Plant #40.
i
04/29 - Generated reuse test samples utilizing Selas, Westinghouse poly-
sulfone, and UOP spiral modules. Feed was composite effluent from
the dyehouse only.
04/30 - Began parametric performance test with Selas and Westinghouse poly-
sulfone membranes. Total plant effluent was feed.
05/06 - Installed DuPont's spiral polyamide membrane module.
05/07 - Removed DuPont module.
05/12 - Parametric performance test completed.
05/15 - Began special tests utilizing Selas, Westinghouse polysulfone, and
Union Carbide's ultrafiltration modules.
05/20 - Tests completed.
05/21 - Departed to Plant #81.
Procedure
The membranes for evaluation were selected on the basis of availability
and the characteristics of the wastewater. The wastewater was prefiltered
through 25-micron cartridge filters prior to entering the mobile laboratory.
The pH was adjusted when necessary to meet the membrane manufacturers
specifications using sulfuric acid as the reagent. Figure F-l shows
schematically the equipment arrangement. Four module types were evaluated:
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
150
-------
TABLE F-2. CHEMICAL ANALYSES OF PLANT #80 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
PARAMETER13
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
J
-
-
450
-
17
-
2069
-
423
32
-
-
11.4
0.057
0.05
1.8
0.15
0.1
0.15
2.5
0.24
2.0
E
5/2/75
397
137
170
1393
7
1960
1362
365
206
27
6100
-
11.6
0.057
0.05
2.5
0.15
0.1
0.15
0.15
0.04
1.1
A
5/6/75
845
320
401
773
12
2208
2175
575
364
35
5000
-
11.6
-
0.05
1.5
0.15
0.1
0.15
0.18
0.04
2.0
a Grab samples of combined plant effluent.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (Mmho/cm), and pH (unitless).
151
-------
TABLE F-3. CHEMICAL ANALYSES OF PLANT #80 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Q
5/8/75
744
314
388
1623
11
2830
2776
660
609
42
9000
-
11.9
-
0.05
2.7
0.15
0.1
0.15
0.5
0.04
1.6
K
5/9/75
602
626
307
2540
15
3500
3579
810
590
30
11000
-
12.0
-
0.05
2.8
0.15
0.1
0.15
0.42
0.08
1.2
a
Grab samples of
combined plant effluent.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
152
-------
PRODUCT 8 CONCENTRATE
en
CONCENTRATE RETURN
PRODUCT RETURN
WESTINGHOUSE
U . 0 . P
DUPONT
UCARSEP
25/<.
FILTRATION
pH ADJUST
8 SPARGE
FEED
TANK
3TE 1
*w~irt ^M
t
SUMP
V,
[HYPERRLTRATION LABORATORY]
Figure F-l. Flow schematic for equipment set-up at Plant #80.
-------
the dual-layer dynamic membrane on Selasa ceramic tubes, the spiral-wound
cellulose acetate membrane manufactured by UOP*5, the tubular polysulfone
ultrafiltration membrane by Westinghousec, and an experimental spiral-wound
polyamide membrane by DuPont. The membranes, with the exception of the
Selas module #10 and the experimental DuPont module, had been previously
exposed to waste streams at other plant sites.
REUSE
The dynamic, the polysulfone ultrafilter, and the spiral-wound cellulose
acetate membranes were all used to generate samples for reuse evaluation.
A sample of dyehouse wastewater was drawn from the sewer and pumped through
a 25-micron filter into the mobile laboratory- The pH was adjusted to 5
for the cellulose acetate and polysulfone membranes. The dynamic membranes
treated raw feed at a pH of approximately 9. Samples of both product water
and concentrate were taken at 75% and also at 90% recovery.
Both the 75% and 90% recovery samples were evaluated for reuse. How-
ever, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course,
represent the more severe test of reuse. Because membranes do not separate
100% of the dissolved material, the 10% by volume residue is only about
eight times as concentrated as the plant composite wastewater (instead of
the volumetric factor of ten).
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of
purified product water evaluated for reuse were obtained near the end of
the concentration (90%), and thus contain more chemicals than the average
product water would have. In fact, for these membranes the mixed product
water from a full-scale hyperfiltration plant would contain only about one-
third of the contaminants shown by the analyses listed in Tables F-4 and
F-5.
The three types of membranes were not tested simultaneously and there-
fore did not process composite waste with exactly the same characteristics.
The collection of the samples for reuse took about five hours. Concentrating
the feed in the cellulose acetate/polysulfone system was accomplished by
withdrawing cellulose acetate permeate and recycling polysulfone permeate
back to the feed tank. This was done because the polysulfone is an ultra-
filter and is expected to exhibit low rejections for salts and some dyes.
The concentrated residue in both cases contained about 0.5% dissolved
solids and was highly colored. Since it may not always be desirable to
attempt direct reuse or reclamation of the concentrate, the 90% recovery
concentrate was used in the treatability tests.
Selas Corporation of America, Flotronics Division.
Universal Oil Products, RDGA Division.
c
Westinghouse Membrane Systems was sold to Union Carbide.
E. I. DuPont, Permasep Division.
154
-------
TABLE F-4. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE3 AT PLANT #80
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
c
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
711
4/29/75
144
52
22
102
1
634
634
254
0
0
800
0.08
9.0
<0.001
0.13
0.47
2.48
0.35
0.11
0.46
<0.1
1.57
Selas
Concentrate
712
4/29/75
1128
300
282
320
70
4880
4807
1380
750
580
4600
0.27
8.0
<0.001
0.07
<0.01
3.80
0.58
0.44
1.77
0.58
1.43
a Reuse tests conducted in Plant #80 dye laboratory. Feed is
, combined effluent from dyehouse only.
Selas module contained ceramic tubes with dynamic membranes.
C All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
155
-------
TABLE F-5. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #80
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
UOPb
Product
713
4/29/75
208
105
42
-52
5
472
472
96
0
0
830
0.055
4.0
<0.001
0.05
<0.01
2.68
0.41
0.11
1.09
0.15
2.10
c
Westinghouse
Product
714
4/29/75
268
105
61
-40
54
1900
1900
260
10
0
2250
0.07
4.2
<0.001
0.12
0.86
4.03
0.64
0.27
6.58
0.42
1.55
UOP/West
Concentrate
715
4/29/75
468
120
78
-85
170
4650
4645
370
65
20
5500
0.03
3.6
<0.001
<0.01
0.72
7.75
0.76
0.58
9.91
1.78
1.62
Reuse tests conducted in Plant #80
effluent from dyehouse only.
UOP module contained spiral-wound
dye laboratory. Feed is combined
cellulose acetate membranes.
-------
REUSE EVALUATION
Since the fibers processed by Plant #80 are cotton and polyester, the
waste stream contains many chemicals associated with the scouring, desizing,
and dyeing of these fibers and their blends. Because of this there was
little likelyhood that chemicals could be recovered from the concentrated
residue. The analyses results for the purified product and the concentrated
residue at the 90% recovery level by the cellulose acetate and by the
dynamic membranes are presented in Tables F-4 and F-5, respectively.
Reuse of Product Water
As a stringent test of reuse of the product water, the 90% recovery
samples were evaluated. The analyses of the product water (Tables F-4 and
F-5) indicate that the dynamic and cellulose acetate hyperfiltration
membranes produce a product water with less organic and inorganic impurities
than the polysulfone ultrafilter.
Laboratory evaluation for continuous range dyeings were run using
product water to make up the dyebath. A control run was made using regular
plant process water. A critical shade was chosen for each of the three dye
systems: disperse/vat, disperse/sulfur, and disperse/reactive. The fabric
used in each evaluation was 65/35 polyester/cotton poplin. The shades,
with the dyes in the formulations, are shown in Table F-6.
The test dyeings were carried out in a laboratory range using standard
operating procedures.
The reuse of product water in the dyebath did not effect these shades
and was considered to be suitable for plant use. Shade variations were not
more than expected when repeating the same dyeing with regular plant water.
Reuse of Concentrate
The concentrates were evaluated for content of reusable dyestuff. The
evaluation consisted of running white fabric through the concentrate as the
dye pad, with no addition of dye. All other chemicals were included. Cloth
samples were taken after the thermosol to check for yellowing. The pre-
cipitation or agglomeration of dyestuff in the concentrate caused "dye
spots." It is not known if special handling of samples would permit uniform
dye application. Recycle of dyestuff in the concentrate was not considered
practical based on these tests.
MEMBRANE PERFORMANCE
The engineering performance test of membranes was begun on April 30,
1975, utilizing the composite waste from the total plant as the feed. The
pH was near 12 and was left unchanged for the first 82 hours of the test
due to pH controller problems. The pH control was partially restored and
pH was maintained at 7 - 10 for the remainder of the test. The Selas and
Westinghouse polysulfone modules were used, but the UOP spiral module was
removed from the system. The performance of the membranes was monitored by
157
-------
TABLE F-6. PRODUCT WATER REUSE EVALUATION
Shade Dyes in Formulation
Blue Poly. Blue D (1329) 2.90 g/£
Sody Rubine FGLS 0.50 g/£
Eastman Yellow GLSW 0.16 g/£
Sol. Blue FSBA 2.60 g/£
Sand Violet NBWM 0.60 g/£
May Olive TANM 0.60 g/l
Brown Poly, Blue D (1329) 40.00 g/£
Latyl Orange 2GFST 28.00 g/£
Sody Rubine FGLS 4.00 g/£
Sody Brown FLCL 66.00 g/£
Sody Tan RWCF 100.00 g/£
Poppy Seed Poly. Pink B 40.00 g/£
Eastman Yellow GLSW 7.50 g/£
Lev Red E2B 5.50 g/£
Lev Yellow EG 5.00 g/£
158
-------
periodic measurements of the product water flow rate through the membranes
and the percentage conductivity rejection. The polysulfone and the dynamic
Zr-PAA membranes were fed from a common tank. The volumetric recovery was
allowed to rise to -x-88% by the withdrawal of Selas product water and was
maintained at 88% throughout the test.
Dynamic Membrane
Four modules of Selas ceramic tubes with dynamic Zr-PAA membranes were
evaluated. The performance is summarized in Figure F-2, a plot of flux and
rejection throughout the test period. The characteristic initially rapid
flux decine is evident. One of the modules, #10, was equipped with new
membranes. Module #4 was equipped with an old membrane that had already been
used at several other plant sites.
The erratic flux and rejection performance is probably due to the
widely varying feed pH throughout the test. The flux used for design cost
projections is 1.5 m/d (37 gallons/ft2/d) at 45°C and 6.8 MPa (1000 psig) .
While the flux generally declined, the conductivity rejection increased.
Both phenomena may be the result of the formation of a fouling layer of
residue formed on the membrane surface from the constituents in the waste-
water.
The conductivity rejection is a measure of the separation or filtration
of electrolytes by the membrane. The filtration efficiency for larger
organic molecules is usually higher than for the electrolytes. Grab samples
of the concentrate and the product water passing through the membranes were
obtained during the 200-hour performance tests and analyzed to indicate the
filtration efficiency for several constituents. The results of analyses
for four pairs of samples are shown in Tables P-7 through F-10.
The 95 - 99% rejection of organics, indicated by COD, BOD, and color
comparisons between the concentrate and product samples are greater than
the conductivity rejections. The rejection of metals is very high, as
indicated in all cases where results are significantly above the limit of
detection.
Polysulfone Ultrafilter
The results of the performance test with the Westinghouse tubular
ultrafilter are shown in Figure F-3. The unit was run at conditions
specified by the manufacturer: pressure =1.7 MPa (250 psig); temperature =
32 - 41°C; pH = 6.7 - 12; and reject flow rate « 13 - 14 dm3/min (3.4 -
3.7 GPM). The high rejection and low fluxes shown in Figure F-3 are probably
due to a combination of membrane compaction and the formation of a self-
rejecting fouling layer. No washing procedures were attempted at Plant #80.
Tables F-7, F-8, and F-10 show analyses of Westinghouse product and
concentrate samples enabling an evaluation of removal efficiency.
159
-------
100.0
z
o
60.0
UJ
-y
UJ
a:
20.0
A
J.
e
120.0 _
O NO. 4, VB 3.28-4.27
A NO. 9, V* 4.59 m/g
O NO. IO,V«4.59m/fc
J-^
1:80.0
M
C
«
O
x40.0
u.
0.0
(
O NO. ll,V*3.ei-4.59nli
It *
A A
•^ ^V
>kr U% *•
Ta
o o
O ^AA
w
» DQQ&a 0 a° °
\b °G 'Jf<* *jf o° -
1 1 1 1 1 1
3 60 120 180 240 300 36<
4.0
3.0 \
M
i<5v
c
2.0^
X
1.0 «*•
0.0
TIME (hours)
Figure F-2.
Hyperfiltration of combined effluent at Plant #80
by Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 46°C; pH = 5.5 - 12;
recovery = 88%.)
160
-------
TABLE F-7. PERFORMANCE PARAMETERS OF WESTINGJOUSE AND SELAS MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #80
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
— 1
Westinghouse
Product
G
5/1/75
426
150
216
1128
0
2223
1966
525
64
3.6
6000
-
11.6
-
-
0.06
-
-
-
-
0.04
0.02
o 1 b
Selas
Product
H
5/1/75
51
47
25
708
0
900
854
120
1
0.13
3100
-
11.4
-
-
0.06
-
-
-
-
0.04
0.02
West/Selas
Concentrate
F
5/1/75
1721
635
762
1158
6
3965
3705
1265
1682
0.87
9000
-
11.6
0.057
0.05
1.0
1.9
0.1
1.1
3.1
0.92
3.8
a Westinghouse module contained tubular polysulfone ultrafilter membranes,
b Selas module contained ceramic tubes with dynamic membranes.
C All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
161
-------
TABLE F-8. PERFORMANCE PARAMETERS OF SELAS AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #80
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
C
5/5/75
93
48
43
1055
0.5
1685
1416
473
1
0.17
5800
-
11.8
-
-
0.06
-
-
0.15
-
-
0.02
Westinghouse
Product
D
5/5/75
747
344
344
1523
2
4750
2150
2150
164
0.5
9000
-
• 11-. 8
-
-
0.18
-
•
0.15
-
0.08
0.02
Selas /West
Concentrate
B
5/5/75
2803
1180
1338
1600
27
7465
6888
2535
3409
0.33
10000
-
12.0
-
0.05
2.3
2.5
0.1
1.4
4.3
2
6.5
Selas module contained ceramic tubes with dynamic membranes.
c Westinghouse module contained tubular cellulose acetate membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
162
-------
TABLE F-9. PERFORMANCE PARAMETERS OF SELAS AND DUPONT MODULES IN
THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #80
TYPE
SAMPLE NUMBER
DATE TAKEN
c
PARAMETER
cob
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
0
5/7/75
241
121
131
3
3
1045
1054
293
181
0.14
1300
-
7.2
-
-
0.12
0.15
0.1
-
-
0.12
0.22
b
DuPont
Product
P
5/7/75
47
22
30
3
0
75
68
65
14
0.69
90
-
8.8
-
-
0.06
0.15
0.1
-
-
0.04
0.02
Selas/DuPont
Concentrate
N
5/7/75
2776
1138
1058
0
100
8830
8906
1950
1571
23
9000
-
6.4
0.057
0.05
3.0
1.0
0.1
0.15
4.4
0.92
7.6
a Selas module contained ceramic tubes with dynamic membranes.
b DuPont module contained spiral-wound polyamide membranes.
C All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (nmho/cm), and pH (unitless).
163
-------
TABLE F-10. PERFORMANCE PARAMETERS OF SELAS AND WESTINGHOUSE MODULES
IN THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #80
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a
Selas
Product
L
5/9/75
81
68
87
88
0
605
597
143
17
0.17
950
-
10.5
-
-
0.06
0.15
0.1
-
-
0.04
0.02
b
Westinghouse
Product
M
5/9/75
913
44
374
88
43
6998
7376
633
267
1.5
9000
-
9.75
-
-
1.5
0.15
0.1
-
-
0.08
4.2
Selas/West
Concentrate
R
5/9/75
2659
550
1121
88
149
1243
12840
1830
1161
24
11000
-
9.2
0.057
0.15
3.9
5.4
0.1
1.6
5.7
1.2
10.2
Selas modules contained ceramic tubes with dynamic membranes.
Westinghouse modules contained tubular polysulfone ultrafilter membranes.
All results are in mg/SL, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
164
-------
IOO.OL.
Q(D
§50.0
REJEC"
0.0
Q
Q Q
_ 1 0?L ._L_ 1 1 1
45.0r Q TUBULAR, REJECT FLOW = 13-14 dm/inin (3.4-3.7 6PM)
1.5
30.0
(0
c
_o
o
o>
'5-0
0.0
i
(D__
~*T
60
120 ISO
TIME (hours)
240
•o
1.0 \
CM
»N6
0.5
0.0
300
Figure F-3.
Hyperfiltration of combined effluent at Plant #80
by tubular Westinghouse modules with a polysulfone
membrane. (P = 1.7 MPa (250 psig); T = 32 - 41°C;
pH = 6.7 - 12; recovery = 88%.)
165
-------
Spiral Polyamide
During engineering performance tests, an experimental DuPont spiral-
wound polyamide module was installed and run for about twenty-four hours.
The module was removed and returned to the manufacturer at his request.
Chemical analyses showing a comparison between the permeate and concentrate
are shown in Table F-9.
166
-------
APPENDIX G
PLANT #81
The on-site tests conducted from May 21, 1975, to June 25, 1975, were
to obtain the following information: (1) plant laboratory evaluation of
reuse, and (2) engineering performance data with membranes. Reuse of
both the purified product water and the concentrated residue was evaluated
in laboratory tests conducted by Plant #81 personnel. The treatability of
the concentrated residue was evaluated in bench-scale tests, Appendix J.
The production parameters of Plant #81, given in Table G-l, provide a
basis for evaluation of the results of the project. The factors are
important in the evaluation of the practicality of scale-up from the pilot
plant.
FIBERS AND CHEMICALS
The wet finishing processes at Plant #81 involve the scouring, bleach-
ing, dyeing, and finishing of cotton and cotton/polyester blended fabrics
on continuous ranges. The principal classes of dyes are: sulfur, vat,
fiber reactive, disperse, and napthol.
About 40% of the 30,682 m3/d (8,100,000 gallons/day) total water usage
is in the dyehouse. Allowing for evaporation in drying, the composite waste
stream is at least 50% composed of scouring, bleaching, and desizing
wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based
on a monthly average for the summer of 1975, of plant wastewater discharge
parameters are: BODu, = 950 mg/SL; COD = 2050 mg/&; total suspended solids =
150 mg/Jl; total dissolved solids = 1900 mg/&; pH = 11.0; temperature = 110°F.
Table G-2 presents the results of analyses for a grab sample of composite
wastewater (excluding printing operations) obtained during the period of
on-site testing. Plant #81 is classified as Subcategory 8, complex
manufacturing.a
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category- EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
167
-------
TABLE G-l. PLANT #81 PRODUCTION CAPACITY PABAMETERS
QUANTITIES USED
Materials: cotton, cotton/polyester
Water (total to plant), m3/day 30,682
(galIons/day) (8,100,000)
Water (to dyehouse), m3/day 12,121
(gallons/day) (3,200,000)
Dyes, kg/day 4,545
(pounds/day) (10,000)
Auxiliary Chemicals, kg/day 7,319
(pounds/day) (16,100)
Ehergy (for process steam), joules/day 12.8 x 1012
(Btu/day) (12.2 x 109)
UNIT COSTS
Water, C/m3 5
($/1000 gallons) (0.19)
Fuel Oil, C/107 joules 1.1
($/106 Btu) (1.18)
168
-------
SCHEDULE AND PROCEDURE
Schedule
The mobile laboratory arrived at Plant #81 on May 21, 1975. The
utilities were connected and the system was placed in operation on May 27.
Initially, one-gallon (3.8A) samples of purified product and concentrate
were collected for reuse evaluation in the plant laboratory. A 19& sample
of concentrate was later collected for the treatability study.
The following is a list of events at Plant #81:
05/21 - Arrived from Plant #80.
05/27 - Reuse samples generated utilizing Selas Zr-PAA membrane modules.
Composite effluent from plant was feed.
06/02 - Began parametric performance test utilizing Selas hyperfiltration
modules, a Union Carbide ultrafilter, and a Westinghouse polysulfone
ultrafilter. Feed was outflow from the steamer section of a
continuous dye range.
06/04 - Use of Union Carbide and Westinghouse modules discontinued.
06/16 - Ended parametric performance test. Began special tests utilizing
Selas Zr-sodium silicate modules.
06/23 - Ended special tests.
06/25 - Moved to Plant #82.
Procedure
The membranes for evaluation were selected based on availability and
the characteristics of the wastewater. The wastewater was prefiltered
through 25-micron cartridge filters prior to entering the mobile laboratory.
The pH was adjusted when necessary to meet membrane manufacturer specifi-
cations. Figure G-l shows schematically the equipment arrangement.
A new dual-layer dynamic membrane on Selas ceramic tubes was used to
generate the reuse samples from composite wastewater. Dynamic membranes
that had been used previously at other mills were then installed and used
to treat steamer seal water for 200 hours. A Union Carbideb tubular ultra-
filter module with a type 3NJR membrane was evaluated briefly on the
steamer seal wastewater.
Selas Corporation of America, Flotronics Division.
Union Carbide Corporation, Membrane Systems Division.
169
-------
TABLE G-2. CHEMICAL ANALYSES OF PLANT #81 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
750
5/26/75
2477
904
900
385
60
2713
1900
611
1000
275
1080
990
8.6
-
-
2.52
1.13
-
0.002
0.686
0.007
2.49
Grab sample taken does not include effluent from printing operations.
All results are in mg/£, except for color (Pt-Co units)/ turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
170
-------
PRODUCT 8 CONCENTRATE
BLEED TO DRAIN
CONCENTRATED
CONCENTRATE RETURN
PRODUCT
>RETURN
•..n
|
HYPERFILTRATION LABORATORY
_J
TOTALIZING
FLOW METER
* •
9
SPARGE 8
pH ADJUSTMENT
25-MICRON
PREFILTER
STEAMER
WASH WATER
(4) 50 GAL. HOLDING TANKS
Figure G-l. Flow schematic for equipment set-up at Plant #81.
-------
REUSE
The dual-layer dynamic membrane on Selas ceramic tubes was used to
generate samples for reuse evaluation. Five barrels of composite wastewater,
that did not include print shop wastewater, were prefiltered and introduced
into the mobile laboratory without pH adjustment. The hyperfiltration was
conducted until 90% (by volume) of the water was recovered as purified
product water. Dyes, salts, etc., were concentrated in the remaining 10%
of the water. Samples of both the product water and the concentrate were
taken at 75% recovery, and also at the 90% recovery level.
Both the 75% and the 90% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course,
represent the more severe test of reuse. Because membranes do not separate
100% of the dissolved material, the 10% by volume residue is only about
eight times as concentrated as the plant composite wastewater (instead of
the volumetric factor of ten).
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of
purified product water evaluated for reuse were obtained near the end of
the concentration (90%), and thus contain more chemicals than the average
product water would have. In fact, for these membranes the mixed product
water from a full-scale hyperfiltration plant would contain only about one-
third the contaminants shown by the analyses listed in Table G-3.
The collection of the samples for reuse took about twenty-four hours.
The concentration was accomplished by withdrawing product water while
recycling the concentrate. The product water contained moderate concentra-
tions of solids (500 mg/&) and COD (328 mg/£). The concentrate water
contained a high level of dissolved solids (18,010 mg/SL) and COD (17,800
mg/£). The total solids consisted of over 55% of ionic salts, as indicated
by the high percentage of non-volatile substances in the concentrate.
Since it may not always be desirable to attempt direct reuse or
reclamation of the concentrate, the 90% recovery concentrate was used in
the treatability tests.
REUSE EVALUATION
Since the fibers processed by Plant #81 are cotton and polyester, the
composite waste stream contains the many chemicals associated with scouring,
desizing, and dyeing. Even though the likelyhood of direct recycle of the
chemical concentrate from the composite waste is small, both the concentrate
and product water from Zr-PAA membranes were evaluated in laboratory tests.
Reuse of Product Water
As a stringent test of reuse of the product water, the 90% recovery
(least purified) samples were evaluated. The analyses of the product water
172
-------
TABLE G-3. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #81
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
c
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
755
5/27/75
328
1105
-
72
2
500
500
250
0
0
350
0.04
8.6
0.001
0.01
0.1
0.47
0.2
0.1
0.07
0.1
0.01
Selas
Concentrate
756
5/27/75
•
17800
6200
-
1300
210
18010
17810
10870
4000
900
6800
1.4
7.1
0.001
3.97
6.31
9.02
2.12
1.38
7.76
1.59
11.36
a Reuse tests conducted in Plant #81 dye laboratory.
Selas module contained
ceramic tubes with dynamic
^«»^«rvl- -F/-IV- i-vvl nv fP<"— C-O \:
membranes.
mits} . turbidity
•***.,!_ j. JL CIO UIJ. iw£3 fc*4» ^-> j«*» "*^yf f ••---—••— jr — —
(FTU) , conductivity (vmho/cin) , and pH (unitless) .
173
-------
indicates that, in general, the COD and dissolved solids are more than
expected for tap water. The concentration of metals is lower.
The product water was used in the plant laboratory with dispersed/fiber
reactive dye mixtures and dispersed/vat dye mixtures. All reuse tests were
with 65%/35% polyester/cotton fabric (128 x 72 - 50w 50f).
No problems were encountered with the use of the product water in these
laboratory test dyeings. The fastness properties of the dyed fabric were
the same as dyeings with normal plant water.
The specific procedures used by Plant #81 laboratory personnel are
given here. For the reuse evaluation with the dispersed/fiber reactive dye
formulation the procedure used is:
(1) Prepare dye formulation:
Remazol Yellow GL 16.48 gram/liter
Procion Blue H-7G 7.61 gram/liter
Dispersol Yellow D7G 6.96 gram/liter
Latyl Blue BG 24.31 gram/liter
Foron Yellow Brown BM 32.00 gram/liter
Astrotherm AM 7.50 gram/liter
(2) Pad and dry-
(3) Thermosol in roller oven.
(4) Pad through reduction bath.
(5) Pad through oxidation bath.
(6) Wash in Igepon solution T-33.
(7) Rinse and dry.
For the reuse evaluation with the dispersed/vat dye formulation, the
procedure used is:
(1) Prepare dye formulation:
Yellow Ester Oquinon 3JLLN 6.42 gram/liter
Rubine Eastman RL 5W 50% PS 1.20 gram/liter
Blue Foron BGL Pst 1.32 gram/liter
Brown Veranthrene GAP 4.54 gram/liter
Olive Calcoloid TCM Pst 1.14 gram/liter
Orange Instravat 5G 0.62 gram/liter
Astrotherm AM 7.50 gram/liter
(2) Pad and dry.
(3) Thermosol.
(4) Run through chemical pad.
(5) Steam.
(6) Soap.
(7) Rinse.
(8) Dry on dry cans.
Reuse of Concentrate
The concentrates resulting from both 75% and 90% recoveries were evalu-
ated in the labo'ratory for a pad-dry-thermosol-steam procedure. The
174
-------
composite waste concentrate was not suitable. With all dyebaths tested
dinginess and slight discoloration were noted on the blank dyeing sequences:
sulfur, brine (reactive), and caustic/hydrosulfite. No value could be
observed from reuse of the concentrate obtained from the composite waste
stream.
It is possible, when the wastewater and chemicals are recovered by
hyperfiltration, to change the process to (1) achieve faster dyeing cycles,
and/or (2) to eliminate the need for some auxiliary chemicals. For
example, with direct dyeing of cellulose, salt can be eliminated by using
higher concentrations of dye in the dyebath. Excess dyestuffs will be
recovered by the membranes for reuse in the next cycle. Depending on the
amount of fiber dyed and range of colors, this modification may or may not
be practical. Water, chemicals, and energy requirements will play a major
role in the selection of dyeing processes used in the future.
MEMBRANE PERFORMANCE
The Zr-PAA dynamic membranes were operated on pretreated steamer vapor
seal wastewater (Table G-4) for 200 hours beginning on June 2, 1975. Union
Carbide's tubular module with type 3NJR membranes was also briefly evaluated.
The performance of the membranes was monitored by periodic measurements of
the product water flow rate through the membranes and the percentage
conductivity rejection.
The incoming feed was neutralized to pH = 7 - 8 with sulfuric acid and
controlled at that level throughout most of the test. The chemical analyses
of five grab samples taken over the ten-day test period are presented in
Tables G-5 and G-6. Neutralization was discontinued and the pH rose to the
untreated value of near 11 during the latter portion of the test. Table G-4
shows the analyses of a sample of feed taken after neutralization and 25-
micron prefiltration. A volumetric recovery of 80% was achieved by the
withdrawal of product water and was maintained at 80% throughout the 200-hour
test.
Dynamic Membrane
Three modules of Selas ceramic tubes with dynamic Zr-PAA membranes were
evaluated. The performance is summarized in Figure G-2, a plot of flux and
rejection for the test period. The flux declined throughout the test period
with the greatest decline shown in the earlier portion of the test. Re-
jection increased throughout the test. Low conductivity rejection is
accounted for by high feed conductivities (25,000 to 40,000 pmho/cm). The
increase in rejection with time might be explained by the dynamic formation
of a "membrane" from constituents of the feed stream. Module #4 contained
older membranes (8,000 hours) that had been used at several other plants.
This older membrane exhibited a lower initial flux.
The conductivity rejection is a measure of the separation or filtration
of electrolytes by the membrane. The filtration efficiency for larger
organic molecules is usually higher than for the electrolytes. Grab samples
of the feed to the membrane and the product water passing through the
175
-------
TABLE G-4. CHEMICAL ANALYSES OF WASTE FROM THE STEAMER VAPOR SEAL,
RANGE 116, TREATED* FOR MEMBRANE PERFORMANCE AT PLANT #81
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
764
6/4/75
560
131
150
133
100
12732
11350
180
3000
6
18000
0.460
7.6
-
-
1.48
1.61
-
0.005
0.653
0.97
1.75
Grab sample after 25-micron profiltration, followed by neutralization
to pH ^ 7.5.
All results are in mg/SL, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
176
-------
TABLE G-5. CHEMICAL ANALYSES OF WASTE FROM THE STEAMER
VAPOR SEAL, RANGE 116, AT PLANT #81
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol *-
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
757
6/2/75
-
613
996
140
338
34
19305
19122
129
1000
3
540
31.60
11.6
-
1.48
1.13
-
0.002
0.0057
0.009
1.39
763
6/4/75
960
205
265
552
300
16597
16262
116
17500
7
25200
220
12.0
••
1.52
0.968
-
0
0.0041
0.006
1.05
. Grab samples.
All results are in mg/SL, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
177
-------
TABLE G-6. CHEMICAL ANALYSES OF WASTE FROM THE STEAMER
VAPOR SEAL, RANGE 116, AT PLANT #81
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
769
6/6/75
848
13
135
604
80
23429
20195
147
2000
1
32400
-
11.5
-
-
1.70
1.45
-
0.003
0.082
0.097
0.695
774
6/10/75
896
140
180
2543
100
6627
6327
100
1000
9
9000
0
12.2
-
1
0.933
0.806
-
0
0.082
0
1
781
6/12/75
912
367
180
2081
100
6226
6063
105
900
11
9000
0
12.1
-
-
0.933
0.806
-
0
0.007
0.002
1.07
Grab samples.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (umho/cm), and pH (unitless).
178
-------
80.0 _
85
REJECT
Ol
P
P
20.0
60.0,-
•140.4,^4.6*%
-NO. IO,V = 4.9m/s
•NO.II,V=5.2
_L
1
96 144
TIME (hours)
2.5
2.0
192
1.5
1.0
0.5
0.0
•o
240
Figure G-2.
Hyperfiltration of steamer seal waste at Plant #81 by
Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 51°C; pH = 6.8 - 11;
recovery = 80%.)
179
-------
membranes were obtained during the 200-hour performance tests and analyzed
to indicate the filtration efficiency for several constituents. The results
of analyses for three pairs of samples are shown in Tables G-7, G-8, and G-9.
The rejection of organics, indicated by COD/. BOD, and color comparisons
between the concentrate and product samples are greater than the conductivity
rejections. The rejection of metals is very high, as indicated in cases
where results are significantly above the limit of detection.
The flux used for full-scale plant design cost projections is 1.4 m/d
(35 gallons/ft2/d) at 43°C and 6.8 MPa (1000 psig), a value estimated from
the brief run on composite effluent to generate reuse samples.
Union Carbide 3NJR
The Union Carbide unit equipped with type 3NJR membranes was operated,
briefly, in parallel with the Selas modules. The previously unexposed unit
was operated at 0.69 MPa (100 psig) with a feed velocity of 5.2 m/s (17
ft/sec) for approximately twelve hours at a temperature of 40°C. The flux
showed little decline from the 4.0 m/d (100 gallons/ft2/d) initially
observed. During its operation a product sample was collected and its
analyses is included in Table G-10, along with the corresponding concentrate
analyses. These results cannot be explained and should be subject to
verification before conclusions are drawn. These are simple measurements,
and due to limitations of time and budget, it was not possible to resolve
the apparent ambiguities.
180
-------
TABLE G-7. PERFORMANCE PARAMETERS OF SELAS MODULES3 IN THE
MOBILE HYPEKFILTRATION LABORATORY AT PLANT #81b
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
765
Product
6/5/75
272
39
47
98
22
9623
9381
40
2000
8
14400
150.4
7.9
-
-
1.24
1.13
-
0
0.408
0.002
1.52
766
Concentrate
6/5/75
933
644
400
259
400
19001
18453
213
7500
24
21600
141
8.0
—
-
1.52
4.35
-
0.129
3.57
0.388
2.22
a Selas module contained ceramic tubes with dynamic membranes.
b Feed is filtered, neutralized waste from the steamer vapor seal,
Range 116. . . .
C All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
181
-------
TABLE G-8. PERFORMANCE PARAMETERS OF SELAS MODULES3 IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER0
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
770
Product
6/9/75
168
35
32
53
16
9910
9010
47
40
6
10800
30
7.5
-
-
1.41
0.968
-
0
0.571
0.002
1.73
771
Concentrate
6/9/75
1171
295
420
173
200
19543
18888
77
30000
33
21600
51
7.4
-
-
2.52
0.790
-
0.307
5.63
0.437
2.29
a
, Selas module contained
ceramic tubes with
i _§ _ •* i ^ ,
dynamic membranes.
Range 116.
All results are in mg/SL, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
182
-------
TABLE G-9. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #81b
SAMPLE NUMBER
TYPE
DATE TAKEN
c
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
777
Product
6/11/75
120
41
32
245
10
9837
7824
1032
20
5
9000
70.6
11.1
-
-
0.252
0.654
-
0
0.082
0
0.134
778
Concentrate
6/11/75
1200
618
440
1695
200
21336
20350
306
8500
30
21600
0
10.7
—
—
2.81
5.97
-
0.153
2.86
0.243
1.99
a Selas module contained ceramic tubes with dynamic membranes.
b Feed is filtered, neutralized waste from the steamer vapor seal,
Range 116.
° All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm) , and pH (unitless).
183
-------
TABLE G-10. PERFORMANCE PARAMETERS OF SELAS AND UCC MODULES IN
THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #81
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
759
6/3/75
720
39
50
260
14
14664
13987
62
1000
4
10800
201.6
8.6
-
-
1.26
0.968
-
0.003
0.0057
0.003
1.24
Selas/UCC
Concentrate
760
6/3/75
1160
428
330
314
360
24759
23853
804
1000
18
10800
241.2
8.1
-
-
2.07
2.90
-
0.172
1.64
0.397
2.01
ucc13
Product
761
6/3/75
1944
636
280
301
200
22464
22100
356
2500
9
10800
-
8.8
-
-
2.15
3.55
-
0.067
0.753
0.175
1.95
Selas module contained ceramic tubes with dynamic membranes.
UCC module contained type 3NJR membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
184
-------
APPENDIX H
PLANT #82
The on-site tests conducted from June 25, 1975, to July 30, 1975, were
to obtain the following information: (1) plant laboratory evaluation of
reuse, and (2) engineering performance data with membranes. Reuse of both
the purified product water and the concentrated residue was evaluated in
laboratory tests conducted by Plant #82 personnel. Samples of wastewater,
purified product water, and concentrated residue were analyzed by Nardin
Laboratory.a In addition, the treatability of the concentrated residue was
evaluated in bench-scale tests, Appendix J.
The production parameters of Plant #82, Table H-l, provide a basis for
evaluation of the results of the project. The factors are important in the
evaluation of the practicality of scale-up from the pilot plant.
FIBERS AND CHEMICALS
Plant #82 is presently operated to scour, bleach, dye, and finish
cotton and cotton/polyester blended fabrics. The chemicals and dyes used
by the plant are those which are common to the finishing of cotton and
polyester fibers: sulfur, vat, fiber reactive, disperse, and napthol dyes.
Ninety percent of the 6,629 m3/d (1,750,000 gallons/day) total water
usage is in the plant. Allowing for evaporation in drying, the composite
waste stream is at least 85% by volume plant wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based
on a monthly average for the summer of 1975, of plant wastewater discharge
parameters are: BOD5 = 350 mg/£; COD = 570 mg/Jl; total suspended solids =
346 mg/£; total dissolved solids = 2230 mg/£; pH = 8.5; temperature = 90°P.
Tables H-2 and H-3 present the results of analyses for six grab samples
a Division of commonwealth Laboratory, Inc., Greenville, SC.
185
-------
TABLE H-l. PLANT #82 PRODUCTION CAPACITY PARAMETERS
QUANTITIES USED
Materials: cotton, cotton/polyester
Water (total to plant), m3/day
(gallons/day)
Water (to dyehouse), m3/day
(gallons/day)
Dyes, kg/day
(pounds/day)
Auxiliary Chemicals, kg/day
(pounds/day)
Energy (for process steam), joules/day
(Btu/day)
6,629
(1,750,000)
4,545
(1,200,000)
537
(1,184)
8,224
(18,134)
1327 x 109
(1264 x 106)
UNIT COSTS
Water, <£/m3
($/1000 gallons)
Fuel Oil, C/107 joules
($/106 Btu)
1.5
(1.65)
186
-------
TABLE H-2. CHEMICAL ANALYSES OF PLANT #82 WASTEWATER*
a
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
800
7/16/75
717
144
510
77
12
2515
2364
423
170
50
3100
0.04
6.3
-
0.07
1.90
0.89
0.20
0.10
0.28
0.25
1.27
805
7/17/75
897
36
270
1270
13.6
2417
2390
544
180
80
6300
0.11
10.8
-
0.07
3.62
0.17
0.20
0.10
0.05
0.25
0.49
809
7/19/75
196
3
8
57
5
156
152
117
30
10
135
0.03
7.1
—
0.07
0.90
0.10
0.20
0.10
0.02
0.25
0.17
Grab samples of total plant effluent.
All results are in nig/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
187
-------
TABLE H-3. CHEMICAL ANALYSES OF PLANT #82 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a
Grab samples of
7V 1 1 ^*>^K f+ « * *t 4— f9 ** ^**^
810
7/22/75
592
70
116
1260
8
2807
2790
1232
40
30
6900
0.02
10.9
-
0.07
1.88
0.14
0.20
0.10
0.14
0.25
1.12
total plant effluent.
m v* *toi^w f 0 f^ mm **f^ v^4« f ^t **» ^^.*^ n .
815
7/23/75
800
193
250
1930
3
4183
3976
743
240
35
8000
0.02
11.2
-
0.07
1.39
0.24
0.20
0.10
0.09
0.25
0.40
^ — — / ^% A-, **• ^ _^^ J JL-
816
7/2 5/75
310
59
210
91
8
928
736
323
120
40
1100
0.045
7.0
-
0.07
2.16
0.97
0.20
0.10
0.91
0.29
0.89
All results are in mg/Ji-, except for color (Pt-Co units) , turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
188
-------
obtained during the period of on-site testing. Plant #82 is classified as
Subcategory 8, commissioned finishing.a
SCHEDULE AND PROCEDURE
Schedule
Testing was begun on July 9, 1975. One-gallon (3.8£) samples of
purified product and concentrate were collected for reuse evaluation in the
plant laboratory. A 38X, sample of concentrate was later collected for the
biological treatability study.
The following is a summary of events at Plant #82:
06/25 - Arrived from Plant #81; utilities connected.
07/16 - Began parametric performance test with UOP and Selas modules.
07/17 - Reuse test samples generated.
07/29 - Parametric performance test completed.
07/30 - Departed to Plant #83.
Procedure
The membranes for evaluation were selected based on availability and
the characteristics of the wastewater. The wastewater was prefiltered
through 25-micron cartridge filters prior to entering the mobile laboratory.
The pH was adjusted when necessary to meet membrane manufacturer specifi-
cations. Figure H-l shows schematically the equipment arrangement. Two
types of membranes were employed in these tests: the UOP*3 spiral-wound
cellulose acetate membrane and the dual-layer dynamic membrane on the Selasc
ceramic tubes.
REUSE
All types of membranes were used to generate samples for reuse evalu-
ation. A sample of composite wastewater was drawn from the plant sewer,
and pumped through a 25-micron filter into the mobile laboratory. The
hyperfiltration was conducted until 90% (by volume) of the water was recover-
ed as purified product water. Dyes, salts, etc., were concentrated in the
remaining 10% of the water. Samples of both the product water and the
concentrate were taken at 75% recovery, and also at the 90% recovery level.
3 Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
b Universal Oil Products, ROGA Division.
C Selas Corporation of America, Flotronics Division.
189
-------
ID
O
J
WASTE*
L
CONCENTRATE PRODUCT a BLEED
pH ADJUST
a SPARGE
r
CONCENTRATE RETURl
PRODUCT RgTl^RN
FEED
TANK
25/(
FILTRATION
r- U.O.P
HYPERFILTRATION LABORATORY
i
Figure H-l. Flow schematic for equipment set-up at Plant #82.
-------
Both the 75% and the 90% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course,
represent the more severe test of reuse. Because membranes do not separate
100% of the dissolved material, the 10% by volume residue is only about eight
times as concentrated as the plant composite wastewater (instead of the
volumetric factor of ten).
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of :
purified product water evaluated for reuse were obtained near the end of
the concentration (90%) , and thus contain more chemicals than the average
product water would have, in fact, for these membranes the mixed product
water from a full-scale hyperfiltration plant would contain only about one-
third the contaminants shown by the analyses listed in Table H-4.
The two types of membranes were tested simultaneously and therefore
processed composite waste with exactly the same characteristics. The
collection of samples for reuse took about eight hours. The concentration
was accompliahed by withdrawing Selas product while recycling the UOP
product to the concentrate tank.
The product water contained high concentrations of solids (1140 and
82 mg/£.) and COD (94 and 96 mg/Jl) . This was expected because of the high
concentrations in the waste stream and was not indicative of poor membrane
performance.
The concentrate water was very strong, containing 10710 mg/£ total
solids, and 3620 mg/£ of COD. The total solids are mostly salts as indicated
by the high percentage of non-volatile substances in the concentrate. This
data agrees with the percentage of non-volatile salt found in the plant
effluent.
Since it may not always be desirable to attempt direct reuse or
reclamation of the concentrate, the 90% recovery concentrate was used in
the treatability tests.
REUSE EVALUATION
Since the fibers processed by Plant #82 are cotton and polyester, the
waste stream contains the many chemicals associated with the scouring,
desizing, and dyeing of these fibers and their blends. Because of this
there was little likelyhood that chemicals could be recovered from the
concentrated residue. There is the possibility of recovering chemicals
from isolated process waste streams. The analyses results for the purified
product water and the concentrated residue from both the cellulose acetate
and the dynamic membranes are presented in Table H-4.
Reuse of Product Water
As a stringent test of the reuse of the product water, the 90% recovery
samples were evaluated. The analyses of the product water indicates that,
191
-------
TABLE H-4. CHEMICAL ANALYSES OF WATER EVALUATED FOR REUSE AT PLANT #82
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas
Product
796
7/16/75
94
11
17.4
31
2
1140
1135
130
5
8
1300
0.015
618
<0.001
<0.01
<0.01
0.17
0.09
<0.01
0.18
0.04
0.04
Selas/UOP UOP°
Concentrate Product
797
7/16/75
3620
760
729
170
140
10710
10683
1440
450
70
14500
0.09
616
<0.001
0.39
2.74
11.74
1.41
0.33
18.32
2.01
12.23
798
7/16/75
66
26
14.4
27
1
82
82
38
0
0
65
0.07
615
<0.001
<0.01
<0.01
0.66
<0.01
0.04
0.33
0.03
0.04
Reuse tests conducted in Plant #82 dye laboratory.
Selas module contained ceramic tubes with dynamic membranes.
UOP module contained spiral-wound cellulose acetate membranes.
All results are in mg/Jl, except for color (Pt-Co units), turbidity
(FTU), conductivity (nmho/cm), and pH (unitless).
192
-------
in general, the COD and dissolved solids are much more than expected for
tap water.
All of the purified product water generated by the mobile laboratory at
Plant #82 was evaluated in the plant laboratory and found suitable for reuse
in the plant.
The product water was used in the laboratory with acid and disperse
dyes to dye (1) a blue shade on a 70% dacron/30% wool knit, (2) a tan
shade on 100% textured polyester woven fabric, and (3) a brown shade on
a 100% textured polyester woven fabric. Separate dyeings were run with
plant water, and both 75% and 90% recovery product water from both the Selas
and UOP modules. All dyeings were run on a high-temperature pressurized
beaker bath laboratory machine in 250 mX, beakers at a fabric-to-liquor
ratio of 14:1.
No problems were encountered with the use of the product water for
laboratory test dyeings and the fastness properties of the dyed fabric were
the same as those obtained with normal plant water.
Re us e of Concent rate
The concentrates from 75% and 90% recoveries were evaluated in laboratory
tests for a package dye system. The staining caused by the chemicals and
dyes present in the concentrate made the fabric unsuitable for commercial
use. No value could be observed from reuse of the concentrate obtained from
the composite waste stream.
It is possible, when the wastewater and chemicals are recovered by
hyperfiltration, to change the process to (1) achieve faster dyeing cycles,
and/or (2) to eliminate the need for some auxiliary chemicals. For
example, with direct dyeing of cellulose, salt can be eliminated by using
higher concentrations of dye in the dyebath. Excess dyestuffs will be
recovered by the membranes for reuse in the next cycle. Depending on the
amount of fiber dyed and range of colors, this modification may or may not
be practical. Water, chemicals, and energy requirements will play a major
role in the selection of dyeing processes used in the future.
MEMBRANE PERFORMANCE
The UOP cellulose acetate and the dynamic membranes were operated on
pretreated composite wastewater (Table H-2) for 200 hours beginning on
July 16, 1975. The performance of the membranes was monitored by periodic
measurements of the product, water flow rate through the membranes and the
conductivity rejection.
The UOP cellulose acetate and the dynamic Zr-PAA membranes were fed
from a common tank. The incoming feed was neutralized to pH = 7 - 9.5 with
sulfuric acid and controlled in that range. Table H-5 shows analyses per-
formed on feed water after neutralization and 25-micron filtration. The
volumetric recovery was allowed to rise to ^90%, and was maintained there
193
-------
TABLE H-5. CHEMICAL ANALYSES OF WASTEWATER TREATED
FOR MEMBRANE PERFORMANCE TESTS AT PLANT #82
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
800
7/16/75
717
144
510
77
12
2515
2364
423
170
50
3100
0.04
6.3
-
0.07
1.90
0.89
0.20
0.10
0.28
0.25
1.27
816
7/25/75
310
59
210
91
8
928
736
323
120
40
1100
0.045
7.0
-
0.07
2.16
0.97
0.20
0.10
0.91
0.29
0.89
Grab samples of total plant effluent with 25-micron prefiltration,
followed by neutralization to pH ^ 6.5.
All results are in rng/ft, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
194
-------
throughout the remainder of the 200-hour test. The temperature was maintain-
ed at near 30°C, the average temperature of the plant outfall.
Dynamic Membrane^
Three modules of Selas ceramic tubes with dynamic Zr-PAA membranes were
evaluated. The performance is summarized in Figure H-2, a plot of flux and
rejection throughout the test period. One of the modules, #19, was equipped
with new membranes and therefore had a somewhat higher initial flux.
Module #4 was equipped with eighteen-month old membranes that had already
been used at several other plants. This older membrane exhibited a lower
initial flux.
*»
The effect of fluid velocity on flux decline was the subject of para-
metric testing. No significant effects of velocity variation were observed.
The flux of 1.0 m/d (25 gal Ions/ft2/d) at 31°C and 6.9 MPa (1000 psig) is
used in design cost projections.
The conductivity rejection allows measurement of the electrolyte
filtration by the membrane. The filtration efficiency for larger organic
molecules is usually higher than for the electrolytes. Grab samples of
the concentrate and product waters passing through the membranes were obtain-
ed during the 200-hour performance tests and analyzed to indicate the
filtration efficiency for several constituents. The results of analyses for
three pairs of samples are shown in Tables H-6 through H-8.
The high rejections of organics, indicated by COD, BOD, and color
comparisons between the concentrate and product samples are greater than the
conductivity rejections. The rejection of metals is very high, as indicated
in cases where results are significantly above the limit of detection.
Cellulose Acetate Membrane
The performance of the UOP spiral-wound cellulose acetate module is
summarized in Figure H-3, a plot of flux and rejection throughout the test
period. The operating conditions were: 2.1 - 2.6 MPa (300 - 320 psig)
and feed rate of 9.8 - 13 da^/min (2.6 - 3.5 gallons per minute). The
module evaluated had not been previously exposed to wastewater.
The flux declined during the first 50 hours of the test. No washing
procedures were attempted, but the flux achieved a stable value at about
0.2 m/d. The conductivity rejection was in the range of 90 - 95% throughout
the 200-hour test period. The rejection of other constituents was very
high, as indicated by the analyses results in Tables H-6 through H-8.
195
-------
100.0
o
UJ
80.0
60.O
6°'**>~
JQ^T^
-Q—GTG
_a
-^ZT
A*4A°Cfc
I20.0L
•o
CM
CO
c
13
O
O>
80.0.
40.0 i:
NO. 4,V = 3.9
NO. 10, V= 4.2
i NO.I9,V = 3.9"Vi TO 4.5
and 2.27 m/9 BEFORE AND AFTER 7 HR
45
90 135
TIME (hours)
a.
180
225
4.0
TJ
3.0 \
CM
2.0 1
1.0
0.0
Figure H-2.
Hyperfiltration of combined effluent at Plant #82 by
Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.9 MPa (1000 psig); T = 31°C; pH = 4.7 - 9.9;
recovery = 90%.)
196
-------
TABLE H-6. PERFORMANCE PARAMETERS OF SELAS AND UOP MODULES IN
THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #82
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selasa
Product
802
7/17/75
224
28
70
59
4
1459
1476
81
15
20
2500
0.08
6.1
-
0.07
0.96
0.10
0.20
0.10
0.43
0.25
0.32
Selas/UOP
Concentrate
803
7/17/75
3500
460
1300
62
112
10937
10354
1717
660
210
13000
0.11
5.2
-
0.29
27.3
8.25
1.02
0.20
12.6
3.07
8.40
uopb
Product
804
7/17/75
131
38
70
5
2
182
86
105
2
2
110
0.10
5.1
-
0.07
0.56
0.10
0.20
0.10
0.05
0.25
0.02
a Selas module contained ceramic tubes with dynamic membranes.
b UOP module contained spiral-wound cellulose acetate membranes.
° All results are in rng/4, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
197
-------
TABLE H-7. PERFORMANCE PARAMETERS OF SELAS AND UOP MODULES IN
THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #82
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
•a
Selas
product
811
7/22/75
69
8
12
64
2
597
546
398
0
0
980
0.005
6.8
-
0.07
0.63
0.10
0.20
0.10
0.08
0.25
0.08
Selas/UOP
Concentrate
812
7/22/75
1900
140
720
274
103
8251
7658
1407
700
60
10200
0.10
6.8
-
0.33
27.1
8.89
1.20
0.57
3.89
1.18
7.29
UOPb
Product
813
7/22/75
36
1
18
7
2
182
42
159
0
0
49
0.08
6.1
-
0.07
0.37
0.10
0.20
0.10
0.02
0.25
0.01
Selas module contained ceramic tubes with dynamic membranes.
c UOP module contained spiral-wound cellulose acetate membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
198
-------
TABLE H-8. PERFORMANCE PARAMETERS OF SELAS AND UOP MODULES IN
THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #82
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
_ , a
Selas
Product
817
7/25/75
61
2
20
53
2
241
240
142
3
0
550
0.025
7.1
-
0.07
0.49
0.10
0.20
0.10
0.05
0.25
0.04
Selas/UOP
concentrate
818
7/25/75
775
27
290
21
49
4002
4002
842
400
30
5100
0.05
7.2
-
0.18
16.2
3.16
0.63
0.20
3.02
0.74
3.67
uopb
Product
819
7/25/75
49
3
50
10
2
15
14
10
0
0
32
0.025
6.6
—
0.07
0.41
0.10
0.20
0.10
0.02
0.25
0.02
a Selas module contained ceramic tubes with dynamic membranes.
b UOP module contained spiral-wound cellulose acetate membranes.
C All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (umho/cm), and pH (unitless).
199
-------
100.0
85.0
o
UJ
111
cc
70.0
45.0
--- SPIRAL, REJECT FLOW = 9.8-13 dn™?mjn (2.6-3.4GPM)
CM.
«»-
V.
w
c
o
30.0
15.0
46
92 138
TIME (hours)
184
230
1.5
•o
1.0 •*
0.5
X
0.0
Figure H-3.
Hyperfiltration of combined effluent at Plant #82 by
a UOP spiral-wound, module with cellulose acetate
membranes. (P - 2.1 - 2.59 MPa (300 - 370 psig);
T = 30°C; pH = 4.7 - 9.7; recovery - 90%.)
200
-------
APPENDIX I
PLANT #83
The on-site tests conducted from July 30, 1975, to September 4, 1975,
were to obtain the following information: (1) plant laboratory evaluation
of reuse, and (2) engineering performance data with membranes. Reuse of
both the purified product water and the concentrated residue was evaluated
in laboratory tests conducted by Plant #83 personnel. Samples of wastewater,
purified product water, and concentrated residue were analyzed by Nardin
Laboratory.3 In addition, the treatability of the concentrated residue was
evaluated in bench-scale tests, Appendix J.
The production parameters of Plant #83, Table 1-1, provide a basis for
evaluation of the results of the project. The factors are important in the
evaluation of the practicality of scale-up from the pilot plant.
FIBERS AND CHEMICALS
The primary processes at Plant #83 are scouring, bleaching, dyeing, and
finishing of cotton and cotton/polyester blended fabrics on continuous
ranges. The dyes used in the plant are those common to the finishing of
cotton and polyester fibers: sulfur, vat, fiber reactive, disperse, and
napthol dyes.
Ninety percent of the 32,197 m3/d (8,500,000 gallons/day) total water
usage is in wet finishing. Allowing for evaporation in the dyehouse, the
composite waste stream is at least 30% by volume dyehouse wastewater.
WASTEWATER CHARACTERISTICS
The variety of dyes and scouring chemicals used produce a complex and
variable waste stream composition. The wastewater characteristics, based on
a monthly average for the summer of 1975, of plant wastewater discharge
parameters are: BODs = 400 rng/A; COD = 1580 mg/fc; total suspended solids =
170 mg/&; total dissolved solids = 1950 mg/lj pH = 10.3; temperature = 90°F.
Tables 1-2, 1-3, and 1-4 present the results of analyses for six grab samples
Division of Commonwealth Laboratory, Inc., Greenville, SC.
201
-------
TABLE 1-1. PLANT #83 PRODUCTION CAPACITY PARAMETERS
QUANTITIES USED
Materials: cotton, cotton/polyester
Water (total to plant), m3/day
(galIons/day)
Water (to dyehouse) , m3/day
(galIons/day)
Dyes, kg/day
(pounds/day)
Auxiliary Chemicals, kg/day
(pounds/day)
Energy (for process steam), joules/day
(Btu/day)
32,197
(8,500,000)
9,659
(2,550,000)
5,293
(11,644)
21,130
(46,486)
8490 x 109
(8087 x 106)
UNIT COSTS
Water, <=/m3
($/1000 gallons)
Fuel, C/107 joules
($/106 Btu)
3
(6.12)
1.4
(1.51)
202
-------
TABLE 1-2. CHEMICAL ANALYSES OF PLANT #83 WASTEWATER
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
829
8/6/75
1312
404
425
510
26
1800
1783
1204
-
80
1,650
17
11.15
-
0.01
2.4
0.09
0.3
0.02
1.9
3.4
6.0
832
8/8/75
1689
340
330
657
26
1640
1560
1020
-
187
2000
58
11.25
-
0.01
0.38
0.58
0.19
0.1
0.55
0.6
3.5
838
8/11/75
2784
480
-
382
-
1612
1396
1108
-
89
-
-
10.70
—
-
-
-
-
-
-
-
a Grab samples of total plant effluent.
b All results are in mg/fc, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
203
-------
TABLE 1-3. CHEMICAL ANALYSES OF PLANT #83 WASTEWATER
SAMPLE NUMBER
840
843
DATE TAKEN
8/12/75
8/13/75
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
pH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
2112
513
626
1172
712
920
140
10.70
b
Grab samples of total plant effluent.
All results are in mg/Jl, except for color (Pt-Co units) , turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
204
-------
TABLE 1-4. CHEMICAL ANALYSES OF PLANT #83 WASTEWATER°
SAMPLE NUMBER
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
848
8/14/75
1248
393
312
286
26
1392
1192
928
-
58
1200
22
10.70
-
0.60
1.6
0.2
0.02
0.05
2.7
0.4
5.0
852
8/15/75
1344
413
315
427
26
2340
2196
1320
-
67
2700
85
11.15
—
0.1
1.5
0.3
0.48
0.02
0.1
0.4
40
3 Grab samples of total plant effluent.
b All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm) , and pH (unitless),
205
-------
obtained during the period of on-site testing. Plant #83 is classified as
Subcategory 8, commissioned finishing.3
SCHEDULE AND PROCEDURE
Schedule
Testing was begun on August 5, 1975. Initially, one-gallon (3.8£)
samples of purified product and concentrate were collected for reuse evalu-
ation in the plant laboratory. The UOPb module was then taken out of
operation for the remainder of Plant #83's testing program. A 38£ sample of
concentrate was later collected for" the biological treatability study.
The following is a summary of events at Plant #83:
07/30 - Arrived from Plant #82; utilities connected.
s*
08/05 - Began parametric performance test with UOP and Selas modules.
08/07 - Reuse test samples generated.
08/13 - Use of UOP module discontinued.
08/15 - Parametric performance test completed.
08/21 - Began special tests utilizing Selas and Union Carbide modules.
08/28 - Special tests completed.
09/04 - Returned to Clemson University.
Procedure
The membranes for evaluation were selected based on availability and
the characteristics of the wastewater. The wastewater was prefiltered
through 25-micron cartridge filters prior to entering the mobile laboratory.
The pH was adjusted when necessary to meet membrane manufacturer specifi-
cations. Figure 1-1 shows schematically the equipment arrangement. Three
types of membranes were employed in these tests: the UOP spiral-wound
cellulose acetate membrane, the dual-layer dynamic membrane on the Selas
ceramic tubes, and the Union Carbide tubular ultrafilter.
Development Document for Effluent Limitation Guidelines and New Source
Performance Standards for the Textile Point Source Category. EPA-440/1-
74-022-a, US Environmental Protection Agency, Washington, DC, 1974.
Universal Oil Products, ROGA Division.
Selas Corporation of America, Flotronics Division.
Union Carbide.
206
-------
PRODUCT a CONCENTRATE
to
o
BLEED
WASTE
DITCH
«••
COARSE
SCREEN
PRODUCT
CONCENTRATE
RETURN
SPARGE a SETTLING
pH ADJUSTMENT TANK
25 ./c
FILTRATION
SELAS
FEED TANK
[HYPERFILTRATIOJ^ LABORATORY |
Figure 1-1. Flow schematic for equipment set-up at Plant #83.
-------
REUSE
All types of membranes were used to generate samples for reuse evalu-
ation. A sample of composite wastewater was drawn from the plant sewer, and
pumped through a 25-micron filter into the mobile laboratory. The hyper-
filtration was conducted until 90% (by volume) of the water was recovered as
purified product water. Dyes, salts, etc., were concentrated in the remain-
ing 10% of the water. Samples of both the product water and the concentrate
were taken at 75% recovery, and also at the 90% recovery level.
Both the 75% and the 90% recovery samples were evaluated for reuse.
However, for budgetary reasons, only the 90% recovery samples were subjected
to detailed chemical analyses. The 90% recovery samples, of course,
represent the more severe test of reuse. Because membranes do not separate
100% of the dissolved material, the 10% by volume residue is only about
eight times as concentrated as the plant composite wastewater (instead of
the volumetric factor of ten).
The purified product water contains some chemicals, also because the
membranes do not reject 100% of the dissolved materials. The samples of
purified product water evaluated for reuse were obtained near the end of
the concentration (90%), and thus contain more chemicals than the average
product water would have. In fact, for these membranes the mixed product
water from a full-scale hyperfiltration plant would contain only about one-
third the contaminants shown by the analyses listed in Table 1-5.
The two types of membranes were tested simultaneously and therefore
processed composite waste with exactly the same characteristics. The
collection of samples for reuse took about twenty-four hours. The concen-
tration was accomplished by withdrawing Selas and UOP products.
The product water contained high concentrations of solids (885 mg/Jl)
and COD (103 mg/£). This was expected because of the high concentrations
in the waste stream and was not indicative of poor membrane performance.
The concentrate water was very strong, containing 7030 mg/£ total
solids, and 2700 mg/& of COD. The total solids are mostly salts as indicated
by the high (75%) percentage of non-volatile substances in the concentrate.
This data agrees with the percentage of non-volatile salt found in the
plant effluent.
Since it may not always be desirable to attempt direct reuse or
reclamation of the concentrate, the 90% recovery concentrate was used in
the treatability tests.
REUSE EVALUATION
Since the fibers processed by Plant #83 are cotton and polyester, the
waste stream contains the many chemicals associated with the scouring,
desizing, and dyeing of these fibers and their blends. Because of this
there was little likelyhood that chemicals could be recovered from the
concentrated residue. There is the possibility of recovering chemicals
208
-------
TABLE 1-5. CHEMICAL ANALYSES OP WATER EVALUATED FOR REUSE3 AT PLANT #83
(90% Water Recovery)
TYPE
SAMPLE NUMBER
DATE TAKEN
d
PARAMETER
COD
BOD
TOG
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
a Reuse tests conducted
*-* ,-,^T-V 3,_1~ ,,^v*4- 21 -i n^r} <
UOP/Selas
Concentrate
824
8/6/75
2700
210
2000
220
220
7030
6987
1770
1400
770
6800
0.08
7.0
<0.001
<0.01
1.62
0.98
<0.01
0.07
0.39
<0.01
10.5
in Plant #83 dye
jni ral-wound cellx
uopb
Product
826
8/6/75
53
11
43
200
10
74
74
48
10
0.5
83
0.14
6.0
<0.001
<0.01
0.73
<0.01
. <0.01
<0.01
0.16
0.05
0.62
laboratory.
ilose acetate
Selasc
Predict
828
8/6/75
103
8
39
64
10
886
885
76
15
1.0
1550
0.015
6.8
<0.001
<0.09
0.51
<0.01
<0.01
<0.01
0.71
0.09
0.71
membranes.
UUP moauj-e uwjJi.aj.Jicw *>&*• •-—
Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (pmho/cm), and pH (unitless).
209
-------
from isolated process waste streams. The analyses results for the purified
product water and the concentrated residue from both the cellulose acetate
and the dynamic membranes are presented in Table 1-5.
Reuse of Product Water
As a stringent test of the reuse of the product water, the 90%
recovery samples were evaluated. The analyses of the product water indicates
that, in general, the COD and dissolved solids are much more than expected
for tap water.
All of the purified product water generated by the mobile laboratory
at Plant #83 was evaluated in the plant laboratory and found suitable for
reuse in the plant.
The product water was used in the laboratory to dye 55/45 polyester
avril fabric, 100% T-64 polyester fabric, and 100% orlon and multifiber
test cloth. The procedures employed in the test dyeings were standard for
continuous dyeing. All of the purified product water was found suitable
for general reuse as dyehouse process water. No problems were encountered
with color-fastness or any other property.
Reuse of Concentrate
The concentrate water from 70% and 95% water recoveries were evaluated
for process water using exactly the same procedures and chemicals as used
with the product water reuse tests. No reuse value was determined for the
concentrate.
It is possible, when the wastewater and chemicals are recovered by
hyperfiltration, to change the process to (1) achieve faster dyeing cycles,
and/or (2) to eliminate the need for some auxiliary chemicals. For
example, with direct dyeing of cellulose, salt can be eliminated by using
higher concentrations of dye in the dyebath. Excess dyestuffs will be
recovered by the membranes for reuse in the next cycle. Depending on the
amount of fiber dyed and range of colors, this modification may or may not
be practical. Water, chemicals, and energy requirements will play a major
role in the selection of dyeing processes used in the future.
MEMBRANE PERFORMANCE
The cellulose acetate and dynamic membrane were operated on pretreated
composite wastewater (Table 1-2) for 87 and 200 hours, respectively,
beginning on August 8, 1975. The performance of the membranes was monitored
by periodic measurements of the product water flow rate through the membranes
and the conductivity rejection.
The membranes were fed from a common tank. The incoming feed was
neutralized to pH = 7 with sulfuric acid and controlled at that level.
Tables 1-6 and 1-7 show analyses performed on feed water after neutralization
and 25-micron filtration. The volumetric recovery was allowed to rise to
^90%, to obtain samples for reuse evaluation, and was maintained there
210
-------
TABLE 1-6. CHEMICAL ANALYSES OF WASTEWATER TREATED3
FOR MEMBRANE PERFORMANCE TESTS AT PLANT #83
SAMPLE NUMBER
830
835
DATE ^TAKEN
8/6/75
8/8/75
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
1216
335
267
151
36
1984
1844
884
115
1700
126
6.40
0.08
2.4
7.9
0.09
0.5
0.7
0.6
6.3
a Grab samples of combined plant effluent with 25-micron prefiltration,
followed by neutralization to pH ^ 6.5.
b All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
211
-------
TABLE 1-7. CHEMICAL ANALYSES OF WASTEWATER TREATED
FOR MEMBRANE PERFORMANCE TESTS AT PLANT #83
SAMPLE NUMBER
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
839
8/11/75
1632
360
-
0
-
2096
Dissolved Solids 1920
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
808
-
145
-
-
3.95
-
-
-
-
-
-
-
-
-
849
8/14/75
960
367
295
166
52
1720
1634
788
-
176
1700
480
9.25
-
0.1
1.8
6.7
0.17
0.4
0.8
1.15
4.5
a
Grab samples
, followed by
of combined plant effluent with
neutralization to pH
-------
throughout the remainder of the 200-hour test. The temperature was maintain-
ed at near 35°C while the UOP module was in use and at 55°c after it was
removed. The UOP module was removed from service twice for cleaning. At
148 hours, a settling barrel was placed in the feed between the pH adjustment
site and the 25-micron filters. This alleviated the rapid fouling of the
UOP spiral-wound module.
Dynamic Membrane
Three modules of Selas ceramic tubes with dynamic Zr-PAA membranes were
evaluated. The performance is summarized in Figure 1-2, a plot of flux and
rejection throughout the test period. One of the modules, #14, was equipped
with new membranes and therefore had a somewhat higher initial flux.
Module #4 was equipped with fifteen-month old membranes that had already
been used at several other plants. This older membrane exhibited a lower
initial flux.
The effect of fluid velocity on flux decline was the subject of para-
metric testing. At 148 hours, the velocity for Module #10 was reduced from
4.5 m/s (15 fps) to 3.3 m/s (10 fps). This change in velocity had no
discernable effect on the flux decline. The flux used in the design cost
projections is 0.5 m/d (13 gallons/ft2/d) at 37°C and 6.9 MPa (1000 psig) .
The conductivity rejection allows measurement of the electrolyte
filtration by the membrane. The filtration efficiency for larger organic
molecules is usually higher than for the electrolytes. Grab samples of
the concentrate and product waters passing through the membranes were obtain-
ed during the 200-hour performance tests and analyzed to indicate the
filtration efficiency for several constituents. The results of analyses for
three pairs of samples are shown in Tables 1-8 through I-11.
The high rejections of organics, indicated by COD, BOD, and color
comparisons between the concentrate and product samples are greater than the
conductivity rejections. The phenol rejection is about 88%. The rejection
of metals is very high, as indicated in cases where results are significantly
above the limit of detection.
Cellulose Acetate Membrane
The performance of the cellulose acetate membrane module is summarized
in Figure 1-3, a plot of flux and rejection throughout the test period. The
operating conditions were specified by the manufacturer: 2.4 MPa (350 psig)
and a feed rate of 0.8 - 0.9 m3/hr (3.5 - 4 gallons per minute). The
module tested had been used at previous test sites. The module had to be
cleaned twice due to the accumulation of particulates. Flux was severely
effected but rejections remained high throughout the test. It is assumed
that better prefiltration than was available with the mobile laboratory
would solve the problem. The results of, two pairs of samples of product
and concentrate are shown in Tables I-10 and 1-12.
213
-------
100.0 .
z
o
UJ
~>
UJ
a:
75.0.
50.0
o
A
O
A
g 0 —
0^-!*
••MW
A
o N0.
38.0
t
24.0
v
12.0
<
0.0
A NO.
r Q — Na
D
-V
X
4,V = 3.9m/4
IO,V = 4.5 m/i and 3.3 m/8 BEFORE AND AFTER 148 HR
14, V =4.5 m/8
-
-
\ ~~^-A
^~A~A- — A-QQ q \
. AA A0"""^3 r*!» Vn
^^^^^^P^^^&B^^I — ^^"
w ^^.^•^•^^^3*^^^
1
-O-O- •" - A-A—^T o-O -CfcrQt
• Q *• C« I*
0 • y y
• ^
I I 1
1.2
1.0-
•o
0.8 «^
0.6 L
X
0.43
•Ml
u.
0.2
0.0
50
100 150
TIME (hours)
200
250
Figure 1-2.
Hyperfiltration of combined effluent at Plant #83 by
Zr(IV)-PAA membranes on Selas ceramic supports.
(P = 6.31 MPa (920 psig); pH = 4.0 - 9.8;
recovery = 90%.)
214
-------
TABLE 1-8. PERFORMANCE PARAMETERS OF SELAS MODULES3 IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #83
SAMPLE NUMBER
TYPE
DATE TAKEN
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
833
Product
8/8/75
105
23
8
107
A
468
468
324
-
3
1000
5
9.90
-
0.01
0.003
0.02
0.02
0.02
0.005
0.01
0 1
w • 4r
834
Concentrate
8/8/75
3696
310
620
507
260
5160
5080
1752
-
74
4700
157.5
9.60
_
0.15
5.9
13
0.80
0.7
1.2
0.8
25
a Selas module contained ceramic tubes with dynamic membranes.
b All results are in mg/A, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
215
-------
TABLE 1-9. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #83
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
836
Product
8/11/75
40
50
16
248
2
488
488
196
-
2
880
10
9.95
-
0.01
0.003
0.02
0.02
0.02
0.005
0.01
28
837
Concentrate
8/11/75
2900
533
760
353
117
5800
5715
2256
-
71
5200
315
9.35
-
0.15
4.05
20
1.04
0.7
1.65
2.2
28
Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/&, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
216
-------
TABLE I-10. PERFORMANCE PARAMETERS OF SELAS AND UOP MODULES IN
THE MOBILE HYPERFILTRATION LABORATORY AT PLANT #83
TYPE
SAMPLE NUMBER
DATE TAKEN
PARAMETER0
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
•
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
Selas/UOP
Concentrate
845
8/13/75
500
143
232
128
221 '
3176
3138
576
-
47
4000
35
6.80
~
0.15
6.15
12.0
0.48
0.4
0.1
0.2
14
Selas
Product
846
8/13/75
20
8
7
65
6
396
396
176
-
2.5
780
5
7.20
0.01
0.2
0.02
0.02
0.02
0.005
0.01
0.355
uopb
Product
847
8/13/75
30
9
9
26
1
84
84
84
-
2.6
100
5
6.90
0.01
0.003
0.02
0.02
0.02
0.005
0.01
0.0005
a selas module contained ceramic tubes with dynamic membranes.
b UOP module contained spiral-wound cellulose acetate membranes.
° All results are in mg/Si, except for color (Pt-Co units) , turbidity
(FTU), conductivity (pmho/cm) , and pH (unitless).
217
-------
TABLE I-11. PERFORMANCE PARAMETERS OF SELAS MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #83
SAMPLE NUMBER
TYPE
DATE TAKEN
b
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conduc ti vi ty
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
850
Product
8/15/75
57
16
12
121
5
480
480
244
-
4.1
900
375
7.65
-
0.01
0.07
0.02
0.02
0.02
0.005
0.01
20
851
Concentrate
8/15/75
2304
323
750
578
221
4840
4720
1992
-
83
3500
310
7.55
-
0.2
4.5
20
0.90
1
2.15
1.6
31.5
, Selas module contained ceramic tubes with dynamic membranes.
All results are in mg/£, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
218
-------
KX>.Or
z
2
H-
o
UJ
-a
Ul
01
,i
o
.§
X
-J
u.
90X)
800
-
_
1 — i i__ i i i
M>
c
&0
4O
2.0
0.0<
r
t REJECT FLOW =!5<^(n (46PM)
L [SYSTEM
v r IDEPRESSURIZED o
0 '
- \ ' ^--TAP WATER RINSE ^
n 1 1 \
NOO ' ' QQ\
Q:\ Q ^M3)O -
®Q O X x'
—
i i | ii i
) 30 60 90 120 150 180
TIME(hours)
0.3
0.2 ^
1
"E
Ql ><
j
u_
0.0
Figure 1-3.
Hyperfiltration of poiribined effluent at Plant #83 by
cellulose acetate membranes in a UOP spiral-wound
module.
219
-------
TABLE 1-12.
PERFORMANCE PARAMETERS OF UOP MODULES IN THE
MOBILE HYPERFILTRATION LABORATORY AT PLANT #83
SAMPLE NUMBER
841
842
TYPE
Product
Concentrate
DATE TAKEN
8/12/75
8/12/75
PARAMETER
COD
BOD
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
PH
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Magnesium
48
16
44
52
52
52
2.9
6.05
768
147
103
2588
2532
784
52
UOP module contained spiral-wound cellulose acetate membranes.
All results are in mg/i, except for color (Pt-Co units), turbidity
(FTU), conductivity (ymho/cm), and pH (unitless).
220
-------
APPENDIX J
BIOLOGICAL AND CHEMICAL TKEATABILITY
OF HYPERFILTRATION CONCENTRATE
As the technological capabilities of hyperfiltration (reverse osmosis)
for the treatment of textile wastes increase, it has become necessary to
examine the feasibility of chemical and/or biological treatment of the
concentrated wastewater left behind after product water has been recovered
for recycle to the plant.
This appendix is a summary of the study conducted for the South Carolina
Textile Manufacturers Association (SCTMA) to determine the biological and
chemical treatability of textile waste concentrates. A more detailed report
is on file at the SCTMA offices in Columbia, South Carolina. The concen-
trates were obtained from six of the eight textile plants where the mobile
hyperfiltration laboratory was operated.
HYPERFILTRATION
The membranes utilized in the mobile laboratory were manufactured by
Selas, Universal Oil Products, and Westinghouse (now Union Carbide). The
concentrate wastewater examined in this study represent six different textile
plants conducting most of the wet finishing operations found in the textile
industry. The pH range of the raw plant wastewater ranged from 4 to 11. The
operating temperatures ranged from 30°C to 65°C depending on the process
characteristics and hyperfiltration membrane being used. The wastewater was
pretreated by 25-micron prefiltration with cartridge filters and the pH
was adjusted as necessary for the specific membrane system being used.
Membranes effect a separation of the wastewater into a product stream
which is the concentrated residue of impurities after removal of the product
stream. In the systems as operated for these tests, the concentrate was
returned to the raw wastewater holding tank and was thereby recycled through
the system a number of times. The membrane systems utilized in these tests
were operated to achieve from 80 to 92% recovery of product water; that is,
the recycling process was continued until 80 to 92% of the original volume
of wastewater was recovered as clean product water. As a result, the
impurities remained in the 8 to 20% volume of concentrate. The concentrate
was used in this study for biological and chemical treatment.
The characteristics of the membrane concentrates for all six plants
are given in Table J-l. The characteristics of the raw wastewater feed to
221
-------
TABLE J-l. CONCENTRATE WASTE CHARACTERIZATION
to
to
10
Non-metal Analyses
COD
Filtered COD
TOC
BODs
BOD10
BOD15
BOD20
BOD30
Solids
Total
Dissolved
Suspended
Volatile
pH
Color (Pt-Co units)
Turbidity
Conductivity (ymho/cm)
Alkalinity
Hardness
Ammonia Nitrogen
Total Kjeldahl
Nitrogen
Phosphorus
Phenols
#60
2500
935
270
415
515
560
820
3760
3000
760
2030
6.7
1250
43
2000
140
32
24
25
160
1.0
#70
3720
1410
1078
1600
1800
1600
2200
5028
4803
225
2104
6.0
1000
3
3900
456
57
5
11
412
0.40
#40
15285
5753
1547
2200
3500
4500
5000
10028
9853
175
4050
6.6
12044
opaque
9000
587
74
3
6
15
0.52
#80
4032
707
561
300
475
700
425
9870
9785
85
1254
6.8
2618
0.38
9600
182
135
3
6
6
0.1
#81
8871
7942
4140
3745
4700
4450
4700
3000
8702
8347
355
5074
7.0
5618
opaque
5000
341
75
4
10
41
0.1
#82
2496
2487
1606
860
925
1175
1100
450
4334
4106
228
1714
5.0
1826
15
4000
65
97
12
14
3.0
0.1
-------
TABLE J-l. (continued)
to
10
OJ
Metal Analyses
Calcium
Chromium
Copper
Iron
Magnesium
Manganese
Mercury (yg/fc)
Nickel
Zinc
#60
2.4
0.13
0.2
1.3
1.0
0.53
-
0.33
2.9
#70
4.0
0.19
1.2
1.3
6.0
0.08
6.0
0.13
3.4
#40
2.1
8.1
8.6
10.3
12.0
0.28
-
1^2
5.2
#80
5.9
3.1
0.64
12.0
13.0
0.43
5.5
1.9
5.0
#81
3.7
Ii4
0.66
7.0
24.0
1.8
6.0
8. ft
3.0
#82
8.5
-
6.2
2.S
-
0.27
1.0
0^56
20.0
Unless otherwise indicated, all units are in rng/1 with the exception of pH, which
is unitless.
-------
the membrane unit were not monitored. The average value for the feed, based
on the concentrate characteristics and the membrane performance, were cal-
culated (Table J-2).
The raw wastewater feed was drawn from the plant composite sewer and
was not constant. The calculated values are the characteristic of an average
waste stream that would result in the concentrate characteristics that were
measured. The values of membrane rejection, used in calculations, were
observed for each constituent at each mill.
Concentrate treatability results for six plants located in South
Carolina and involved in this study will be discussed in this section. They
are Plant #60, Plant #70, Plant #40, Plant #80, Plant #81, and Plant #82.
The composite waste concentrate from Plant #40 was mixed on a 60/40 basis
with an indigo wash water concentrate obtained from their Plant #40-1 to
observe the effect of indigo on the biological as well as chemical treata-
bility of the Plant #40 mixture. The concentrate from Plant #60 was a
50/50 mixture of concentrates from two membranes: cellulose acetate (UOP)
and hydrous Zr(IV) oxide-polyaerylate (Selas).
ANALYTICAL PROCEDURES
The following is a brief summary description of the chemical analyses
and tests performed during this study. For further description and full
detail of the principles, theories, and techniques involved in each test,
see Standard Methods for the Examination of_ Water and Wastewater.a
Alkalinity
Alkalinity is defined as the capacity of water to accept protons. It
is imparted by the salts of weakly ionized acids and the unionized portion
of weakly ionized bases and/or free bases at high pH values. Alkalinity is
determined by titration to pH 4.5 with standard sulfuric acid solutions,
and is reported in milligrams per liter of sample.
Ammonia Nitrogen
Ammonia nitrogen is the concentration of ammonium and simple amine
structures present in a sample, expressed as milligrams nitrogen per liter
of sample. Ammonia nitrogen is desirable in biological treatment as a
source of nutrient for the microorganism cultures. The level of ammonia
nitrogen required for best treatment has been reported to be, in ratio form,
ppm BOD:ppm NHg-N = 100:5. Ammonia nitrogen is measured by the Nessler
colorimetric technique, which results in the development of a colored
complex whose absorbance is evaluated at 410 nanometers on a Spectronic 20
spectrophotometer.
13th Edition, A.P.H.A., 1971.
224
-------
TABUS J-2. CHARACTERISTICS OF RAW WASTEWATER FEED TO HYPERFILTRATION UNITS
to
10
Analyses
COD
BOD5
TOC
Alkalinity
Hardness
Total Solids
Dissolved Solids
Suspended Solids
Volatile Solids
Color
Turbidity
Conductivity
Phenol
Mercury
Manganese
Calcium
Iron
Nickel
Chromium
Zinc
Copper
Plant #81
925
390
-
39
8
928
890
-
535
562
-
562
0.01
-
0.38
0.79
0.01
0.17
0*31
0.08
2
Plant #82
276
89
170
10
10
553
524
-
211
187
2
492
0.016
-
0.03
0.86
0.30
0.06
-
2
0.02
Plant #60
265
29
97
26
4
390
314
-
206
127
-
227
3
-
0.07
0.58
0.41
0.05
-
-
0.16
Plant #80
541
84
85
38
14
1331
1326
-
192
262
0.04
1433
0.02
-
-
-
-
-
-
-
-
Plant #40
1687
166
606
109
8
1315
1293
-
457
1227
-
1307
0.06
-
-
-
-
-
0.86
0.56
0.90
Plant #70
415
126
215
56
6
560
535
-
242
50
-
444
0.04
-
0.008
0.40
—
—
-
-
-
_. "'" ~-.j ,\....T! " • » - " c i .> '•""•"••";- .nfie ~~ • :.=.-»'« -v-c -~. "..::"-: >"£.•= _ •*>.•*•*:• - _- . -
Calculated from measured membrane performance and concentrate characteristics, Table J-l.
-------
Biochemical Oxygen Demand (BOD)
The BOD represents the organic content of a wastewater sample which is
biodegradable under a given set of circumstances, measured as milligrams
oxygen for biodegradatioh per liter of sample. The BOD is measured by
determining the change in dissolved oxygen (DO) content over a five-day
period of an aliquot of the sample which has been diluted and seeded with
a microorganism culture and nutrients and incubated at 20°C. A correlation
is often made between BOD and COD, in that BOD represents the portion of
the COD which is biodegradable, and the ratio BOD/COD represents the fraction
of biodegradabilityi
Chemical Oxygen Demand (COD)
The COD represents the oxygen required to.totally oxidize the organic
content of a wastewater sample to carbon dioxide and water, expressed as
milligrams oxygen per liter of sample. COD is measured by reacting a
desired and known aliquot of wastewater sample with an excess of potassium
dichromate in 50% sulfuric acid. After a two-hour reflux, the excess
dichrornate is titrated with ferrous ammonium sulfate solution to a ferrion
endpoint. The basic chemical reaction is the oxidation of organics and the
reduction of dichromate to chromic ion.
Color
Color represents a measure of the contamination in a water sample which
is visually detectable. Color may be reported as either apparent color,
which results from investigating a raw sample, or true color, which results
from investigating a filtered sample (the filtration step removes turbidity
from colloids and suspended solids). Color is expressed in Platinum-Cobalt
units (Pt-Co or PCU). For the analyses performed in this work, apparent
color at 410 nanometers on a Spectronic 20 spectrophotometer was found.
Conductivity (Specific Conductance)
Conductivity is the degree to which a liquid sample will conduct an
electric current in the presence of an applied electrical potential, express-
ed as micro-ohms per centimeter. Conductivity gives an indication of the
total ionic content of the sample, since the more electrolyte present, the
higher the conductivity. Conductivity measurements are made using standard
conductance cells and electrical bridges (usually optical or meter null
potentiometer bridges) such as Beckman Instruments and Balsbaugh Laboratories
bridge and cell systems.
Dissolved Oxygen
The dissolved oxygen is the concentration of oxygen which is dissolved
in a water sample, expressed as milligrams oxygen per liter of water.
Dissolved oxygen levels in water can range between 0 mg/i and saturation,
which is 9.1 mg/£ at 20°C. Dissolved oxygen is measured by the membrane
polarographic technique, using a conventional analyzer such as the Yellow
226
-------
Springs Instruments (YSI) Model 54 meter. Changes in dissolved oxygen can
often indicate the presence of a biological culture which may be degrading
a waste sample. This forms the basis of the BOD test.
Hardness
Hardness refers to the characteristic of water which represents the
concentration of calcium and magnesium ions in the water, expressed as
milligrams calcium carbonate per liter of sample. Hardness is determined
by titrating with a standard EDTA solution to the Eriochrome Black T
indicator endpoint.
Metals
The evaluation of the concentrations of individual metals in a wastewater
sample is performed using an atomic adsorption spectrophotometer. The
samples are first treated with acid to solubilize most metal compounds and
the samples are then aspirated into the flame for determination. Comparison
of adsorption characteristics of the samples with standards for the desired
metals are made, and the metal concentration determined from this.
The pH of a liquid is a measure of its acidity or basicidity, and is
defined as the negative base 10 logarithm of hydrogen ion concentration.
Measurement of pH is accomplished using a pH meter with standard electrodes.
Phenols
The phenol concentration as defined in this study refers to the concen-
tration of phenol, ortho- and meta- substituted phenols, and some para-
substituted phenols in a wastewater sample. These are the phenolic compounds
which react with 4-aminoantipyrene solution to yield a gold color, the
intensity of which is proportional to the concentration of phenols present.
The developed color is evaluated on a Spectronic 20 spectrophotometer at
510 nanometers, and is expressed as milligrams phenol per liter of sample.
Phosphorus
Phosphorus as determined for this study refers to the concentration of
ortho-phosphates in a wastewater sample reported as milligrams phosphorus
per liter of sample. Phosphorus is measured by the Stannous Chloride Method,
which produces a highly colored heteropoly acid, molybdenum blue, the
adsorbance of which can be evaluated at 690 nanometers on a Spectronic 20
spe ctropho tome ter .
Dissolved Solids
Dissolved solids represent the concentration of matter in an aqueous
sample which passes through Whatman 42 filter paper and becomes solid when
the filtrate is dried as in total solids. Dissolved solids is composed of
soluble salts and organic compounds, and is expressed as milligrams solid
per liter of sample.
227
-------
Suspended Solids
Suspended solids refers to the concentration of matter in a wastewater
sample which is removed by filtering the sample, expressed as milligrams r»*
solids'per liter of sample. Suspended solids is measured as the difference
between total and dissolved solids. Alternately, a tarred filter may be
used to vacuum filter an aliquot of the sample, the filter dried, and re*^«4|f
weighed. Millipore, Gelman, and Nucleopore Systems are among those commonly
used in the latter technique.
Total Solids
Total solids represent the concentration of matter in an aqueous sample
which remains when the water is removed, expressed as milligrams solid per
liter of sample. Total solids is measured by drying a measured aliquot of
sample in a tarred beaker at 105°C for twenty-four hours, cooling, and
reweighing the beaker.
Volatile Solids
Volatile solids refer to the concentration of solid matter from a total
solids test which volatilizes at 600°C for fifteen minutes, expressed as
milligrams solid per liter of sample. To perform volatile solids, a crucible
is used instead of a beaker. Total solids is first performed, and then the
residue in the crucible is heated for the volatile solids test, cooled, and
reweighed. Volatile solids usually represents the majority of the solid
organic content of a sample, since the organics are oxidized to carbon
dioxide and water at the high temperature used, while most inorganic salts
remain.
Total Organic Carbon (TOC)
The concentration of carbon which is organically bound in a wastewater
sample is referred to as total organic carbon, and is expressed as milligrams
per liter. TOC is determined by first injecting a desired aliquot of the
sample into a 950°C column with special packing. All the carbon, whether
organic or inorganic, is oxidized to CQ^ which flows into an infrared
detection system for measurement. Then inorganic carbon is found by inject-
ing a second aliquot into a 150°C column with packing, in which the inorganic
carbon is oxidized to CO2 and read in the infrared detector. Total organic
carbon is then evaluated as the difference between total carbon and inorganic
carbon.
Turbidity
Turbidity is defined as that quality of a water sample which causes it
to exhibit a cloudy or milky appearance. Turbidity is caused by colloids
and finely suspended solids. Measurement of turbidity is made by determining
the amount of light which a sample scatters when a light source and a
detector are placed ninety degrees apart. Standard turbidity instruments such
as the Hach Model 2100 A Turbidimeter may be used with standards, and the
results expressed as Formazin Turbidity Units (FTU).
228
-------
BIOLOGICAL TREATMENT
Theory of Biological Treatment*
Biological waste treatment systems are operated on the principle that
numerous species of microorganisms are able to consume organic materials in
an aqueous system and utilize these nutrients as food. By this process,
organics are removed from the water and the microorganisms live and reproduce.
If the waste to be treated is of a type that is easily degraded by the
microorganism colonies, the waste is said to be biodegradable. If the waste
cannot be broken down biologically, or shows considerable resistance to such
treatment (as by the presence of toxic metals or chemicals, etc.), it is
said to be relatively non-biodegradable.
There are several methods of determining the biodegradability of a
waste. Perhaps the simplest is to obtain the COD and BOD5 and BOD30 of the
waste, and calculate the BOD to COD percent ratio, or the percent bio-
degradable as
BOD30
% biodegradable = ••_- x 100.
A more accurate measure of the biodegradability is obtained from a biological
treatability study as described in this section. In such a study, the raw
waste, after suitable pH and nutrient adjustments, is fed into a biological
oxidation chamber, which is a bench-scale aeration lagoon. This chamber is
charged with a biological culture which has been acclimatized to the waste
which it is to degrade. Air is bubbled through the chamber since the bio-
culture requires oxygen to assimilate the food supply in the organics. The
reactor effluent is then allowed to become quiescent for a time, which allows
the entrained bioculture to settle out and be returned to the reactor. The
liquid which remains is the clarified effluent (or decantate) and is the
treated sample which is discharged from the biological system either to the
environment or to further treatment steps.
There are several methods of determining the degree of treatment being
achieved in a biological system. The simplest method is to measure the
dissolved oxygen depletion, or the rate at which a mixed sample from the
reactor will consume dissolved oxygen. If almost no DO is consumed, it can
be assumed that biodegradation is not occurring to a great extent. On the
other hand, a significant DO depletion (say, for instance, 1 mg/8, DO in
two - five minutes) indicates that the system is biodegrading the waste.
Measurement of COD and BOD are made throughout the time the system is
operated, with decreases in these parameters in the decantate samples over
the inlet feed samples indicating the degree of biological treatment. The
measurement of settleable solids is also important, since an increase of the
a
Metcalf and Eddy, Inc. Wastewater Engineering, Collection, Treatment
and Disposal. McGraw Hill, New York, NY, 1972.
229
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floe-like settleable mass of solids in the reactor indicates the conversion
of soluble organics into insoluble biomass (insoluble organics plus bacterial
sludge).
Biological Treatability Study - Experimental Methods
The biological portion of the treatability study was conducted using
a batch-fed, fill-and-draw apparatus as shown in Figure J-l. A ten-day
retention time was chosen for the study. The container was acclimated using
6 liters of composite concentrate waste plus biological seed.
After acclimation, the daily sampling schedule was. started. To counter-
act evaporating, deionized makeup water was added to the reactor each day.
The reactor cross-sectional surface area was approximately 300 cm^. On a
daily basis, 1.0 liter was removed in an Imhoff cone and allowed to settle
for one hour. While the 1.0 liter was settling, 0.3 liter of the clarified
liquor was removed from the Imhoff cone (including the settled sludge) were
returned to the reactor. Then 0.6 liter of feed (the composite concentrate
sample described above) was added to the reactor. This procedure, with a
net reactor volume of 6 liters and a daily throughput of 0.6 liter resulted
in a theoretical retention time in the reactor of ten days. Six daily
samples were taken on Monday through Saturday, with no sample taken on
Sunday. Samples of the mixed reactor and of the decantate were composited
over three-day intervals, giving two mixed reactor samples and two decantate
or clarified samples per week.
On approximately day 30 of each study, the reactor was brought to
1000 mg/£ of powdered activated carbon and from that time forward, 100 mg/£,
of carbon were added to the feed each day. This was done to observe whether
carbon added to the system would tend to adsorb any component of the waste,
thereby effecting better purification of the wastewater in the treatment
system.
CHEMICAL TREATMENT WITH ALUM AND CARBON
Theory of Coagulation
Coagulation refers to the unit operation employed in wastewater treat-
ment that invokes the formation of chemical bridges or floes that adsorb,
entrap, or otherwise cause an agglomeration of suspended colloidal matter.
Colloidal particles are small particles which can remain suspended in a
liquid medium for indefinite periods of time. The stability of colloids is
attributed to the fact that they are electrically charged, and thus tend to
repel each other in solution. To bring about coagulation this charge effect
must be reduced. This is usually achieved by one of three techniques3:
Richard D. Ross. Industrial Waste Disposal. Van Nostrand Reinhold, New
York, NY, 1968.
230
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pH Adjustment
and Nitrogen
and Phosphorus
Nutrient Addition
to
w
Feed
Reservoir
Aeration Chamber
Sludge Return
Decantate Sample
for Analysis
Oxygen
Mixed Reactor
"** Sample for
Analysis
Figure J-l. Schematic diagram of a batch fed> biological reactor.
-------
(1) Addition of potential-determining ions or electrolytes which can
react with the colloidal surfaces to decrease the charge.
(2) Addition of polymers. The sub-unites of the polymers ionize and
bring about the removal of particles by adsorption and bridging.
(3) Addition of metal salts which form hydrolyzed metal ions. The
hydrated metal ions undergo a number of reactions all of which are not known.
However, it is believed that these hydrates polymerize and cause adsorption
of colloidal particles onto the hydrate surface, with some added enhancement
of polymer bridging. Also, as the coagulated particles sweep through the
liquid, additional contaminants will usually be removed by enmeshment in the
floe. The two major coagulants used are alum (aluminum sulfate) and ferric
chloride.
Alum Tests
Coagulation with alum, or aluminum sulfate, often results in substantial
purification of wastewater, thus, alum was chosen arbitrarily for use in this
study. Other metal salts such as Fed 3 or (Fe)2(80^)3 could just as well
have been chosen.
No polyelectrolytes were utilized since we were not interested in
optimizing treatment but merely in testing for the feasibility of using
chemical flocculation for hyperfiltration concentrate waste treatment.
In practice, a solution of aluminum sulfate was added to a pH-adjusted
sample of wastewater. The pH is then re-adjusted to a desired level, at
which a floe of hydrated aluminum hydroxide forms. This floe has substantial
adsorptive capacity, and will often carry down many colloidal and dissolved
impurities as it settles out and is removed from the solution.
In the tests conducted for this study, the composite concentrate sample
was adjusted to pH 5 with 1 N_ sulfuric acid. Aliquots were withdrawn and
sufficient aluminum sulfate solution (from a 0.1% stock solution) was added
to the individual aliquots to achieve total alum concentrations in the
samples of 50, 100, 300, and 500 rng/A. Then the pH was re-adjusted to 6.0
(maximum floe density observed) with 1 N[ NaOH and the treated samples were
stirred (flocculated) for fifteen minutes. The floe was then allowed to
settle with no stirring for forty-five minutes.
Theory of Carbon Treatment
Carbon treatment is a wastewater technique which is often used in
treating industrial wastes. Activated carbon is carbon which has been treat-
ed to form large surface areas for a given weight of carbon. This large
surface area tends to promote adsorption of organic materials from the water.
As would be expected, the larger the concentration of activated carbon, the
greater the adsorption.
Carbon Study
A carbon adsorption isotherm was performed on this composite concentrate
waste using (pre-washed, filtered, and dried Hydro Darco C) powdered activated
232
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carbon. Aliquots (20°C) of the composite concentrate wastes were placed in
beakers under a gang stirrer. Sufficient powdered activated carbon (accur-
ately weighed) was added to the individual beakers to achieve concentrations
of carbon in the samples of 500, 2500, and 5000 mg/A. The samples, along
with a blank to which no carbon was added, were stirred under the gang
stirrer for one hour, and then filtered through two circles of Whatman Number
42 filter paper (0.6y).
DISCUSSION
Biological Treatability
As a general rule , it has been found empirically that the ratio of
BODs to nitrogen to phosphorus in a textile wastewater should be approximately
100:5:1, respectively, in order to provide sufficient nutrients for the bio-
degradation of wastes in an aerated lagoon. Consequently, the BODs, ammonia
nitrogen, and phosphorus content of each concentrate sample was determined
during the initial acclimation stage of each study to allow time for any
nutrient additions to the feed concentrate that might be necessary before
the actual sampling schedule was started.
The normalized (based on BOD5 as 100) average nutrient ratio for the
concentrates as received in the laboratory (before the study) was 100:30:10.
Plant #81, Plant #70, and Plant #82 had low phosphorus concentrations
(100:1:1) with Plant #40 and Plant #80 exhibiting sufficient ratios (approxi-
mately 100:9:1) and Plant #60 concentrate showing a high ratio (100:150:60).
Phosphorus addition was accomplished for the deficient Plant #81,
Plant #70, and Plant #82 samples by adding the required amount of Na2HPOit
(pH adjusted) to the concentrate feed samples.
The overall BODs ranges for the nutrients present in the concentrate
samples varied from a low of 270 mg/£ to a high of 3745 mg/fc (see Table J-l) .
Nitrogen concentrations varied from 3 mg/A to 24 mg/fc and phosphorus varied
from 3 mg/Jl to 160 mg/JZ..
The Plant #81 concentrate required fairly constant day-to-day addition
of 1 N_ HC1 (equivalent to 36 kg of concentrated HC1 per cubic meter of
concentrate, overall) to keep the pH from constantly rising throughout the
study. This was considered to be an unusual problem since O>2 in the system
as a by-product of the biodegradation process would be expected to lower the
pH (due to carbonic acid buildup) rather than raise it. Apparently, some
basic by-product was constantly produced during the biodegradation of
Plant #81 "s concentrate.
The overall average ammonia nitrogen removal during the studies (from
acclimation to shutdown) was 3.8% with Plant #70 exhibiting the lowest
removal (-38%) and Plant #60 showing the highest removal (93.3%).
Eckenfelder, W. W., and D. J. O'Connor. Biological Waste Treatment.
Pergammon Press, New York, NY, 1961.
233
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As previously mentioned, the BODag/COD ratio or percent biodegradability
can sometimes furnish insight into the feasibility of biological treatability,
The overall average percent biodegradability for the six mills was 40% with
Plant #80 showing the lowest percentage (18%) and Plant #70 giving the high-
est percentage (59%) . The values of this ratio correspond fairly well with
the actual biological treatability results for each mill obtained through
this study.
The dissolved oxygen (DO) content in the samples was monitored daily.
The DO data is extremely important since the oxygen demand for an aerated
lagoon is considered in determining the aeration and total aerator horsepower
requirements. The overall average DO uptake was 46 mg/i/hr at the beginning
of the study; 21 mg/&/hr was the lowest value observed (Plant #60) and
120 mg/£/hr was the highest value observed (Plant #81). At the end of the
study, the overall average DO uptake was 8.0 mg/A/hr with 3.0 mg/A/hr being
the highest observed uptake (Plant #40). The average DO uptake was consis-
tently observed to be greater at the beginning of a study than at the end.
This was attributed to the fact that the bacteria were experiencing
exponential growth (therefore requiring more oxygen) at the beginning of a
study as well as the fact that the concentration of biodegradable organics
present in the concentrate feed was greater at the beginning of a study than
at the end.
Settleable solids, measured on a daily basis throughout each study,
exhibited an average overall settling rate (all mills) of 38 m&/Jl/hr (0.9
gallon/100 gallons waste/day).
Chemical Treatability
Alum—
Treatment with alum was essentially ineffective up to 500 mg/i with the
average COD- removal being only 32.2%. The overall average BODs removal was
27.3% and the average color removal was only 33%.
Carbon—
Treatment with activated powdered carbon at the 5000 mg/i level
exhibited the same average percent removal of 8005 and COD as did alum
treatment at 500 mg/fc. Carbon removed twice as much apparent color (66.6%)
as alum, as would be expected.
Comparison of Treatment Methods
Table J-3 provides an overall picture of the effectiveness of the
treatment methods utilized in this study (Biological vs Chemical Treatment)
in treating the hyperfiltration wastewater concentrates from the six textile
mills studied.
For the biological study, carbon addition to the reactor seemed to have
little effect on decreasing the COD or BODs, although there was a signifi-
cant overall average (all mills) increase in the percent apparent color
removal (from 19.7% before carbon to an average 30.5% removal after carbon
234
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TABEE J-3. A SUMMARY OF OVERALL BEST RESULTS FOR TREATMENT METHODS
to
w
ui
Percent Removal
Plant
Biological Study
BOD5
COD
Color
Biological Study with
Carbon Added
BOD5
COD
Color
Alum Treatment
BOD5
COD
Color
Powdered Activated Carbon
BOD5
COD
Color
#60
86
44
16
97
72
56
9
10
0
61
73
62
#70
89
60
0
92
63
0
27
23
9
29
19
67
#40
39
29
0
36
35
0
14
23
0
76
69
67
#80
95
83
27
99
88
51
60
78
76
72
60
71
#81
98
65
75
99
66
76
15
14
48
35
32
80
#82
97
64
0
95
63
0
38
45
65
23
52
53
a Percent removal based on
1000 mg/H carbon addition
b feed>
Unfiltered or "apparent"
the results
Removal
color.
. i a
for the
based on
*_*_ _ V*. •_ .!_
entire period
including time
decantate sample compared to
_i ^_ _J__^_ _j_ Cf
\ A / n .!_-. _ii
before
the raw
and after
reactor
based on decanted sample after floe settling compared with the feed.
Data for the carbon treatment based on the best overall treatment, 5000 mg/i in all cases.
Removal based on a treated filtered sample compared with the untreated filtered raw feed.
-------
addition) . Carbon had no measureable effect in removing apparent color from
the Plant #70, Plant #40, and Plant #82 concentrate samples.
Alum treatment was ineffective exhibiting an overall 27.2% removal of
BODs with Plant #60 exhibiting the least BODs removal (9.2%) and Plant #80
giving the best treatment (60% removal). An overall average of only 32.2%
of the COD was removed by alum treatment with results ranging from 9.6% for
Plant #60 to 78% for Plant #80. The overall average color removal was 33%
using alum with results ranging from 0% for Plant #60 and Plant #40 to 76%
for Plant #80.
Carbon treatment was not very successful with the overall average
removal being 49.4% with results ranging from 22.7% for Plant #82 to 76.1%
for Plant #40. The overall average COD removal using carbon was 50.6% with
results ranging from 18.7% at Plant #70 to 72.7% at Plant #60. The color
removal using carbon was acceptable considering the fact that a concentrate
waste was being treated. The overall average color removal was 66.6% with
results varying from 52.7% at Plant #82 to 79.8% at Plant #81.
CONCLUSIONS
From the descriptions and data presented in this section, it appears
that:
(1) Hyper filtration produces a concentrated wastewater which can be
treated by conventional waste treatment techniques.
(2) Long-term biological treatment is a feasible technique for treating
the concentrate from hyper filtration.
(3) Addition of powdered activated carbon to the concentrate during
biological treatment is of limited utility in decreasing total organics in
both the mixed reactor and decantate samples, but can significantly reduce
color.
(4) Alum in concentrations up to 500 mg/SL is ineffective in decreasing
the organic loading or physical color of the concentrate.
(5) The addition of powdered activated carbon to the concentrate
samples (as a chemical treatment method and not as an adjunct to biological
treatment) was relatively ineffective in lowering organic loading yet did
remove significant amounts of color. The degree of color removal was shown
to increase as the concentration of carbon was increased up to and including
5000 mg/H.
236
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TECHNICAL REPORT DATA
11 lease read Inunctions on the reverse before completing)
. HEPORT NO.
EJPA-600/2-78_-047
. TITLE AND SUBlT?~LE " ~ "
Hyperfiltration for Renovation of Composite Waste-
water at Eight Textile Finishing Plants
3. RECIPIENT'S ACCESSION NO.
5. REPORT DATE
March 1978
6. PERFORMING ORGANIZATION CODE
. AUTHOR(S) ——
Craig A. Brandon, John J. Porter, and Donald K.
Todd*
8. PERFORMING ORGANIZATION REPORT NO.
. PERFORMING ORGANIZATION NAME AND ADDRESS
South Carolina Textile Manufacturers Association
Suite 1700, Bankers Trust Towers
Columbia, South Carolina 29201
10. PROGRAM ELEMENT NO.
1BB036; ROAP 21AZT/8
11. CONTRACT/GRANT NO.
Grant S802973
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 8/74-10/77
14. SPONSORING AGENCY CODE
EPA/600/13
15 SUPPLEMENTARY NOTES (*) All three authors are from Clemson University. IERL-RTP
project officer is Max Samfield, Mail Drop 62, 919/541-2547.
16. ABSTRACT The report giveg resuits of field evaluations of hyperfiltration at eight
plants as a way to renovate composite wastewaters from textile finishing plants. The
evaluations included performance assessment of different types of commercially
available membranes, reuse of both renovated water and waste concentrates, and
the treatability of wastewater concentrates by conventional means. On-site field
tests involved a mobile hyperfiltration laboratory. Both cellulose acetate and dyna-
mic membranes, when used with the manufacturers' recommended pretreatment,
proved feasible for wastewater renovation. When 90% of the feed was recovered, the
renovated water was satisfactory for reuse in scouring, bleaching, dyeing, and
finishing. Successful reuse of the residual concentrates, 10% of the feed, containing
significant quantities of dyes and chemicals, was not generally demonstrated. How-
ever, treatability of the residual concentrate by conventional waste treatment pro-
cesses produced effluent equivalent in quality to current composite plant discharges.
Preliminary operating costs are projected for full-scale systems utilizing cellulose
acetate membranes to treat composite wastewater. Savings may" be possible from
recycled process water, recovery of chemicals and dyestuffs, and use of recycled
water at, or near, operating temperature (instead of lower temperature fresh water).
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Pollution
Waste Water
Treatment
Textile Industry
Textile Processes
Filtration
Textile Finishing
Fluid Filters
Membranes
Cellulose Acetate
Scouring
Bleaching
Dyes
- ^ -^^^XJ-J.*-. J- .ftflfr-^j l*.«ja|j
'3. DISTRIBUTION STATEMENT
Unlimited
b.lDENTIFIERS/OPEN ENDED TERMS
Pollution Control
Stationary Sources
Hyperfiltration
Dynamic Membranes
COS AT I Field/Group
13B
14B
11E
13H
07D
13K
11G
111
07A
11C
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
243
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
237
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