EPA-600/2-77-169
September 1977
Environmental Protection Technology Series
                                 DEMORALIZATION  OF
          SAND-FILTERED SECONDARY EFFLUENT BY
        SPIRAL-WOUND REVERSE OSMOSIS PROCESS
                                 Municipal Environmental Research Laboratory
                                      Office of Research and Development
                                     U.S. Environmental Protection Agency
                                             Cincinnati, Ohio 45268

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                RESEARCH REPORTING SERIES

Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
gories were established to facilitate further development and application of en-
vironmental technology. 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 TECH-
NOLOGY series This series describes research performed to develop and dem-
onstrate instrumentation, equipment, and methodology to repair or prevent en-
vironmental degradation from point and non-point sources of pollution. This work
provides the new or improved technology required for the control and treatment
of pollution sources to meet environmental quality standards.
This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.

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                                        EPA-600/2-77-169
                                        September 1977
DEMORALIZATION OF SAND-FILTERED SECONDARY EFFLUENT

                         BY

        SPIRAL-WOUND REVERSE OSMOSIS PROCESS
                         by

                   Chi ng-1in Chen
                   Robert  P.  Miele

  County Sanitation Districts of  Los Angeles  County
             Whittier, California 90607~
              Contract No.  14-12-150
                   Project Officer

                  Irwi n 0. Kugelman
            Wastewater Research Division
     Municipal  Environmental  Research Laboratory
               Cincinnati, Ohio   45268
    MUNICIPAL ENVIRONMENTAL  RESEARCH  LABORATORY
        OFFICE OF RESEARCH AND  DEVELOPMENT
       U.S. ENVIRONMENTAL  PROTECTION  AGENCY
              CINCINNATI,  OHIO   45268

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                                   DISCLAIMER
     This report has been reviewed by the Municipal Environmental Research
Laboratory, U.S. Environmental Protection Agency, and approved for publica-
tion.  Approval does not signify that the contents necessarily reflect the
views and policies of the U.S. Environmental Protection Agency, nor does
mention of trade names or commercial products constitute endorsement or
recommendation for use.
                                    11

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                           FOREWORD
     The Environmental Protection Agency was created because of
increasing public and government concern about the dangers of pollution
to the health and welfare of the American people.   Noxious air, foul
water, and spoiled land are tragic testimony to the deterioration of
our natural environment.  The complexity of that environment and the
interplay between its components require a concentrated and integrated
attack on the problem.

     Research and development is that necessary first step in problem
solution and it involves defining the problem measuring its impact, and
searching for solutions.  The Municipal Environmental Research Laboratory
develops new and improved technology and systems for the hazardous water
pollutant discharges from municipal and community sources, for the pre-
servation  and treatment of public drinking water supplies, and to mini-
mize the adverse economic, social, health, and aesthetic effects of
pollution.  This publication is one of the products of that research;
a most vital communications link between the researcher and the user
community.

     One of the goals of wastewater treatment is renovation of waste-
water so that it can be reused.  It is expected that partial deminerali-
zation of conventionally treated wastewater will be required if the waste-
water is reused for any purpose which requires high quality water.
Among the techniques for demineralization that which is newest but shows
the most potential is reverse osmosis.   In this process water  is forced
through a membrane which can reject salts.  The permiability of these
membranes is low so high pressure  is required to achieve an economical
production rate.  Special configuration of the membrane and its support
system are required to withstand the high pressure  and maintain a high
ratio of membrane surface to system volume.   In the studies reported  in
here a reverse osmosis system using a spiral membrane-support  configura-
tion was tested for its efficacy in demineralization of secondary
effluent.
                                  Francis T.  Mayo, Director
                                  Municipal  Environmental  Research
                                   Laboratory

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                                   ABSTRACT


     A 22.7 cu m/day (6,000 gallons/day) spiral-wound reverse osmosis pilot
 ilant, was operated at the Pomona Advanced Wastewater Treatment Research
 :acility on the sand-filtered secondary effluent.  The pilot plant study
 (as conducted under optimum operating conditions based on previous studies.
 luring the first year of operation, all the system performance parameters,
 ;uch as salt rejection, water recovery, and product water flux rate, were
only slightly decreased from their initial values.  However, the salt
rejection and product water flux rate were substantially reduced to almost
half of their initial values after a two year operation period.  During this
same two year period, the water recovery was found to decline about 15 per cent
of its initial value.

     A cost estimate for a 37,850 cu m/day (10 MGD) plant for August, 1973
cost figures indicated that for membranes with only one-year life the process
cost was about 16.5(^/1,000 liters (63.6^/1,000 gallons).  However, the cost
could be substantially reduced to 12.4<£/1,000 liters (47.5^/1,000 gallons)
for membranes with two-year life.  Both cost estimates did not include the
costs for sand filtration pretreatment and brine disposal.

      This report was submitted in fulfillment of Contract No. 14-12-150 by
the County Sanitation Districts of Los Angeles County under the sponsorship
of the U.S. Environmental Protection Agency.  This report covers a period
from July 1971 to June 1973.
                                      IV

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                         CONTENTS
Foreword .....................    i i 1
Abstract .....................     "> y
Figures ......................     vi
Tables ......................    Y! ]
Acknowledgments ..................   vm
   1. Introduction ................     1
   2. Conclusions .................     3
   3. Recommendations ...............     5
   4. Pi lot Plant Description ...........     6
   5. Pilot Plant Operation ............    10
   6. Results and Discussions ...........    13
   7. Process Cost Estimate ............    33
References	     37

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                            FIGURES


Number

   1    Configuration  of spiral-wound membrane
          module
   2   Schematic flow diagram of the  reverse
          osmosis pilot  plant  	
   3   Salt rejection and feed pressure  variation
          vs.  operational time under constant
          flux rateoperation	     14

   4   Salt rejection and product water  flux variation
          vs.  operation time under constant
          operating pressure 	     20

   5   Monthly averages of the R.O.  pilot plant
          performance parameters  (corresponding to
          the period of 5900 to 17528 hours of
          operation)	     29
                              VI

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                            TABLES


Number                                                     pag<

   1    Evaluation of the Lead Module Membrane
          in Pressure Vessel  No.  1 at 4,450
          Hours  of Operation	     19

   2    Average Water Quality  Characteristics
          (October 15,  1971  to March 2,  1972)	     31

   3    Typical Ion Rejection  Values (%)  at
          Different Period of Operation	     32

   4    Process Cost Estimate  for  37,850
          Cu M/Day (10  MGD)  Spiral-Wound
          Reverse Osmosis  Plant  	     36
                              vn

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                         ACKNOWLEDGMENTS

    This study was jointly sponsored by the U.S.  Environmental
Protection Agency and the County Sanitation Districts of
Los Angeles County.

    Mr.  Harold H. Takenaka,  former U.S. EPA Project Engineer at
Pomona Advanced Wastewater Treatment Research Facility,  was  in-
strumental in initiating the pilot plant study.

    The  advice and suggestions given by Dr. James  E.  Cruver  of
Gulf Environmental Systems Company during the course  of  the
study were important contribitions to the success  of  the study.

    The  untiring efforts of  both the operating and laboratory
staff of the Pomona  Advanced Wastewater Treatment  Research
Facility are gratefully acknowledged.
                              vn

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                            SECTION 1

                          INTRODUCTION

     As part of the continuing development program for the
application of the reverse osmosis process to wastewater de-
mineralization, the Gulf Environmental  Systems Company con-
ducted a special  research study,  on a  short-term basis,  on the
effects of various pretreatrnent systems on the membrane  perform-
ance under the U.S. EPA Contract  No.  14-12-831.   The study was
mostly performed  at the Pomona Advanced Wastewater Treatment
Research Facility concurrently with other reverse osmosis pilot
plant studies.

     The Gulf Environmental  Systems Company concluded their pre-
treatment study on the contract expiration date of July  31,
1971.  They indicated in their contract final report that an
activated carbon  adsorption  pretreatment was clearly not neces-
sary for a successful reverse osmosis  system operation.'1)  In
the same report,  they further demonstrated that a sand filtra-
tion process could provide an equally  satisfactory pretreatment
for a reverse osmosis system operation.

     This study was initiated to  confirm the findings of the
Gulf Environmental Systems Company on  an extended long-term
basis, and also to achieve the following specific objectives:

     A.  To establish the effective life of the membrane of
a spiral-wound reverse osmosis system  in demineralizing  a
sand-filtered secondary effluent:

     B.  To determine the reliability  of the process perform-
ance ; and

     C.  To obtain the operating  and design data for making
a realistic process cost estimate.

     The study was conducted with the  same reverse osmosis pilot
plant previously  used by the Gulf Environmental  Systems  Company
in their pretreatment study.  The pilot plant was a  spiral-
wound membrane system and had a nominal production capacity of
22.7 cu m/day (6,000 gallons/day).  The pilot plant  had  accumu-
lated a total of 2,503 hours of on-stream operation  before the
Gulf Environmental Systems Company terminated their  study on
July 31, 1971.  This extension study had added another 15,025

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hours of operation to the pilot plant to  accomplish  a  total  of
17,528 hours (equivalent to a  two-year period)  of  on-stream
operation.   The study was formally completed  as  of June  11,
1973.

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                           SECTION-2

                          CONCLUSIONS

    The following conclusions can be drawn from the pilot plant
study:

    A.  The spiral-wound reverse osmosis system operated suc-
cessfully on the secondary effluent of Pomona Water Reclamation
Plant with only sand filtration pretreatment.  The effective
membrane life for the operation was approximately one year.

    B.  The pilot plant maintained 90 percent or more of salt
rejection, 326 1/sq m/day (8 gal/sq ft/day) or more of product
water flux, and 75 percent or more of water recovery under an
average operating pressure of 34.5 Kg/sq cm (500 psi) during
the first year of operation.

    C.  The product water flux rate decline was controlled by a
daily air-tap water flushing and a three-times-a-week chemical
cleaning.  Three types of cleaning solutions, namely, Biz
enzyme detergent, sodium perborate and sodium ethylenediaminete-
traacetate (EDTA), were found to perform equally well.  However,
as recommended by the membrane manufacturer at the middle of the
study, only EDTA cleaning solution was used for the membrane
cleaning during the second year of operation.

    D.  The water flux rate decline could be minimized by main-
taining a minimum brine flow of 15 1/min (4 gpm).

    E.  The water recovery could be enhanced by a partial re-
cycling of the brine to the feed stream.

    F.  The overall reductions in the salt rejection, water  re-
covery, and product water flux rate during the two years of  on-
stream operation were approximately 51 percent, 15 percent,  and
50 percent, respectively.

    G.  The product water quality prior to the start of serious
membrane deterioration was excellent.

    H.  The total process cost estimate for a 37,850 cu m/day
(10 M6D) plant is about 16.54/1,000 liters (63.64/1 ,000 gallons)
However, if the membrane effective life can be improved from one
year to two years, then the process cost can be substantially

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reduced to 12.44/1,000 liters (47. 5cVl ,000 gallons).   Both cost
estimates do not include the costs  for sand filtration pretreat-
ment and brine disposal.

    I.   A comparison of total process costs,  including pre treat-
ment costs,  between two different pretreatment schemes for the
spiral-wound reverse osmosis process indicates that the sand
filtration pretreatment scheme is somewhat less expensive than
the carbon adsorption pretreatment  scheme.

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                           SECTION 3

                        RECOMMENDATIONS

    The relatively short membrane life as concluded from this
pilot plant study on the wastewater demineralization is  rather
discouraging.   An optimum membrane life would  be three years,
if the process is to be practical and economical for the appli-
cation to the  wastewater demineralization.(2)   Therefore, it is
highly recommended that further studies be pursued  primarily in
the areas of membrane improvement.  Other parameters such as
pretreatment methods, membrane cleaning solution and frequency,
feed pressure, brine recirculation , membrane  module configura-
tion, and brine flow rate should  also be thoroughly evaluated
and investigated.

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                              SECTION  4


                       PILOT  PLANT  DESCRIPTIOI
      The 22.7 cu rn/day  (6,000 gpd) spiral-wound reverse osmosis
 pilot  plant consisted of four steel pressure vessels 3.0 m  (10
 ft)  long by 10 cm  (4 in) in diameter, each of which contained
 three  ROGA spira1-wound membrane modules.  Each module had  a
 5.6  sq m (60  sq ft) of  high flux membrane cast on D-601 sail-
 cloth  backinn, 1.1 mm (0.045 in) polypropylene Vexar brine
 spacers, and  melamine-treated tricot product water channels.
 The  average water  permeability coefficient value of the membrane
 modules was 2.5xlO"s g/sq cm/sec/atm.  Figure 1 shows the con-
 figuration of the  spiral-wound membrane module.  The total   mem-
 brane  area in the  pilot plant system was 67 sq m (720 sq ft).

      The schematic flow diagram of the 22.7 cu m/day (6,000 gpd)
 reverse osmosis pilot plant is shown in Figure 2.   The sand-
 filtered secondary effluent was chlorinated to provide 1  to 2
 mg/1  of residual  chlorine and acidified to pH close to 5 using
 sulfuric acid before being fed to the reverse osmosis system.
 The  pilot plant system was in a 2-1-1 array,  as shown in Figure
 2, to  maintain sufficient brine flow rates in the  downstream
 modules.

      The brine was partially recycled to maintain  an apparent
 water  recovery at  the level  of 75 to 80 percent.   This brine re-
 cycling slightly  increased the inorganic and  organic matters in
 the  feed and thus  might cause adverse effect  on membrane foul-
 ing.  A minimum brine flow of 15 1/min (4 gpm)  was  maintained
 during the  system operation  to avoid concentration  polarization
 of the membranes.

     An Apco back pressure unit was used to regulate the system
operating pressure. Sufficient sample valves  were  installed on
the pilot plant  system,  so that samples  from  the  raw feed  (sand-
filtered  secondary effluent),  blended feed (mixture  of sand-
 filtered  secondary effluent,  chlorine solution,  sulfuric  acid,
and recycled brine),  brine and product streams  could be taken
regularly.   Instrumentation  was  included to measure  the tem-
perature  and the  pressure  of  the blended feed,  brine,  and  prod-
uct streams.   A  proportional  chemical  feed pump was  used  to add

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                                 BACKING
                                 MATERIAL
                                               SEE DETAIL-A
                                                 PERMEATE
                                                   TUBE
     SPACER
                                                 GLUE
             MEMRANE
                         DETAIL-A
Figure I. Configuration of spiral-wound membrane module.

                             7

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CO
                                                         SECONDARY
                                                         EFFLUENT
             PUMP
                                      RECYCLED BRINE
             PRESSURE
              VESSEL I
             PRESSURE
              VESSEL 2
                                  PRESSURE
                                   VESSEL 3
PRESSURE
 VESSEL 4
            "I
                                                                     •

                                                                    1
WASTE
'BRINE
                  PRODUCT
                   WATER
     Figure 2. Schematic flow diagram of the reverse osmosis pilot plant.

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sulfuric acid to the blended feed stream for pH control.   The
pump rate was regulated by a pH controller.   An Advance  gas
chlorinator was employed for chlorine addition.

     The pilot plant system was designed and constructed  to  be
cleaned regularly without disassembly of manifolds.   A chemical
cleaning solution was made up in a cleaning  tank and was  then
circulated through the pilot plant by a centrifugal  booster  pump.
Enough valves were provided in the pilot plant system so  that
each pressure vessel could be cleaned individually or the system
could be cleaned as a series-para 11 el array.  Tap water  or air-
tap water mixture could be introduced for flushing just  ahead  of
the pressure vessel array during cleaning cycle or downtimes.

     The pressure sand filter used in the pretreatment system  was
a standard package designed by L.A.  Water Conditioning Company,
City of Industry, California.  The filter was 76.2 cm (30 in)  in
diameter and had about 45.7 cm (18 in) depth of sand.  The sand
bed with an effective size and a uniformity  coefficient  of
approximately 0.5 mm and 1.6, respectively,  was supported by a
layer of graded gravel.  The hydraulic loading rate of the sand
filter was maintained at 2 Ips/sq m  (3 gpm/sq ft).  The  filter
was normally backwashed once a day.

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                           SECTION 5


                     PILOT PLANT OPERATION
OPERATING CONDITIONS
    At the beginning of this study, the pilot plant was operated
at a constant product flux rate of 407 1/sq m/day (10 gal/sq
ft/day) to simulate the actual plant operation.   The operating
pressure was frequently adjusted to maintain such constant flux
rate operation.  The operating pressure was found to vary from
24.2 Kg/sq cm (350 psi) to 48.3 Kg/sq cm (700 psi) to produce a
407 1/sq m/day (10 gal/sq ft/day) flux rate during the first
5,900 hours of operation.  Due to the lack of an adequate control
mechanism to automatically make the necessary operating pressure
adjustment, the constant flux mode of operation  was converted to
a constant 34.5 Kg/sq cm (500 psi) operating pressure mode of
operation starting at 5,900 hours of on-stream operation.

    The initial performance parameters under the constant
operating pressure operation were as follows:

    A.  Product water flux rate (adjusted to 25°C) : 488 1/sq
        m/day (12 gal/sq ft/day).

    B.  Water recovery (defined as "100 x flow rate of product
        stream/flow rate of raw feed stream:) :  80 percent.

    C.  Salt rejection (defined as "100 x conductivity of
        product stream/conductivity of blended feed stream") :
        97 percent.

    The sand-filtered secondary effluent was chlorinated to
provide 1 to 2 mg/1 chlorine residual and acidified to a pH
close to 5 using sulfuric acid for biological growth and chemi-
cal precipitation controls, respectively.  The minimum brine
flow was regulated at 15 1/min (4 gpm) and the recycled brine
flow was maintained at 10 1/min (2.7 gpm).

MEMBRANE CLEANING PROCEDURES

    The reverse osmosis pilot plant operation was started out
with a daily tap-water flushing and a twice-a-week chemical
                               10

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solution cleaning cycle.   This membrane cleaning schedule was
practiced routinely throughout the first 2,500 hours  of on-
stream operation.  However,  it was found necessary to increase
the frequency of the chemical  solution cleaning to three times
a week to maintain the desired performance level.   This new
cleaning frequency was equivalent to a cleaning interval of  815
liters of product water per  square meter of membrane  surface
area (which was about 20  gallons per square foot of membrane
surface area).

     Three types of chemical  cleaning solutions--Biz  enzyme-
detergent, sodium perborate  and sodium ethylenediaminetetraace-
tate (EDTA)--were tested  during the first 7,900 hours of on-
stream ope r at ion.

     However, the Biz enzyme-detergent (contained  some small
amount of sodium perborate)  and the sodium perborate  solution
were subsequently found corrosive to the cellulose acetate mem-
brane according to Cruver'3)  of the Gulf Environmental Systems
Company.

     Consequently, only the  EDTA cleaning solution was used  as
the cleaning agent for the membranes throughout the rest of  the
pilot plant operation.  The  concentrations and constituents  of
the various cleaning solutions used were as follows:

     A.  Biz enzyme-detergent solution:

     a.  2"'. of Biz enzyme-detergent

     B.  Sodium perborate solution:

     a.  2% of sodium perborate
     b.  0.15% of Triton  X-100 (non-ionic detergent)
     c.  0.0015% of carboxy  methyl cellulose

     C.  EDTA solution:

     a.  l/o of EDTA (tetra sodium salt)
     b.  0.15% of Triton  X-l00
     c.  0.0015% of carboxyl  methyl cellulose

     The pH of all the cleaning solutions was adjusted  to 7.5 to
8-0 to minimize the membrane hydrolysis reaction.   The  cleaning
solutions were prepared with warm tap water (40°C to 60°C)  to im-
prove the cleaning efficiency.

     The chemical cleaning solution was first flushed  through all
the reverse osmosis pressure vessels for five minutes,  then the
solution was flushed  through each individual  pressure  vessel  for
10 minutes, and  finally the solution was flushed  through the
                               11

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entire system again for another five minutes.   Therefore, the
total flushing time for the pilot plant was about 50 minutes.
The flushing rate for the cleaning solution was regulated at the
level of 37.9 1/min (10 g p m) .   After the chemical solution clean-
ing cycle, the system was thoroughly rinsed with tap water in the
same procedure as the chemical  cleaning solution.  Therefore, the
downtime required for daily membrane cleaning  ranged from 50 to
100 minutes depending on whether the chemical  cleaning was prac-
ticed along with the daily tap-water flushing  or not.

SAMPLING AND MONITORING PROCEDURES

     During the week days (Monday through Friday), the following
operating parameters were monitored routinely:

     A.   The conductivities of the feed, product, and brine
streams  of each pressure vessel .

     B.   The rate of product  flow from each pressure vessel.

     C.   The pressure difference through each  pressure vessel.

     Daily (including Saturday and Sunday) measurements were per-
formed on the following parameters:

     A.   The temperature of the blended feed water.

     B.   The pH values of the blended feed and  brine streams.

     C.   The chlorine residual  of the blended  feed streams.

     D.   The total  pressure difference through  the pilot plant
system.

     E.   The total  product flow before and after the membrane
cleaning.

     F.   The conductivities of the blended feed and the final
product  streams.

     G.   The total  and recycled brine flows.

     H.   The feed operating pressure.

     I.   The total  on-stream  operation time.

     Besides the above routine daily monitoring procedures, some
grab samples from the raw feed, blended feed,  product and brine
streams  were also taken every Thursday at 8:00  A.M. for water
quality  analyses.
                               12

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                            SECTION 6

                     RESULTS AND DISCUSSIONS
CONSTANT PRODUCT FLUX OPERATION

     Figure 3 shows the variations  of the salt rejection and the
feed pressure during the first 5,900 hours  of on-stream operation
The product flux was maintained at  a constant rate of 407 1/sq
m/day (10 gal/sq ft/day) during the first 5,900 hours of opera-
tion.  As indicated in Figure 3,  the feed pressure required to
maintain the above constant product flux rate was approximately
31.7 Kg/sq cm (460 psi) during the  first 1,000 hours of opera-
tion.  However,  the required feed pressure  rapidly increased to
as high as 47.6  Kg/sq cm (690 psi)  during the next 400 hours of
operation.  Because of this high  feed pressure development, the
system was depressurized for a 72 hour period after 1,430 hours
of operation.  During the depressurization  period, a constant
tap water flushing through the system was maintained.  After
this depressurization treatment,  the feed pressure was reduced
to the previous  level of 31.7 Kg/sq cm (460 psi) to maintain the
407 1/sq m/day (10 gal/sq ft/day) product flux.  The pressure
remained at about 27.6 to 34.5 Kg/sq cm (400 to 500 psi) until
2,200 hours of operation.

     Between 2,200 to 3,600 hours of operation, the system re-
quired 31.1 to 38.0 Kg/sq cm (450 to 550 psi) to maintain the
constant flux of 407 1/sq m/day (10 gal/sq  ft/day).  Then it
became necessary to gradually increase the  feed pressure to as
high as 48.3 Kg/sq cm (700 psi).   Two 24 hour and two 72 hour
depressurization periods on tap water between 3,600 and 4,450
hours of operation were not successful in reducing the feed
pressure to the  initial operating level.

     At the 3,844 hours of operation, the membrane modules were
inspected.  Several brine seals were "blown," so they were re-
taped in place.   The "blown" brine  seals probably resulted from
the high operating feed pressure.  At 4,000 hours of operation,
the membrane modules were again inspected.   The inspection
showed that the  modules were very clean with the barber-pole
type outer wrap  tape and the brine  seals were in excellent con-
dition.  However, the condition of  the brine channels could not
                                13

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                                                 • •
                                             • • •   •   •
                                .•.
                                          ••
                                                                       ..
         SS    SS    SS    SS    SS     SSSS

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                                                                         SE     EE    BBB
               200
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                                                                       1200
                                                      1400
                                                 1600
Figure 3. Salt rejection and  feed pressure variation vs. operational time under constant flux
          rate operation.

-------
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Figure 3. Continued.

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Figure  3. Continued.

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  UJ
  OC
  CL

  O
  UJ 400
  UJ
  u.
400 PSI  FEED
 PRESSURE
                                 450 PSI  FEED PRESSURE
        B B
   BBB   SSS   SSS   SSS    SSS    SSS
                               _L
                                 I
      4800
      5000
5200        5400

    HOURS ON STREAM
                                                       5600
                                                       5600
                                                                                6000
Figure 3. Continued.

-------
be determined without opening the modules.  The reason for the
high feed pressure required to maintain 407 1/sq m/day (10
gal/sq ft/day) product flux was not readily apparent.

     After the 72 hour depressurization at 4,450 hours of opera-
tion, it was decided to operate the system at 27.6 Kg/sq cm
(400 psi) feed pressure for a month period in an attempt to im-
prove the "A" (water permeability coefficient) value.   At this
time, the lead module in the pressure  vessel  No. 1 was replaced
with a new module.  The old module was sent to the Gulf
Environmental System Company for membrane evaluations.  The re-
sults are shown  in Table 1.

     During the  month long period of constant 27.6 Kg/sq cm (400
psi) feed pressure operation, the product water flux rate (at
25°C) increased  from about 305 to 366  1/sq m/day (7.5  to 9
gal/sq ft/day) which was an encouraging trend.  The constant
feed pressure was subsequently increased to 31.1 Kg/sq cm (450
psi) for another month of trial operation.  The product water
flux rate was improved from 366 to 448 1/sq m/day (9 to 11
gal/sq ft/day) as a result of this feed pressure increase.
Therefore, the system operation was converted from a constant
product flux rate operation to a constant feed pressure opera-
tion after 5,900 hours of on-stream operation.

CONSTANT FEED PRESSURE OPERATION

     At all times after 5,900 hours of operation, the  reverse
osmosis pilot plant system was operated at a  constant  34.5
Kg/sq cm (500 psi) feed pressure.  The variation of the salt re-
jection and the  product water flux rate throughout this series
of constant feed pressure operation are shown in Figure 4.  As
indicated in this figure, the initial  product water flux rate
was about 448 1/sq m/day (11 gal/sq ft/day).   However, the flux
rate started to  decline at about 7,000 hours  of operation.

     At 7,266 hours of operation, the  No. 2 pressure vessel was
inspected because its salt rejection was about 3 percent lower
than the other three vessels.  The inspection showed that two of
the three modules had experienced "blown" brine seals.  The
three modules looked relatively clean  and the outer wrap tapes
were in excellent condition.  The blown brine seals were retaped
in place and the system was put back in operation.  Experience
at Pomona had shown that the barber-pole type of outer wrap tape
could successfully maintain module integrity  when used in treat-
ing municipal wastewater.

     As shown in Figure 4, there was a sudden decrease in prod-
uct water flux rate at 7,445 hours of  operation.  This might be
the result of excessive membrane fouling due  to the poor
                               18

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                                    TABLE 1

              EVALUATION OF THE LEAD MODULE  MEMBRANE IN PRESSURE

                   VESSEL NO.  1 AT 4,450 HOURS OF OPERATION
Feed Solution
and
Membrane Condition
2,000 mg/1 NaCl Solution
Before Membrane Cleaning
Feed
Press ure
(psi)
415
"A" Value Salt Rejection
(g/cm2/sec/atm) %
1.25X.O-5 93.4
2,000 mg/1  NaCl  Solution         420          1.81X10'5               94.3
After Membrane  Cleaning


Notes:  1.  The  membrane  was  cleaned with an  enzyme-detergent  (Biz)  at  60°C
          with  pH  adjusted  to  7.

       2.  The  module  was  opened after the  tests,  and  there was  a  brownish
          film  on  the membrane with very little,  if  any,seal ing  evidence.

       3.  1  psi  =  0.069  Kg/sq  cm.

-------
   100
_                I

Q

                   •                ••
                 •  •i


                         ~~       ^               —           '~"~*~~****~~W^           •  _ • w
                       •
o
LU
UJ
cr


5
<
    90h                B-BIZ FLUSH
                      ~~»-72HR. TAPWATER
    12
O
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lO
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X
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cc
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••        •  *•••«•
 •• •      . *   *      • -       • _ _       ..              •.
                      E-EDTA FLUSH

                      S- SODIUM PERBORATE FLUSH
                       I-GFD = 40.7 l/sqm/day
                                                                                              •  •
            ss   sss   ssssss    sss   sss    sss   sss   sssss


                  I            I      	I	I	I	I	I
    5800        6000        6200        6400        6600        6800        7000        7200        7400

                                            HOURS ON STREAM



  Figure 4. Salt rejection and product water flux variation vs. operation time  under constant

            operating  pressure.

-------
       100
    UJ
    
-------
       100
    o
    UJ
    —>
    UJ
    (T
    <
    CO
       90
        80 •
    O
    o
    IO
    CM
PO   Q
     -  10
    X.
    a:
    UJ


    I
    8

    8
    IT
    O.
              E  E  E    E   E
                       I
              EEE    EEE    EEEEE


               I	I	i	
                                                           '   t
                            EEE   EEEE   E   E.EE    E
        900O
9200
                                  9400
9600         9800


     HOURS ON STREAM
lopoo
10,200
10,400
10,600
       Figure  4. Continued.

-------
ro
oo
         100
     o
     UJ

     UJ
     o:

     |3  90
     <
         80
     O
     o
     IO
     CVJ
a
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°.  .0
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-------
   100
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o
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    90 •
    80
O
e

IO
CM
O

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s
cr
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       E  E
 • •• •

EEE
        •  E E

        E
EEE   EEE   EEE    EEE    EEE    EEE    EEE    E
   12,200
12,400
              12,600
       12,800         13,000        13,200


             HOURS ON STREAM
13,400
13,600     13,800
  Figure 4.  Continued.

-------
ro
en
         90
     g

     o
     UJ

     UJ
         80
         70
     o
     o
     \f>
     CM
O


*   .0
X
     cc
     UJ
     O
           EE    EEE    EEE    EEE
 6
13,800
                                            EEE   EEE    EEE    EEE    EEE



                                           _J _ I - 1 - 1
                                                                                                    EEE   EE
                      14,000
                             14,200
I4.4OO         14,600


     HOURS ON  STREAM
                                                                          14,800
                                                                                 15,000
I5.20O      15,400
       Figure 4. Continued.

-------
   80
O
UJ
->
UJ
cr
CO
    60 -
O
O
m
W
o
u.

®  10
X
oc.
IU

I
O


O
O
                                                                    •  •
                                                                                •        •                •
                                                                                1  -              -.   •
             EEE    EEE    EEE    EEE    EEE   EEE
                                                                  EEE    E  £• •    E.EE
                               _L
                                             I
                                                                       I
    15,400
15,600
15,800
16,000        16,200        16,400


     HOURS ON STREAM
                                                                                  16,600
                                                                  16,800
                                                                                         17,000
  Figure  4. Continued.

-------
IV)
        70
    O
    UJ

    UJ
    cc
    <
    U)
        60
        50
    O
    o
    10
    CM
        8

    X
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    UJ


    I
    O

    O
    o
    cr
    a.
EEE    EEE    EEE
       17,000
        17.2OO
17,400
17,600         17,800


    HOURS ON STREAM
18,000
18,200
18,400     18,600
     Figure  4. Continued.

-------
secondary effluent quality.  The turbidity and the dissolved
chemical oxygen demand (DCOD) of the sand-filtered secondary
effluent were as high as 22 JTU and 76 mg/1,  respectively, dur-
ing the two week activated sludge plant upset period between
7,421 and 7,737 hours of pilot plant operation.   In spite of the
poor quality secondary effluent, the module cleaning, using so-
dium perborate solution, was able to maintain the product water
flux rate between 265 to 366 1/sq m/day (6.5  to  9 gal/sq ft/day).

     At 8,096 hours of operation, the membrane modules in the
system were inspected again.  The results  of  the inspection
showed that feed ends of the lead modules  in  pressure vessels
No. 1 and No. 2 were covered with suspended solids and other de-
bris, which were easily removed by applying a high pressure
stream of tap water.  No serious scaling to the  extent of caus-
ing a severe restriction of the brine flow was found.  The brine
seals and the outer wrap tape were in good condition.  A 72 hour
depressurization on chlorinated tap water  allowing the module
inspection was able to improve the product water flux rate
si i gh11y.

     As indicated in Figure 4, the salt rejection maintained at
95 percent or more for the first 7,400 hours  of  on-stream opera-
tion.  Since then, the salt rejection gradually  decreased to
about 90 percent at 9,000 hours of operation.  Similarly, the
product water flux rate was maintained at  407 1/sq m/day (10
gal/sq ft/day) or higher practically throughout  the first 7,400
hours of operation, and then it decreased  to  about 326 1/sq
m/day (8 gal/sq ft/day) at 9,000 hours of  operation.   This
amounted to a 6 percent reduction in salt  rejection and a 20
percent reduction in product water flux rate  during the first
year pilot plant operation.

     The salt rejection was maintained at  the level of 90 per-
cent between 9,000 and 10,600 hours of operation.  However, the
product water flux rate was found to decrease from the level of
326 1/sq m/day (8 gal/sq ft/day) to the level of 285 1/sq m/day
(7 gal/sq  ft/day)  during the same operation period.

     During the period between 10,600 and  12,600 hours of opera-
tion, the  product water flux rate was found to hold steady at
the level  of 285 1/sq m/day (7 gal/sq ft/day) while the salt re-
jection was found  to decrease rapidly from 90 percent to 80 per-
cent .

     The product water flux rate started to reverse its down-trend
at 12,600  hours of operation (in the month of November, 1972),
as shown in Figure 5.  This up-trend continued for a period of
3,200 hours, and it was finally decreased  again  at 15,800 hours
of operation.
                               28

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  100
                                                           WATER RECOVERY
                                                           PRODUCT WATER  FLUX
        I GFD = 40.7 l/sq m/doy
    /    /    ,
    /72   /72   /72
                                         MONTH/YEAR
Figure 5. Monthly averages of the R.O. pilot plant performance parameters (corresponding to the
         period of 5900 to 17528 hours of operation).

-------
     The phenomenon of the product water flux rate reversal
could very well indicate that some physical destructions of  the
membrane structure had taken place inside the membrane modules.
The damaged membranes could lose the ability to function.   Con-
sequently, some brine water would be able to flow through  the
membrane and contaminate the product water, thus causing a poor
salt rejection.  After 15,800 hours of operation (corresponding
to the month of March, 1973), the salt rejection, product  water
flux rate, and the water recovery were all  found to decrease
rapidly, as shown in Figure 5.   The pilot plant was finally
terminated on June 11, 1973, after a total  of 17,528 hours of
on-stream operation.   The total  reduction in salt rejection,
water recovery, and product water flux rate during the two
years of on-stream operation period were approximately 51  per-
cent, 15 percent, and 50 percent, respectively.

WATER QUALITY CHARACTERISTICS

     The typical  water quality  characteristics of the sand-
filtered secondary effluent, which was used as the raw feed  to
the reverse osmosis pilot plant  study, are  shown in Table  2.
The concentration of the nitrate ion in the raw feed was so  low
that the 30 percent rejection,  as indicated in Table 2, might
not demonstrate the true rejection capability of the reverse
osmosis system.  It is also shown in Table  2 that both organic
matter and turbidity were quite  effectively removed.  However,
those high rejection values during the initial period of opera-
tion were found to decrease rapidly after approximately 9,000
hours of on-stream operation.
     Table 3 shows the typical  ion rejection values at t
different periods of operation.  As indicated in Table 3, :.
chloride and nitrate rejections dropped to zero after about
two years of operation.
                               30

-------
                            TABLE 2

             AVERAGE WATER QUALITY CHARACTERISTICS

               (October 15, 1971 to March 2, 1972)
Analysi s
Na
K
Ca
Mg
Cl
so,
P04-P
NH3-n
N03-N
TCOD
DCOD
TDS
Turbidity
(JTU)
Raw F
(mg/
94.
12.
57.
11.
80.
65.
10.
18.
0.
31 .
25.
496

2.
eed
1)
5
0
2
4
6
0
3
6
09
7
1


1
Bl ended
Feed
(mg/1)
175
21
103
21
155
534
19
33
0
57
50
1 ,127

3
.0
.9
.9
.8
.4
.0
.8
.1
.10
.1
.0


.3
Product
(mg/1)
13.
1 .
0.
0.
18.
4.
0.
1 .
0.
0.
0.
52

0.
8
4
94
34
9
9
26
8
07
95
56


03
Bri ne
(mg/1)
323
41
211
41
301
1 ,038
37
63
0
99
85
2,099

8
.0
.2
.3
.8
.0

.5
.6
.16
.8
.8


.0
Rejecti on
U)
92
94
99
98
88
99
99
95
30
98
99
95

99
Notes:  1.  Raw Feed is sand-filtered secondary effluent.

       2.  Analysis on once a week grab samples taken at
          8:00 A.M.

       3.  Difference between raw feed and blended feed is
          due to HjSO^ addition, chlorination and brine
          reci rculat ion .
                                31

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              TABLE 3




TYPICAL ION REJECTION VALUES (:;) AT




   DIFFERENT PERIOD OF OPERATION

Ion —
Sodi urn
Potassi urn
Ammonia Nitrogen
Cal ci um
Magnes i um
Chi ori de
Nitrate Nitrogen
Sulfate
Phosphate
Total COD
Dissolved COD
TDS
Appro
6,500
90
94
95
99
98
84
30
99
98
99
99
95
ximate Hours
12,000
72
80
75
90
85
33
13
88
85
85
86
79
on Stream
17,500
43
38
39
40
48
0
0
47
33
48
37
41
                 32

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                            SECTION 7

                      PROCESS COST ESTIMATE


     The pilot plant studies at Pomona Research Facility have
successfully demonstrated the technical  feasibility of apply-
ing the spiral-wound reverse osnosis  system to the deminerali-
zation of the sand-filtered secondary effluent.  A process  cost
estimate for this application is prepared on the basis of the
pilot plant operation results.   The major assumptions made  for
this cost estimate are listed as follows:

     A.  The blended influent TDS for  the  reverse osmosis
        system is about  1200 mg/1;

     B.  The water recovery  for  the  process  is  about  80
        percent;

     C.  The product water flux  rate is approximately  407
        1/sq m/day (10 gal/sq  ft/day)  at  25°C;

     D.  The process is capable  of rejecting  90  or  more
        percent of the influent  TDS;

     E   One percent EDTA  solution is  used as the membrane
        cleaning  solution,  with  pH  of  the solution ad-
        justed to 7.5  to  8.0 wijh sulfuric acid  at a
        temperature of 40 to  60  C;

     F.  The  membrane  cleaning is performed three times a
        week,  or  at an interval  of  815 liters of product
        water  per square  meter of membrane area  (20 gallons
        per  square  foot of  membrane area);
    G. The membrane life  is one year;

    H. The capital cost is amortized for 20 years at 5 per-
       cent interest rate; and

    I. The estimate is based on August, 1973 material  and
       construction costs.
                              33

-------
      The  initial  capital  cost  including  the  feed  pumps,  mem-
 branes,  pH  controllers,  chlorinators,  chemical  feed  pumps,
 booster  pumps,  brine  recirculation  pumps,  and  a  post  treatment
 system  for  final  pH adjustment  is about  3.66 million  dollars  for
 a  37,850  cu  m/day  (10  MGD)  spiral-wound  reverse  osmosis  plant.
 The  membrane  cost  alone  is  about  1.15  million  dollars.

      Since  the  membrane  has  only  one year  of useful  life, the
 membrane  replacement cost  is  estimated to  be about 8.24/1,000
 liters  (31.54/1,000 gallons).   However,  if the membrane  life  can
 be improved  to  two years,  then  the  membrane  replacement  cost  can
 be substantially reduced  to  4.04/1,000 liters  (15.44/1,000
 gal 1ons ).

      The  annual maintenance  material cost  is based on 5  per-
 cent  of  the  capital cost,  excluding the  cost of membranes.  The
 labor requirements include:

      A. One  man-hour per  cleaning schedule for a  378.5 cu
        m/day  (0.1 MGD) section of  the plant with a  labor
        rate of $10,000 per  year; and

      B. Three man-years for  operating the 37,850  cu m/day
         (10  MGD) plant at  the same  labor rate of  $10,000
        per year.

      The  total  power cost  (14/kwh)  for the 37,850 cu m/day (10
 MGD)  plant operation is estimated to be  about 2.04/1,000 liters
 (7.84/1,000  gallons).   The unit costs for the various chemicals
 used  in the  reverse osmosis  process  are  estimated as follows:

      A. EDTA =  $1.21/Kg ($0.55/lb);

      B. Triton  X-100 non-ionic detergent = $0.84/Kg ($0.38/lb);

      C. Carboxy methyl  cellulose -  $0.97/Kg ($0.44/lb);

      D. Sulfuric acid  » $0.04/Kg ($0.02/lb);  and

      E. Chlorine = $0.09/Kg  ($0.040/lb).

     According to the  above chemical costs, the total expenses
 for the process operation will amount to  2.444/1,000 liters
 (9.14/1,000 gallons).   This total chemical  cost can be broken
down into the following three different categories:,

     A.  Membrane cleaning - 1.54/1,000 liters (5.64/1,000
        ga11ons ) ;
                               34

-------
     B.  Acidification for chemical  precipitation control  -
         0.8^/1,000 liters (3.0c/l,000 gallons); and

     C.  Chlori nation for biological growth control  =
         O.U/1,000 liters (0.5c/l,000 gallons).

     Table 4 summarizes the various  items of the process cost
estimates.  As indicated in Table 4, the total  process cost is
approximately 1 6.6C/1,000 1iters (63.6/1,000 gallons) for one
year membrane life.  The cost can be reduced to about 12.4c/
1,000 liters (47.5^/1,000 gallons) by improving the  membrane
life to two years.  Both cost estimates do not  include the costs
for the sand filtration pretreatment  and the brine disposal.

     This pilot plant study has shown that the  secondary efflu-
ent from an activated sludge plant can be successfully de-
mineralized by a spiral-wound reverse osmosis process with only
sand fi 1 tration pretreatment, instead of the carbon  adsorption
pretreatment. ('*)  The difference in  the total  process costs, in-
cluding the pretreatment costs, between the sand filtration
(IcVl.OOO liters or 4
-------
                            TABLE 4

PROCESS COST ESTIMATE FOR 37,850 CU M/DAY (10 MGD) SPIRAL-WOUND

                     REVERSE OSMOSIS PLANT


Amortization of Capital       c/1 .000 gallons    c/1 ,000 1iters

  $3.66 X 10G;
  20 years @ 5%                     8.8               2.3

Operation and Maintenance

  Chemicals (H2S04, C12
  and cleaning  agent)               9.1               2.4

  Membrane Replacement

   One-year membrane life          31.5               8.2

   Two-year membrane life          15.4               4.0

  MaintenanceMaterials              3.4               0.9

  Power                             7.8               2.0

  Labor                             3.0               0.8

Total Process Cost:
  One-year membrane life           63.6              16.6

  Two-year membrane life           47.5              12.4
                              36

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                           REFERENCES
1.  Cruver,  James  E.,  Beckman,  James  E.,  and Bevege,  Eleanor,
   "Water Renovation  of Municipal  Effluents by Reverse
   Osmosis."   Final  Report to  the  Office of Research and
   Monitoring, Environmental  Protection  Agency.   Project
   #EPA 17040 EOR Contract #14-12-831  (February,  1972).

2.  Dryden,  Franklin  D., "Mineral  Removal by Ion  Exchange,
   Reverse  Osmosis,  and Electrodialysis. "  Presented at
   workshop on Wastewater Reclamation  and Reuse,
   South Lake Tahoe,  California (June,  1970).

3.  Cruver,  James  E.,  Gulf Environmental  Systems  Company,
   San Diego, California.  Private communication.

4.  Chen, Ching-lin and Miele,  Robert P., "Demineralization
   of Carbon-treated  Secondary Effluent  by Spiral-Wound
   Reverse  Osmosis Process."   Final  Report to  the Office
   of Research and Development, U.S. Environmental Protection
   Agency.   Contract  No. 14-12-150.
                              37

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                                   TECHNICAL REPORT DATA
                                read Infirm lions on the rci inr hclnri- t ii>/if!ftint;
                                                           13. RECIPI ENT'S ACCE SSI Of* NO.
  EPA-600/2-77-169
 •1 II i Li. AIMU SDH 1 I I Lt
 Demineralization of Sand-Filtered  Secondary Effluent
 by  Spiral-Wound Reverse Osmosis Process
  All I HOXi;,)
  Ching-lin Chen and Robert P. Miele
 LJ PLHI UHMING ORGANIZATION NAMt AND ADDRESS
 County  Sanitation Districts of Los Angeles  County
 Whittier,  California  90607
             5 REPORT DATE
              September 1977( Issuinq  Date]
             6. PERFORMING ORGANIZATION CODE
                                                           !. PERFORMING ORGANIZATION REPORT NO
                                                           1O. °ROGRAM ELEMENT NO.
              IBC611
             '11. CONTRACT GRANT NO.
                                                            14-12-150
   SPONSORING AGS NCY NAME ANO ADDRtSS
  Municipal  Environmental Research Laboratory--Cin.
  Office  of  Research & Development
  U.S.  Environmental Protection Agency
  Cinti,  OH    45268
              13. TYPE OF REPORT AND PERIOD COVERED
         0H   I	£1 n aj  Report  7/71-6/73	
              14. SPONSORING AGENCY CODE
               EPA/600/14
 15. SUPPl t Ml N I AHY NOTES
   Project Officer:  Irwin J. Kugelman  (513-684-7631)
 16. ABSTRACT
            A 22.7 cu m/day (6,000 gallons/day)  spiral-wound reverse osmosis  pilot
  plant,  was operated at the Pomona Advanced  Wastewater Treatment Research Facility
  on  the  sand-filtered secondary effluent.  The  pilot plant study was conducted  under
  optimum operating conditions based on  previous  studies.   During the first year of
  operation, all  the system performance  parameters,  such as salt rejection, water
  recovery,  and product water flux rate, were only  slightly decreased from their
  initial  values.   However, the salt rejection and  product water flux rate were
  substantially reduced to almost half of  their  initial values after a two year
  operation  period.  During this same two  year period,  the water recovery was  found
  to  decline about 15 per cent of its initial  value.
          A cost  estimate for a 37,850  cu m/day  (10  MGD)  plant for August,1973  cost
  figures  indicated that for membranes with onjy  one-year life the process cost  was
  about  16.5471,000 liters (63.5<£/1000 gallons").  However, the cost could be  sub-
  stantially reduced to 12.4<£/1,000 liters (47.5c/l,000 gallons) for membranes with
  two-year life.   Both cost estimates did  not include the costs for sand filtration
  pretreatment and brine disposal.
                               KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
 Demineralizing
 Desalting
 Filtration
 Water  Reclemation
b.IDENTIFIERS-OPEN ENDED TERMS

 Membrane Fouling
 Reverse Osmosis
COSATI Held/Group


   13B
 8. LJIL; rmuunoN STATEMENT

  Release  to  Public
19 SECURITY CLASS r This Report i
   Unclassified
                                                                        21 NO. OF PAGES
     46
                                             20 SECURITY CLASS / This
                                                 Unclassified
                                                                        22. PRICE
EPA Form 2220-1 (9-73)
                                            38
                       US GOVtOrtMIPHIBIIIICOfflCE 1977- 7S7-OS6/6S14

-------