WATER POLLUTION CONTROL RESEARCH SERIES
12060EHU03/71
Reconditioning
of
Food Processing Brines
ENVIRONMENTAL PROTECTION AGENCY • WATER QUALITY OFFICE
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WATER POLLUTION CONTROL RESEARCH SERIES
The Water Pollution Control Research Series describes the
results and progress in the control and abatement of pollu-
tion of our Nation's waters. They provide a central source
of information on the research, development, and demon-
stration activities of the Water Quality Office, Environ-
mental Protection Agency, through inhouse research and grants
and contracts with Federal, State, and local agencies, re-
search institutions, and industrial organizations.
Inquiries pertaining to the Water Pollution Control Research
Reports should be directed to the Head, Project Reports
System, Office of Research and Development, Water Quality
Office, Environmental Protection Agency, Washington, B.C. 20242,
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Reconditioning of Food Processing Brines
by
National Canners Association
Research Foundation
Western Research Laboratory
Berkeley, California 94710
for the
WATER QUALITY OFFICE
ENVIRONMENTAL PROTECTION AGENCY
Program # 12060 EHU
Grant # WPRD - 134 - 01 - 68
March, 1971
For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, D.C. 20402 - Price 75 cents
Stock Number 5501-0092
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EPA Review Notice
This report has been reviewed by the Water Quality Office,
EPA, and approved for publication. Approval does not signi-
fy that the contents necessarily reflect the views and poli-
cies of the Environmental Protection Agency, nor does mention
of trade names or commercial products constitute endorsement
or recommendation for use.
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ABSTRACT
Storage brines and processing waters from the production of canned
ripe olives and glass packed green olives were treated with activated
carbon. The reuse potential of reconditioned brines was evaluated.
Reconditioned storage brines can be used to store freshly harvested
olives for commercially significant periods. Canned samples pre-
pared from olives stored in reconditioned brine were of good quality.
Reconditioned brines of lower salt content were reused with no de-
tectable effect on the quality of the final product.
Estimates for commercial application of activated carbon treatment
of storage brines show a cost per ton of olives stored of $3.64 when
capital costs are amortized over 10 years for a cannery storing
5, 000 tons of olives annually. This value can also be expressed as
a cost of $36 .40 for each 1, 000 gallons of reconditioned brine pro-
duced. Ten olive canneries reconditioning brine and sending spent.
carbon to a centrally located reactivation facility would have a cost
of $1.28 per ton of olives stored or $12. 80 for each 1, 000 gallons of
reconditioned brine produced.
This report was submitted in fulfillment of Grant 12060 EHU under
the partial sponsorship of the Federal Water Quality Administration.
Key Words: Olive brines, brines, canneries, brine disposal, acti-
vated carbon, reclaimed water, industrial waste,
waste treatment.
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CONTENTS
Section Page
I Conclusions 1
II Recommendations 3
III Introduction 5
IV Design Phase 11
V Construction Phase 13
VI Operational and Evaluation Phase 19
VII Discussion 41
VIII Acknowledgments 53
IX References 55
X Patents and Publications 57
XI Appendices 59
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FIGURES
PAGE
1 SCHEMATIC DRAWING OF BRINE
RECONDITIONING UNIT 15
2 OVERALL VIEW OF BRINE RECON-
DITIONING UNIT 16
3 LOWER PORTION OF BRINE RECON-
DITIONING UNIT WITH ACCESSORY
COMPONENTS IN BACKGROUND 17
4 CARBON SLURRY TANK AND BLOW CASE 1?
5 PLOT OF ABSORPTION SPECTRA OF
OLIVE BRINE SAMPLES 23
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TABLES
No. Page
I Problem Areas Investigated During Operation
of Brine Reconditioning Unit at Four Locations 19
II Observations and Analytical Results for Treat-
ment of High Salt Content Storage Brine with
Activated Carbon 24
III Observations and Analytical Results for Treat-
ment of Low Salt Content Storage Brine with
Activated Carbon 25
IV Observations and Analytical Results for Treat-
ment of Storage Brine for Storage Experiments 26
V Observations and Analytical Results for Treat-
ment of Salt-Free Storage Brine with Activated
Carbon 26
VI Observations and Analytical Results for Treat-
ment of Storage Brine with Activated Carbon
Conditioned with Salt-Free Storage Brine 27
VII Observations and Analytical Results for Treat-
ment of Storage Brine During Extended Periods
of Continuous Operation 28
VIII Activated Carbon Treatment of Brine Used to
Store Imported Green Olives 29
IX Reconditioning of Strong Lye Rinse Water
with Activated Carbon 30
X Treatment of Processing Water with Activated
Carbon 31
XI Activated Carbon Treatment of Transport Brine 31
XII Observations on Regeneration of Spent Carbon
from the Brine Reconditioning Unit 33
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TABLES (Cont'd.)
No.
XIII
XIV
XV
XVI
XVII
XVIII
XIX
XX
XXI
XXII
XXIH
XXIV
XXV
XXVI
Analytical Results on Regenerated Carbon
Activated Carbon Treatment of Storage
Brine Using Carbon Water Washed Before
Furnace Reactivation
Activated Carbon Treatment of Storage
Brine Using Carbon Unwashed Before
Furnace Reactivation
Comparison of Efficiencies of Various
Types of Carbon in Reconditioning
Storage Brine
Analysis of Activated Carbon After Second
Furnace Reactivation Cycle
Small Scale Olive Storage Experiments
Flavor Ranking of Canned Ripe Olives
Basis of Calculation of Carbon Column
Size, Carbon Inventory and Carbon Re-
generation Requirements
Analysis of Samples Collected at
Sampling Ports - Lindsay
Measurement of Suspended Solids
Measurement of Light Transmission
at 450 Nanometer Wavelength
Analysis of Samples Collected at
Sampling Ports - Madera
Salometer Readings on Experimental
Olive Storage Brines
Iron Level in Influent and Effluent Salt Solu-
tions From Activated Carbon Treatment of
of Storage Brines
Page
34
35
35
36
36
39
40
47
67
68
69
70
73
74
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SECTION I
CONCLUSIONS
Strong sodium chloride brines used for storage of olives can be re-
conditioned and reused on a commercial scale.
The volume of brine which can be reconditioned and reused is 20, 000
gal. per ton of fresh activated carbon.
Reconditioned brine can be stored in the absence of freshly harvested
olives for six weeks before reuse.
The quality of the final product from processing of olives stored in
brine reconditioned by treatment with activated carbon is equivalent
to the quality of products from olives stored in virgin brines.
Lower salt content processing waters can be reconditioned for reuse
by treatment with activated carbon.
The cost of reconditioning olive storage brines for reuse is estimated
at $1. 28 per ton of raw olives when capital costs are amortized over
a period of ten years and the scale of operation is 50, 000 tons of
olives per year -
The cost of reconditioning olive storage brines for reuse is estimated
at $3.64 per ton of raw olives when capital costs are amortized over
a period of ten years and the scale of operation is 5, 000 tons of
olives per year with a single use of activated carbon.
Activated carbon used for brine reconditioning can be reactivated
through at least two cycles with no loss in efficiency.
The color of the reconditioned brine is the best criterion of reuse
potential of the five analytical indices (salt content, chemical oxygen
demand, pH, color and total acidity) investigated.
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SECTION II
RECOMMENDATIONS
The olive canning industry should give serious consideration to
activated carbon treatment of storage brines on the basis of placing
brine reconditioning units in each processing plant and by operating
a centrally located carbon reactivation plant cooperatively. As a
second choice alternative, brine reconditioning units should be in-
stalled and operated in those plants where the saline pollution po-
tential is most critical; these units to have no reactivation capa-
bility- Further research should be conducted on the utility of
carbon reconditioning of processing waters to reduce the volume
of discharge of these waste materials.
Further research should be conducted on the utilization of recon-
ditioned storage, brines-as canning, brines. A-promising .use of
reconditioned storage brine is as a canning or bottling brine after
adjustment of pH and salt content to appropriate levels. The use
of reconditioned brine as storage brine would utilize an equivalent
amount of salt to that employed in increasing the salt content of
storage brines during the period just after addition of freshly har-
vested olives to storage tanks containing diluted, reconditioned
brine.
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SECTION III
INTRODUCTION
The growing and processing of olives for oil and for preservation by
canning is a small but substantial part of the California agricultural
economy. It has been estimated that there are 32, 000 acres of
olives grown in California. The annual hand-harvested crop pro-
duced by this acreage has a gross value of $15, 000, 000. The annual
gross value of olive products produced in California has been esti-
mated at $40, 000, 000.
A brief review of the major steps in the production of canned ripe
olives will serve to indicate the nature and magnitude of the olive
industry's waste disposal problem. Olives are harvested in the
late fall period of mid-September to early November. The olives
are trucked to processing plants where they are size-graded by
diverging cable type graders, usually into five sizes. Because pro-
cessing cannot keep pace with the harvest, they must be stored in
large tanks and processed in salt brines (covered with sodium chlo-
ride solution). The concentration of brine used depends on the va-
riety of olive being stored. The brine is generally 4 to 5 percent
concentration for Mission, Manzanillo and Barouni varieties and
3 to 4 percent for Sevillano and Ascolano varieties. The concen-
tration of the brine is gradually increased over a period of thr^e
to four weeks to a level of 8 to 9 percent for the smaller sized va-
rieties and 7 to 8 percent for the Sevillano and Ascolano varieties.
The majority of the olives are stored in the brine for 1. 5 to 6 months,
At some plants, Mission and Manzanillo varieties are stored for as
long as ten months (in this case the brine concentration is increased
to 10 percent).
When olives are to be processed they are transferred from the sto-
rage tanks to shallow concrete or wooden vats, which hold about
one ton of olives. The olives are treated with three to eight chan-
ges of dilute sodium hydroxide (lye) solutions. The first lye is
usually 1 to 1.5 percent in concentration and the subsequent solu-
tions are 0.5 to 1 percent concentration. Between applications,
which usually last for 1.5 to 3 hr; the olives are covered with
water which is vigorously aerated by compressed air, or the
drained olives are exposed to air for 4 to 24 hr. The object of the
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lye treatment of olives is to hydrolyze the bitter principle (oleuro-
pein). The aeration at slight alkalinity oxidizes the tannins and
causes the olives to develop a black color- The olives are washed
with a number of changes of water until they are practically free
of sodium hydroxide (pH 7.3 to 7.8). The washed olives are
stored for 1 to 2 days in 2. 5 percent brine before they are size-
graded a second time and sorted.
The olives are canned in enamel-lined cans using a hot 2. 5 to 3 per-
cent sodium chloride solution to fill the can to the desired headspace
level. The brine frequently contains up to 3 oz of ferrous gluconate
for each thirty gal. of brine to fix the color of the canned olives.
The cans are generally closed in a steam flow type double seamer
to achieve a good level of vacuum after retorting and cooling. The
sealed cans are placed in retort cars or baskets and heated in
closed retorts at 240 °F for one hr. The cans are cooled with cold
potable water and then dried, labeled and cased.
The popularity of pitted olives is increasing and at present accounts
for a substantial fraction of the total production. The olives are
pitted after curing and the second size grading stage. Two different
makes of machines align the olives in a vertical position. A coring
tube produces a loose cylindrical section of pit and flesh. A punch
pin moves in from the opposite side from the coring tube to push
out the pit segment. These pitting machines have a capacity of
about 800 olives per min.
Green ripe olives are prepared from fruit taken directly from the
tree. The olives are treated with two lye solutions, the first for
about 18 hr and the second for 24 hr. The olives are washed with
three changes of water each day for three days. The washed olives
are treated with 3 percent sodium chloride solution for two days,
with 3 to 4 changes of the brine. The olives are then size-graded
and sorted. The remainder of the operation is identical to that of
the canned, black, ripe olives.
The third type of preserved olives (packed in glass jars) are the
Spanish green type product. These olives are prepared from full
sized fruit of the smaller sizes of Manzanillo or Sevillano variety.
The green colored fruit is treated in shallow tanks with 1. 5 to 2
percent sodium hydroxide until the lye has penetrated to a depth of
one-half to two thirds of the space between the skin and the pit. The
olives are then washed with cold water for 12 to 24 hr until almost
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all of the lye is removed. The water changes are made with minimum
contact iof.the olives with air to avoid darkening of skin color- The
washed olives are placed in 50 to 60 gal. oak barrels which are filled
with strong sodium chloride solutions (5 to 6 percent for Sevillano and
12 tb 15 percent for Manzanillo). The barrels containing Sevillano
olives are treated with rock salt until the concentration reaches 7 to
8 percent. The olives undergo bacterial fermentation which produces
lactic acid. The fermentation proceeds over a period of 60 to 120
days. The acid acts as a preservative and with other fermentation-
produced compounds imparts the characteristic flavor of the Spanish-
type olive. When the olives have developed the desired color, flavor
and acidity (about 1 percent total and at a pH of 3. 8), they are drained
of brine, size-graded mechanically and sorted on slowly moving belts.
The Spanish olives are packed in jars by hand, rinsed with water in
the jars by machine and filled with 7 percent sodium chloride solution
before capping.
It is obvious from the above outline of olive processing methods that
the spent brines and alkaline solutions constitute a considerable
volume of strong wastes. It has been estimated that nine olive com-
panies in the Central Valley used 4, 300, 000 Ib of sodium chloride
and 740, 000 Ib of sodium hydroxide to preserve 21, 000 tons of
olives in the 1961-62 season. Some 226 million gallons of water
were discharged during these operations. A simple calculation
shows that the ratio of sodium chloride used divided by the volume
of water discharged would give a level of 2300 ppm of sodium chlo-
ride as the average concentration in discharge water.
The Central Valley Water Quality Control Board passed resolutions
in 1963 which establish discharge requirements for most of the olive
processors in the San Joaquin Valley. In substance, the resolutions
say that if waste waters from any processing operation are dis-
charged in such a way that pollution of stream or ground water
would occur, the salt content must not be more than 175 ppm.
Substantial quantities of sodium salts (chloride, hydroxide) are used
in many food processing operations. The disposal of the saline li-
quid wastes from these operations, without causing water pollution,
is a problem of increasing complexity. The primary difficulty in
the disposal of saline liquid wastes is the non-biodegradable charac-
ter of sodium chloride and sodium hydroxide. The only economical
"solution" to the disposal of saline liquid wastes at present is the
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discharge to salt water receiving bodies or dilution with large vol-
umes of fresh water- Many food processors at inland locations have
inadequate fresh water dilution capacity available to assimilate dis-
charges of saline liquid wastes from their operations. These food
processors must change their production methods and/or disposal
practices to reduce the discharge of saline wastes in order to meet
water quality standards.
The work described in this report is confined to the treatment and
re-use of brines generated during the production of canned olives.
The preserved olive industry was selected for this initial study due
to the urgent need for ways to alleviate the critical pollution poten-
tial of saline liquid wastes discharged from canning plants in the
Central Valley of California. Substantial quantities of salt are also
used in the production of pickles, sauerkraut and other foods in
many areas of the United States. Information developed in this de-
monstration grant should be useful in the solution of potential water
pollution problems of all sectors of the food processing industry
which use brines in direct contact with food materials.
Increased total saline loads from population growth and changes in
agricultural practices, as well as more stringent discharge require-
ments, are responsible for the critical disposal problem in the
Central Valley of California. Long range research has been under-
way for several years (at the University of California, Davis and at
the National Canners Association Western Research Laboratory) to
develop storage systems for freshly harvested olives which do not
contain appreciable quantities of sodium chloride. These systems
(acidified water containing bacteriostatic organic compounds; che-
mical fertilizer salt solutions; or controlled atmosphere and tem-
perature storage) would produce waste streams which could be dis-
posed of more readily than sodium chloride brines. This research
is in an exploratory or developmental stage and, even if successful,
would require five to ten years to become the general commercial
practice of the olive canning industry. Until these methods are
fully developed and tested on a commercial scale, it will be neces-
sary to reuse or to dispose of strong saline brines in a way which
will insure that water quality standards are met.
The existing technology for handling and disposal of food processing
brines was reviewed and evaluated in 1967 by the NCA Staff. The
most promising method for the immediate relief of saline pollution
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problems was concluded to be based on exploratory research done
at the Western Utilization Research and Development Division, USDA.
Small volumes of spent olive storage brines were passed through a
column containing activated carbon. The purified brine was used
successfully by a commercial canner to store freshly harvested olives,
The final canned product from olives stored in the reconditioned brine
was of acceptable quality. The high-lights of this exploratory study
have been published (l).
Further developmental work on the use of activated carbon for re-
conditioning olive brines was reported from the USDA (2, 3). The
major objectives of this project were the preparation on a commer-
cial scale of reconditioned olive storage and processing brines and
evaluation of their reuse potential.
The reuse potential of reconditioned brines was to be established by
direct observation of the results of reuse on the quality of the final,
canned, olive product. A set of conventional measurements on the
brine samples was selected as indicators of gross changes in brine
composition after various treatments and re-use applications. The
analyses were of the type that could be done readily in a cannery to
serve as a quality control tool or as an indication of the suitability
of reconditioned brines for reuse.
The composition of storage brines and processing waters is dif-
ferent for each individual olive canning plant. Different varieties
of olives (the four principal varieties are Mission, Manzanillo,
Sevillano and Ascolano) require different strengths of brine to
avoid skin shrivel problems during storage. Certain plants in the
olive industry use low salt content brines, fortified with lactic acid,
to store olives. To obtain representative operational experience
the brine reconditioning unit was installed at four different locations
during the demonstration grant period.
The economics of reconditioning olive brines by activated carbon
treatment appeared attractive based on figures derived from small
scale studies. The larger scale operations described in this re-
port were necessary to demonstrate technical feasibility on a com-
mercial scale as well as to develop more accurate cost figures.
A storage system for olives has been under investigation since 1966
by Vaughn and co-workers at the University of California, Davis (4).
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The storage solution contains no added sodium chloride and de-
pends on a mixture of lactic acid, acetic acid, benzoic acid (and,
in some cases, sorbic acid) and anaerobic conditions to control
the multiplication of undesirable bacteria and yeast. The system
has been used successfully in the production of commercial lots
of Sevillano olives, but with other varieties an undesirable soft-
ening of the product has been noted.
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SECTION IV
DESIGN PHASE
The activated carbon treatment unit used in exploratory studies of
brine reconditioning by the USDA in Albany, California was a ver-
tical glass tube 2 in. in diameter (i.d. ) and 16 ft in length. The
contact time was 50 min with a flow rate of 1 gpm/ft2 of carbon bed
area. The fresh carbon feed rate was 0.40 lb/100 gal. of brine.
The unit was operated with the fresh carbon contacting the partially
treated brine counterflow operation. The design of the pilot scale
brine reconditioning unit was based on the following requirements:
Flow rate: 0.36 to 2.5 gpm/ft2
Capacity: 30 to 210 gph
Contact time: 15 to 100 min
Fresh carbon feed rate: 0 to 250 Ibs/hr
The design developed to meet the above requirements had the fol-
lowing specifications:
Main carbon column volume: 28 ft3
Main carbon column diameter: 16 in.
Main carbon column height: 20 ft
Carbon slurry feed tank volume: 8 ft3
Pressure vessel volume: 4 ft
Operating pressure of blow case: 50 lbs/in.2
Carbon hopper width: 16 in.
Carbon hopper height: 63 in.
The original design for the pilot scale unit was made by the USDA.
Near the start of the project, it was found that severe corrosion
occurred in stainless steel equipment exposed to mixtures of car-
bon and salt brine. It was necessary to convert the original draw-
ings which had specified stainless steel as the material of construc-
tion to drawings based on fiber glass reinforced food grade resin.
A company manufacturing plastic equipment provided a set of
drawings which served to obtain bids from potential suppliers
of the pilot scale brine reconditioning unit.
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SECTION V
CONSTRUCTION PHASE
The California Blow-Pipe and Steel Company of Escalon was selected
as the primary contractor. The sub-contractor for the fabrication
of the plastic components was the Heil Process Equipment Corpora-
tion of Cleveland, Ohio. Working drawings for the plastic compo-
nents and the steel support structure were prepared, reviewed and
modified before construction began.
The plastic components were fabricated in Houston, Texas and
shipped to Escalon where they were mounted in the steel support
structures. One section of the support structure housed the main
column section, the carbon addition hopper and the spent carbon
drain section. A second support section housed the carbon feed
tank and the blow case. The major components of the brine recon-
ditioning unit were transported horizontally on a 40 ft flat bed truck.
At the site a crane lifted the sections from the truck and placed them
in the normal (vertical) operating position. The support structure
and enclosed sections were secured with four guy lines.
A 1500 gal. capacity plastic swimming pool served as an influent
brine settling tank. Brine was delivered from the settling tank
(through a stainless steel cloth filter) with a Moyno pump (Model
Number 1 L, 3 SSQ) rated at 0.5 to 3.5 gpm. The brine was pumped
to the bottom of the carbon column through a hose line and distri-
buted with a circular, perforated stainless steel pipe.
Compressed air was supplied by a 1 horsepower air compressor
(ingersoil-Rand Model 1 HPCl) at 50 Ib pressure. A control
panel having a manifold of pressure regulators and valves was
used to control air pressure to the blow case and to the air activated
valves. Copper tubing was used to deliver compressed air to the
Keystone valves. An open plastic tank was provided for preparation
of carbon-water slurries.
The overflow return from the hopper to the slurry tank was trans-
ported through a 2 in. polyvinyl chloride pipe. The carbon was
held in the column by polyethylene beads and stainless steel cloth.
The effluent brine was delivered to collecting tanks through a 1 in.
hose. Sampling ports on the side of the main column spaced 2 ft
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apart starting 4 ft up from the bottom end of the column (number 1
for the lowest and 5 for the highest) were used to collect samples
representative of brine at various levels in the carbon bed. A
schematic drawing of the major components of the brine recon-
ditioning unit is shown in Figure 1.
Figures 2 through 4 show the final assembled unit as it appeared
on location in Lindsay. Figure 2 shows an overall view of the unit
and accessory equipment. Figure 3 was taken at ground level and
shows the air compressor, delivery pump and influent brine tank
in the left background. Figure 4 is of the carbon slurry prepara-
tion tank and pressure blow case.
All necessary accessory components (air compressor, delivery
pump, piping, guy cable and turnbuckles, compressed air reduc-
tion manifold and control panel, activated carbon, plastic float
screen and filter cloth) were purchased and delivered to Lindsay,
California where the unit was located initially.
The brine reconditioning unit and accessories had a total capital
cost of $15, 000. The unit had an activated carbon capacity of
1000 Ib.
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FRESH CARBON
SLURRY FEED—"
HOPPER
=COMPRESSEDAIR
OPERATED VALVES
^^-VENT PIPE
S
INF.
TANK
INFLUENT BRINE-*
AIR
COMPRESSOR
I
FEED PUMP
EFFLUENT BRINE—-
o
LU
DO
O
CO
DC
<
O
SPENT
CARBON
DISCHARGE
10 FEET
CARBON SLURRY
'PREPARATION TANK
CARBON
.^SLURRY
BLOWCASE
EFF.
TANK
FIGURE 1 SCHEMATIC DRAWING OF BRINE RECONDITIONING UNIT
( NOT TO SCALE)
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FIGURE 2. OVERALL VIEW OF BRINE RECONDITIONING
UNIT
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FIGURE 3.
LOWER PORTION OF BRINE
RECONDITIONING UNIT WITH
ACCESSORY COMPONENTS
IN BACKGROUND
FIGURE 4.
CARBON SLURRY TANK AND
BLOW CASE
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SECTION VI
OPERATIONAL AND EVALUATION PHASE
A number of problem areas were investigated during the operational
phase of the project. The brine reconditioning unit was operated at
four locations in California for the reasons stated in the Introduction.
The major problem areas studied during the operational phase were:
treatment of storage brines of various composition, treatment of
processing waters, analytical indicator of reuse potential, carbon
reactivation and reuse potential, quality of brines produced, and
estimation of the cost of the process on a commercial scale. The
problem areas investigated are tabulated in Table I along with a
listing of the site of each investigation and a reference to the sec-
tion of the report where observations are recorded or results are
described.
Table I
PROBLEM AREAS INVESTIGATED
DURING OPERATION OF BRINE RECONDITIONING
UNIT AT FOUR LOCATIONS
Location
Lind s ay
Vis alia
Problems Investigated
Treatment High Salt Content,
Medium B.O-D. Content
Storage Brine
Storage of Olives in
Reconditioned Brines
Storage of Reconditioned
Brine in Absence of Olives
Treatment of Low Salt Content,
High Lactic Acid Content
Storage Brines
Treatment of Imported
Spanish Olive Brine
Treatment of Olive
Processing Waters.
Text Reference
Table II
Page 37
Page 36
Table III
Table VIII
Tables IX, X,
XI
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Location
Madera
Problems Investigated
Treatment of Storage Brine
For Storage Experiments
Treatment of High B.O.D.
Content, Salt-Free Storage
Brines
Text Reference
Table IV
Table V
Oroville
Treatment of High B.O.D.
Content, High Salt Content
Storage Brines After Carbon
Conditioning With Salt Free
Storage Brine
Continuous Operation of Unit
With High B.O-D. Content,
Medium Salt Content Storage
Brine
Table VI
Table VII
Carbon Regeneration Tests
Evaluation of Activity of
Furnace Regenerated Carbons
Iron Content in Carbon Treated
Storage Brines
Storage of Olives in Brines Re-
ceiving Various Extent of Treat-
ment
Tables XII, XIII
Tables XIV,
XV, XVI
Appendix
Table XVII
Determination of Usefulness of
Analytical Measurements in
Predicting Brine Quality
Development of Values for
Cost Estimates
Page 44
Table XX
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Treatment of Storage Brines
The brine reconditioning unit was used first in Lindsay, California
(starting in September, 1968) to process high salt content olive
storage brines which had been used on olives stored during the 1967
season. The column section of the unit was charged with 1000 Ib of
CAL Type 12 x 40 activated carbon (Pittsburgh Activated Carbon
Company, Calgon Corporation) by making a water slurry of the
carbon in the feed tank, delivering the slurry to the blow case, and
immediately forcing the slurry with compressed air to the carbon
slurry hopper at the top of the column. The only operational prob-
lem encountered with the unit occurred when carbon settled out of
suspension and deposited in the lower region of the blow case, re-
stricting carbon delivery to the top of the column. It was possible
to mix separated carbon slurries using pulses of compressed air
in the blow case before sustained pressure was applied to force the
slurry to the hopper at the top of the column.
The influent brine was delivered to a plastic swimming pool to al-
low larger sized suspended material to settle out. The intake pipe
to the delivery pump was covered with 400 mesh stainless steel
hardware cloth to remove finely divided suspended solids.
In the initial experiments, an influent flow rate of 2 - 3 gpm was
used. Later experiments used lower flow rates to utilize the car-
bon adsorption capacity more completely by increasing the contact
time.
The following analyses were performed on as many representative
samples of brine and processing water as time and availability of
trained personnel allowed: l) Chemical oxygen demand (C.O.D. );
2) Suspended solids (SS); 3) Color; 4) pH; 5) Total acidity; and
6) Salt content. The C.O.D. method was that described by Jeris
(5) and while this method is not considered a Standard Method it
gave good agreement with C.O.D. values determined by the Stan-
dard Method on identical samples.
It was expected that one or a combination of the analyses listed
above would correlate well with the reuse potential of recondi-
tioned olive brines. The experimental details for the analyses
listed above will be found in an Appendix to this report.
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Numerous samples were taken during the operation of the brine
reconditioning unit from the various sampling ports. Analysis
of these samples showed consistent trends in the variables with
depth of carbon.
The analysis for color is typical of the results obtained in a series
of samples taken from the five sampling ports over a period of ten
minutes. A representation of the strip chart recording of the visi-
ble light absorption spectra as a continuous trace for a series of
brine samples is shown in Figure 5. In general all analyses made
of samples taken from the sampling ports showed gradients simi-
lar to the color analysis represented by Figure 5. For this rea-
son results from port sampling are generally omitted from the
tabulated data in this report and are listed in the Appendix.
A total of 12,750 gal. of storage brine was put through the unit
over a period of fourteen days of intermittent operation. The
flow rate was from 2 to 3 gpm. Six 60-Ib portions of fresh car-
bon were added at intervals during this period after spent carbon
had been removed. Samples of influent brine, brine at various
sampling ports on the column and effluent brine were collected
and analyzed. The observations and analyses made during this
period are tabulated in Table II and in the Appendix.
A total of 10, 000 gal. of low salt content olive storage brine was
processed with the activated carbon column at Visalia. The flow
rate through the carbon bed was maintained at 1.25 gpm. The in-
fluent brine came from two separate 5000 gal. storage tanks.
The results of measurements on the treated brine from these tanks
are tabulated in Table III.
-22-
-------
600
560
520 480 440 400
WAVE LENGTH MILLIMICRONS
FIGURE 5. PLOT OF ABSORPTION SPECTRA OF OLIVE
BRINE SAMPLES
-23-
-------
TABLE II
OBSERVATIONS AND ANALYTICAL RESULTS FOR
TREATMENT OF HIGH SALT CONTENT STORAGE
BRINE WITH ACTIVATED CARBON
Effluent
Volume,
Gallons
Influent
270
630
1,350
2,010
2,910
3, 150
3,270**
3,390
3,750
4, 110
4,660
Influent
5,630
5,930
6,230
7, 175
7,200**
7,775
8, 075
8,375
8,400
8,700
9,000
9, 150
9,650
9, 800**
10,985**
Influent
11,225
12, 105
12,750
C.O.D.,
mg/liter
18, 000
800
5, 000
*
9, 100
10,200
9, 000
10, 500
5,400
11,200
12,400
10,700
16, 800
10,400
11,400
10,700
13, 100
14,800
6,600
11, 100
11,400
7, 900
10, 800
17, 800
13, 100
*
*
6,600
18,900
11,300
19,000
18, 900
Total
Acidity, NaCl
g Lactic Content,
pH Acid/ 100 g %
4.3
8.0
6.8
7.4
5. 1
4.6
ii
4.8
6.2
4.5
ii
4.2
4.2
4.3
4.0
4.3
4.2
4.4
6.7
4.2
ii
4.5
3.9
4. 1
4.0
1 1
3.9
7. 1
4. 1
4.2
4.4
4. 1
0.39
0 *
*
*
*
*
*
*
*
*
0.20
0.32
0.35
0.31
0.37
ii
0.38
0.21
0.01
0.35
0.38
0. 14
0.37
0.38
ti
ii
0.41
0.03
0.41
0.42
0.48
0.41
5.5
5. 1
5.5
ii
5.4
5.5
5.4
ii
ii
5.5
"
ii
6.2
5. 8
6.0
ii
ii
6.2
ii
11
n
6.0
n
n
n
*
*
5.6
6.0
5.6
*
*
Color,
Visual
Dk . yellow- grn .
Cloudy
ii
n
ii
n
n
Lt. yellow- grn.
Cloudy
Lt . yellow- grn .
Cloudy
Light grey
Dk . yellow- gr n .
Cloudy
n
ii
1 1
it
Light grey
Cloudy
1 1
n
n
ii
Light grey
Cloudy
ii
Light grey
Dk . yellow- gr n .
Cloudy
Lt. yellow- grn.
ii
*Not measured.
**60 Ib of
fresh carbon
added.
-24-
-------
TABLE III
OBSERVATIONS AND ANALYTICAL RESULTS FOR
TREATMENT OF LOW SALT CONTENT STORAGE
BRINE WITH ACTIVATED CARBON
Effluent
Volume ,
Gallons
Influent
834
1,670
2,500
3,340
4, 170
5, 000
Influent
5,834
6,670
7,500
8,340
9, 170
10,000
C.O.D.
mg/
liter
22,300
10,700
20,500
21, 900
21,900
22, 100
22, 100
25,200
23,800
22,300
21, 100
21,700
21,500
21,900
, ss,
mg/
liter
64
98
36
51
51
28
30
49
25
34
13
33
56
79
PH
4.0
5.6
4.2
4. 1
4.0
n
11
4. 1
4.0
4. 1
n
ii
n
n
Total
Acidity,
g Lactic
Acid/ 100 g
0.42
0.07
0.41
0.42
n
ti
M
0.39
0.38
ti
n
u
0.39
n
Nad,
Content
%
1.65
1.45
1.45
1.60
1.60
1.60
1.65
2. 15
1.95
2. 15
u
n
n
2.20
, Color,
Visual
Dk.Brwn
Colorless
Lt. yellow
ii
ii
u
u
Dk.Brwn
Lt.yellow
Yellow
u
"
n
M
Light
Trans -
mittance ,
%
33
100
n
u
n
u
n
27
100
90
84
73
78
88
Initial carbon charge: 180 Ib fresh, 820 Ib used (See Table II)
After moving the brine reconditioning unit to Madera, the column
was filled with 900 Ib of fresh carbon. The results obtained during
the treatment of 2000 gal. of storage brine at a flow rate of 2 gpm
are tabulated in Table IV.
The results of treating salt-free storage brine with activated car-
bon using a flow rate of 2 gpm are tabulated in Table V. The ben-
zoic acid content was measured during this experiment. The in-
fluent brine had 0. 126 percent benzoic acid, while a sample taken
after 1000 gal. of effluent had been collected showed 0. 012 percent
benzoic acid.
An additional 4, 800 gal. of high salt content storage brine were
pumped through the carbon bed with a flow rate of 2 gpm in the Madera
final study to determine the effect of the salt-free brine on carbon
activity. The results from this experiment are tabulated in Table VI.
-25-
-------
TABLE IV
OBSERVATIONS AND ANALYTICAL RESULTS
FOR TREATMENT OF STORAGE BRINE
FOR STORAGE EXPERIMENTS
Effluent
Volume,
Gallons
Influent
400
800
1,200
1,600
2, 000
C.O.D. ,
mg/liter
25,400
4,600
14,600
18,200
27,500
25, 000
PH
3.7
8.5
7.2
6.0
4.0
3.8
NaCl
Content ,
%
6.3
5.2
5. 1
4.6
6.4
6.5
Color ,-
Visual
Dark purple
Colorless
n
ii
n
n
Initial carbon charge: 900 Ib fresh, 100 Ib used (See Table XI)
TABLE V
OBSERVATIONS AND ANALYTICAL RESULTS
FOR TREATMENT OF SALT-FREE STORAGE
BRINE WITH ACTIVATED CARBON
Effluent
Volume ,
Gallons
Influent
400
800
1,200
C.O.D.,
mg/liter
45, 100
20, 600
16,400
31,400
PH
4. 1
5. 1
4.6
4.2
Total
Acidity,
g Lactic
Acid/ 100 g
1.04
0.28
0.73
1.25
Color,
Visual
Yellow
Colorless
n
1 1
NaCl content was less than 0. 1 percent in all samples.
Initial carbon charge: 1000 Ib used (See Table IV)
-26-
-------
TABLE VI
OBSERVATIONS AND ANALYTICAL RESULTS
FOR TREATMENT OF STORAGE BRINE
WITH ACTIVATED CARBON CONDITIONED
WITH SALT-FREE STORAGE BRINE
Effluent
Volume ,
Gallons
Influent
1,
1,
2,
2,
2,
400
800
200
600
000
400
800
Influent
3,
3,
4,
200
600
000
Influent
4,
4,
400
800
C.O.D. ,
liter
19,
11,
8,
10,
11,
10,
12,
12,
31,
25,
24,
20,
16,
8,
7,
400
500
500
400
500
200
500
800
500
900
500
500
000
500
000
PH
4.
3.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
4.
8
8
3
5
6
3
4
7
7
5
7
6
8
6
5
Total Light
Acidity, NaCl Trans-
g Lactic Content, Color, mittance,
Acid/ 100 g % Visual %
0.
0.
0.
0.
0.
0.
i
0.
0.
0.
0.
0.
0.
0.
0.
22
76
35
31
32
27
i
28
41
31
28
29
27
10
07
7
7
7
6
7
7
8
7
6
7
8
8
8
.4
.8
.6
.3
.0
.4
.0
.0
.9
.9
"
"
.3
.3
.4
Dk. purple
Milky white
n
ii
n
Colorless
"
n
Dk. purple
Lt. purple
"
Med . purple
Dk. purple
Med . purple
"
53**
50
75
69
57
100
100
100
43 **
87
91
74
57**
81
80
** Influent samples diluted with five parts of water.
Initial carbon charge: 1000 Ib used (See Table V)
The longest periods of continuous operation of the brine recondition-
ing unit and the largest quantity of brine for a single carbon loading
were accomplished at Oroville.
Table VII tabulates the results obtained during the processing of
19, 110 gal. of storage brine with a single 1000 Ib activated carbon
charge. No sampling from individual ports was made during the
operations at Oroville. The flow rate was 2 gpm for the first 3510
gal. and then 0.75 gpm until the end of the run at 19, 110 gal.
-27-
-------
TABLE VII
OBSERVATIONS AND ANALYTICAL, RESULTS FOR
TREATMENT OF STORAGE BRINE DURING
EXTENDED PERIODS OF CONTINUOUS OPERATION
Effluent
Volume,
Gallons
Influent
60
180
420
720
1,680
1,920
3,030
3,510
3,750
4,230
4,470
4,950
5, 190
Influent
5,670
6,060
9,255
9,615
10,335
Influent
11,415
12, 135
13,215
16,455
Influent
17,355
18,615
19, 110
C.O.D.,
rag/
liter
39, 100
100
2,300
2,500
13,200
23, 500
23,000
34,500
34, 100
41,500
37,000
37,800
34, 100
35, 000
32,500
35,400
33,700
24,400
24.400
24,000
30, 900
28,300
32,500
31,700
25,200
24,000
24,400
12,600
31,700
SS,
mg/
liter
431
7
330
333
266
333
334
327
537
344
489
424
372
469
380
487
387
435
389
395
504
486
435
328
563
446
446
433
552
PH
4.5
7.3
7.9
7.5
6.7
5.9
11
4.4
4.6
4.5
4.4
ii
ii
4.5
4.3
4.4
4.5
4.3
4.2
ii
ii
4. 1
5.7
4.6
4.5
4.4
4.2
4.3
ii
Total
Acidity,
g Lactic
Acid/ 100 g
0.48
0.02
0. 14
0.02
0.05
0. 11
0. 13
0.56
0.44
0.48
ii
ti
0.45
ii
.49
0.46
0.42
0.39
0.41
0.39
0.42
0.45
0. 11
0.39
0.30
0.35
0.37
0.35
*
NaCl
Content ,
%
5.0
<0. 1
4.5
5.3
5.0
5. 1
4.6
4.8
5.9
4.6
5.6
4.4
4.6
ii
4.4
*
3.8
*
3.6
2.2
5.6
5.0
4.6
4.8
5.4
5.5
5.6
5.7
7.4
Light
Trans-
mi tta nee,
%
1
97
98
99
86
77
48
73
67
56
62
45
50
45
15
50
46
36
26
27
9
28
78
20
5
32
46
44
15
* Not recorded
Initial carbon charge: 1000 Ib fresh.
-28-
-------
The results obtained in the activated carbon treatment of olive brine
used to store Spanish-style green olives are tabulated in Table VIII.
The flow rate used, was 2 gpm.
TABLE VIII
ACTIVATED CARBON TREATMENT OF BRINE
USED TO STORE IMPORTED GREEN OLIVES
Effluent
Volume,
Gallons
Influent
90
210
330
450
510
570
C.O.D.,
mg/
liter
19, 100
2, 000
6, 000
7,800
8, 800
8, 100
8,400
SS,
mg/
liter
234
22
98
63
53
100
89
PH
3.5
9.1
8.7
8.4
8.0
7.9
7.7
Total
Acidity ,
g Lactic
Acid/ 100 g
0.83
-------
TABLE IX
RECONDITIONING OF STRONG LYE RINSE WATER
WITH ACTIVATED CARBON
Effluent
Volume ,
Gallons
Influent
75
150
225
300
375
450
525
600
675
750
825
C.O.D., SS>
mg/
liter
4,400
500
1,400
1,400
1,400
1,700
2,000
1,500
2,200
1,800
1,900
2,200
m§/
liter
138
< 1
< 1
1
7
3
12
18
15
12
22
26
PH
12.5
9.5
11. 1
12.0
12.4
12.4
12.4
12.4
12.4
12.5
12.5
12.5
NaOH,
g/
100 g
0.83
0.03
0.04
0. 19
0.69
0.70
0.71
0.80
0.80
0.80
0.80
0.80
NaCl
Content,
%
0.45
0.01
0.01
0. 10
0.23
0.21
0. 13
0.24
0.32
0. 17
0.22
0.20
Light
Trans-
mittance ,
%
62**
96
82
62
63
49
52
67
57
48
41
19
** Influent diluted with five parts of water
Initial carbon charge: 180 Ib fresh, 820 Ib used (See Table III)
water was returned in clean bins for a reuse potential evaluation. A
flow rate of 2 gpm was used. A summary of the analytical results
are tabulated in Table X.
Afresh water backwash of approximately 720 gal. was used to reduce
the lye concentration on the carbon before treatment was started on
brine which had been used to transport olives from the final washing
tanks to the can filling equipment. A charge of 120 Ib of fresh carbon
was loaded into the brine reconditioning unit. The transport brine
was pumped through the carbon at a flow rate of 2 gpm. The flow
rate and screen were checked at intervals; the rate needed adjust-
ment periodically because of clogging of the wire cloth filter on the
influent line by suspended solids in the transport brine. This was
the only time this problem occurred during the project.
The results of this experiment are tabulated in Table XI.
-30-
-------
TABLE X
TREATMENT OF PROCESSING WATER
WITH ACTIVATED CARBON
Effluent
Volume ,
Gallons
Influent
60
180
300
420
540
640
C.O.D. ,
mg/
liter
6,400
800
2,000
2,000
2,300
2,900
2,800
PH
9-3
12.0
11. 8
11.6
11.3
11.2
11. 1
NaOH,
g/per
100 g
.022
.334
. 138
.087
.065
.058
.055
NaCl
Content,
%
0. 11
0.05
0. 10
0. 12
0. 12
0. 11
0. 12
Light
Trans-
mi ttance ,
%
55**
100
87
93
95
94
91
** Influent sample diluted with ten parts of water
Initial carbon charge: 100 Ib fresh, 900 Ib used (See Table IX)
TABLE XI
ACTIVATED CARBON TREATMENT OF TRANSPORT BRINE
Effluent
Volume,
Gallons
Influent
80
200
320
440
C.O.D. ,
mg/
liter
740
500
<20
<20
500
SS,
ms/
liter
200
< 1
11
ii
ii
PH
7.2
10.3
10.0
9.7
10. 1
NaOH,
i/
100 g
0
0.044
0.007
0.007
0.011
NaCl
Content,
%
3. 10
0.02
2.20
2.27
3.05
Light
Trans-
mi ttance ,
%
54
100
ii
11
- ii
Carbon bed backwashed with 720 gals, of water before use.
Initial carbon charge: 100 Ib fresh, 900 Ib used (See Table X)
-31-
-------
Iron Levels in Carbon Treated Brines
There was some concern about the level (8 to 16 ppm) of iron in re-
conditioned brine (caused by elution from the carbon) as a source of
off-flavor in stored olives. Pairs of samples of influent and efflu-
ent from operation of the brine reconditioning unit at Oroville were
collected and the iron level determined. The results are tabulated
in the Appendix. The iron is present in the carbon due to the iron
content of the coal from which the carbon was prepared; only part
of the iron is removed by washing procedures used in the carbon
manufacture.
Evaluation of Furnace Regenerated Carbon
Approximately 1000 Ib of carbon (dry wt) in the form of a slurry in
brine was removed from the brine reconditioning unit after treating
19, 110 gal. of strong storage brine (See Table VII). The slurry was
placed in 55 gal. metal drums and washed for 24 hr by placing fresh
water hoses at the bottom of the drums and introducing water at the
rate of 100 gph. The overflow spilled over the sides of the drum and
was collected in the tank field gutter system. At the end of the wash-
ing period the carbon was placed on 40 mesh screening for dewatering.
The moist carbon was transported to Brisbane, California for regene-
ration.
A second 1000 Ib lot of spent carbon (dry wt) from the experiments
at Madera (See Tables IV, V, and VI, stored for thirteen weeks)
was regenerated at the same time as the washed carbon described
above; this material was designated as unwashed.
The summary of the carbon regeneration as reported by the BSP
Corporation is tabulated in Table XII (the discrepancies in values
for dry wt of carbon found by NCA and BSP Corporation were not
resolved due to loss of identity of tared containers) and the analytical
results on the regenerated carbon in Table XIII.
The reactivated carbon was used to recharge the carbon bed section
of the brine reconditioning unit in two separate operations. The
first batch was the water washed, reactivated carbon which was
used to recondition brine as summarized in Table XIV. The flow
rate was 2 gpm for the first 480 gal. then 1 gpm for the remainder
of the run. The unwashed, reactivated carbon was used to recondition
-32-
-------
TABLE XII
OBSERVATIONS ON REGENERATION OF SPENT
CARBON FROM THE BRINE RECONDITIONING UNIT
Operation
Washed
Unwashed
Analysis, as Received
Percent Moisture 14.6
Apparent Density (A. D.), g/cc . 589
Dry carbon, Ib 638
Regenerated Product (A. D. ) .470
Improvement (Change in
A.D.), Percent 25
Furnace Temperature, °F
27. 1
.544
974
.457
19
Stage
Scrubber
H - 1
2
3
4
5
6
Loss, Ib/hr
200
800
1000
1650
1700
1750
.26
200
1050
1400
1750
1730
1720
.63
Shaft speed 1.3 RPM, Zero draft, 30 hr operation time. Some
smoking observed on unwashed material, afterburner not used.
-33-
-------
TABLE XIII
ANALYTICAL RESULTS ON REGENERATED CARBON*
Sample
Identity
Molasses
Number
Measurement
Ash
Content
Iodine
Number
A.D.
g/cc
Water-washed
Before Re-
generation
Water-washed
After Re-
generation
Salt-loaded
Before Re-
generation
Salt-loaded
After Re-
generation
Virgin
246
232
5.92
6.47
787
.510
845
.499
208
262
230
7.30
455
571
8.21
870
8.5
1000
,490
.710
*Values reported by Calgon Center, Pittsburgh Activated Carbon
Company, Pittsburgh, Pa. 15230.
brine as summarized in Table XV. The flow rate was 1.25 gpm. A
comparison of the efficiencies of virgin; water-washed, reactived;
and unwashed reactivated carbon is shown in Table XVI. The com-
parison was made on the basis of analysis of effluent brine for each
carbon type after 5, 000 gal. of brine of similar composition had been
treated using approximately the same flow rate (See Tables VII, XIV
and XV). It is recognized that this comparison of efficiencies is of
doubtful utility due to single measurements of variables.
A number of small scale samples were regenerated and evaluated by
the Pittsburgh Activated Carbon Company. Analysis of carbon put
through a second furnace activation cycle on a small scale is tabu-
lated in Table XVII.
-34-
-------
TABLE XIV
ACTIVATED CARBON TREATMENT OF STORAGE BRINE USING
CARBON WATER WASHED BEFORE FURNACE REACTIVATION
Effluent
Volume ,
Gallons
Influent
240
480
600
840
Influent
1,920
3,200
5,073
C.O.D.,
mg/
SS,
liter mg/liter
32,900
S.D.*
S.D.
5, 000
19,000
33,300
25,300
32,900
32,500
496
S.D.
S.D.
S.D.
489
466
477
452
507
PH
4.2
8.7
5. 1
4.8
5.2
4.2
4. 1
4.3
4. 1
Total
Acidity,
g Lactic
Light
NaCl Trans -
Content, mi ttance ,
Acid/ 100 g % %
.547
S.D.
.253
.309
.211
.464
.492
.422
.436
5.7
6. 1
6. 1
6. 1
5.9
7.5
7. 1
7.5
7.5
22
71
45
40
22
20
74
64
66
* 3-D. - Sample delayed in delivery to Berkeley Laboratory;
accuracy of results were uncertain.
Initial carbon charge: 1000 Ib reactivated.
TABLE XV
ACTIVATED CARBON TREATMENT OF STORAGE BRINE USING
CARBON UNWASHED BEFORE FURNACE REACTIVATION
Effluent
Volume,
Gallons
Influent
1,870
3,670
5,496
C.O.D
mg/
liter
28,600
16,500
21,500
26,700
.,
SS,
mg/liter
440
457
406
457
pH
4.
6.
4.
4.
5
1
8
3
Total
Acidity,
g Lactic
Acid/ 100 g
.337
.03
.211
.351
NaCl
Content,
%
6.0
6.0
6.0
6.0
Light
Trans-
mi ttance ,
%
25
87
93
97
Initial carbon charge: 1000 Ib reactivated.
-35-
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TABLE XVI
COMPARISON OF EFFICIENCIES OF VARIOUS TYPES
OF CARBON IN RECONDITIONING STORAGE BRINE
Light
C.O.D. reduction, SS reduction, Transmittance,
Carbon Type % % %
Virgin
Water Washed
Reactivated
12.6
2.4
13.7
(2.2)*
50
66
Unwashed,
Reactivated 17.8 2.3 95
*Value increased as did others at 5190 and 5496 gal. , resp.
TABLE XVII
ANALYSIS OF ACTIVATED CARBON AFTER
SECOND FURNACE REACTIVATION CYCLE
Analysis
Molasses Iodine A.D.,
Carbon Sample Number Ash Number g/cc
Spent
Laboratory Regeneration*
210
272
4.51
6.12
413
930
.640
.460
Laboratory Regeneration
after washing** 345 6.42 789 .452
*Steam/Air at 1750 CF for 42 min; the volume yield was 94. 5% .
**Washed with tap water for 16 hr, rinsed with de-ionized water,
regenerated as stated above; the volume yield was 95.5%.
Storage of Reconditioned Brine Without Olives
To get the most efficient use of a commercial scale carbon column unit
it would be desirable to operate it several months before freshly har-
vested olives are received for storage. For this type of operation, it
would be necessary to store reconditioned brine in the absence of olives
for periods of three to six months. It has been demonstrated on many
occasions that used olive storage brines develop yeast, mold and bac-
terial growth in the absence of green olives. These changes in the
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storage brine make it unsuitable for reuse because olives stored in
such brines produce a final product of inferior flavor and texture.
There was considerable question about the storage performance of
carbon-treated brine in the absence of green olives.
The first 5450 gal. of reconditioned brine described in Table II were
stored in a redwood tank starting on October 24, 1968. The pH of
the brine was adjusted from 4.1 to 3.7 by the addition of 20 gal. of
37 percent (food grade) hydrochloric acid. The brine in this storage
tank developed a yeast or mold pellicle after 3 to 4 weeks of storage.
The brine in the tank was reported by plant personnel to have an un-
desirable odor after three months of storage; however, project
personnel could detect no significant undesirable odor on smelling
the brine after three and four months of storage.
The 10, 000 gal. of storage brines treated by the carbon column at
Visalia as described in Table III were stored in two 5,000 gal. tanks.
The reconditioned brine had an average salt content of 1. 8 percent,
a pH of 4.0 and a total acidity of 0.29 percent. These storage brines
were adjusted to lower pH's by the addition of a mixture of lactic and
acetic acids. The brine in the two tanks was circulated by pumping
to break up surface growth of yeasts and molds. The brine had a
good odor and appearance to project personnel after six weeks of
storage in the absence of green olives.
No systemic observations were made on reconditioned storage
brines stored in the absence of olives at Madera. It was reported
that one of the tanks of reconditioned brine (See Table IV) developed
an objectionable odor after approximately two months of storage and
the brine was pumped to an evaporation pond.
The most detailed observation on storage of reconditioned storage
brines was made in Oroville. Brines having storage periods of 4,
36 and 64 days were used in olive storage experiments. The brine
with the longest storage period developed an odor described as
"brassy" by the plant personnel. Due to this odor, the plant manage-
ment was reluctant to run full scale storage experiments in this re-
conditioned brine and only small scale (100 Ib lots) storage was in-
vestigated.
Storage of Olives in Reconditioned Brine
The experimental storage of fifteen tons of olives in 1,530 gal. of
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reconditioned brine (See Table II; effluent from the last 1500 gal.
treated was used) was followed with intense interest. The olives
used were medium Manzanillos and the brine had a starting salometer
reading of 24° at the time storage started on October 23, 1968; the
salt content of the brine was increased to 30° during the first two weeks
of storage by the addition of sodium chloride. After three months of
storage, the salt concentration was raised to 10 percent (40° salometry).
A sample of olives was taken from the storage tank each week and ex-
amined for signs of spoilage or shrivel. The olives appeared to be
undergoing a normal fermentation and storage behavior- Small por-
tions of the stored olives were processed and canned on December 23,
1968; February 24, 1969; and on April 24, 1969- A control sample
of olives from normal storage tanks was obtained for each of the
canning periods of the experimental olives.
At the end of the storage experiment, the olives were used in com-
mercial production. There was no report of any quality defect in
these olives as they were marketed in routine fashion.
Due to the fact that the olives prepared from those stored in recon-
ditioned brine might have an unusual content of potential spoilage
microorganisms, a sterility test was run on canned olives. Cul-
tures were prepared from the experimental sample and a commer-
cial sample which served as a control (pH 6.45 and 6.55, respec-
tively) in three types of media with incubation at 30 and 50°C. No
growth was observed in any cultured sample from the olives. Mi-
croscopic examination of the contents of cans after 6 days of incu-
bation at 30°C (all cans remained flat) detected a few bacterial
cells. The canned olives were judged to be commercially sterile.
A series of ten 100 Ib samples of freshly harvested Giant Sevillano
olives were stored in three types of reconditioned storage brines.
Some characteristics of these storage brines are tabulated in Table
XVIII- Samples of reconditioned storage brine from three tanks
[representing the last 5000 gal. of effluent described in Table VII
(69- 1); the first 2000 gal. of effluent described in Table XIV (69-3);
and the last 1000 gal. of effluent described in Table XV (69-2)] was
diluted with fresh water to a salometer reading of 12°; 10 gal. of
this brine was used for each of the ten 100 Ib lots of olives. The
ratio of brine volume : olive weight was twice that of normal com-
mercial practice but was necessary for the configurations of the 32
gal. pails used and the companion redwood floats which keep the
olives submerged.
The sodium chloride content of the brine was increased by the ad-
dition of salt by the schedule shown in the Appendix. The olives
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TABLE XVIII
SMALL, SCALE OLIVE STORAGE EXPERIMENTS
Type Carbon Brine to Post-Recondi-
Storage Pail Used in Carbon Ratio; tioning Storage
Code Number Reconditioning Gallons : Pounds Time, Days
69 - 1 A Fresh 14 : 1 64
B
C
D
69 - 2 A Salt-Loaded 2:1 36
B Reactivated
C
69 - 3 A Water - Washed 5:1 4
B Reactivated
C
were judged to be undergoing a normal storage in all three types of
brines. Approximately 30 Ib of olives were removed from each
storage pail, put in plastic screen bags and carried through a com-
mercial lye cure, oxidation, rinsing, and canning. The total sto-
rage period for olives in these samples of reconditioned brine was
4. 5 months.
Quality of Canned Olives From Storage in Reconditioned Brines
Samples of olives taken from the storage tank in Lindsay on April
24, 1969, were prepared and canned by Consolidated Olive Growers
personnel; these samples had die code 3 D 685/BD 61 and were
marked Tank 419 with paint on the sides of the cans. A commercial
sample of medium Manzanillo olives of the same storage period
was used as a comparison sample.
-39-
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The canned olives were presented to a taste panel of 16 people for
difference testing (triangle presentation). Three samples (two
identical and one different) were presented on four consecutive days.
Of the total of 64 judgments, 24 correct matchings of the identical
samples were obtained. Since a purely random result would yield
21.33/64 correct judgments, it can be concluded that the samples
from olives stored for six months in reconditioned brine were not
significantly different in flavor from the samples from olives
stored in virgin brine.
A more extensive test of the storage of freshly harvested olives in
reconditioned brines of various extent of treatment and storage
period after reconditioning was conducted at Oroville.
The samples from the three different reconditioned brines and a
control sample from commercial production (all Giant Sevillano
olives) were presented to a panel for flavor preference ranking in
eight daily sessions with random order of presentation (l = best,
4 = worst flavor). Two series of tests were made, one having re-
plicates of the 69- 1 series which represented the potentially poorest
quality storage brine. The results of these quality ranking tests
are tabulated in Table XIX. A flavor ranking of 2. 50 would be ex-
pected if the samples presented were judged to be identical in fla-
vor .
TABLE XIX
FLAVOR RANKING OF CANNED RIPE OLIVES
Storage Brine : Carbon
Code No. Ratio, Gallons : Pounds
69-1
69-2
69-3
A 14 : 1
B
D
B 2:1
C
B 5:1
CONTROL 1st Test
2nd Test
Post Reconditioning Flavor
Storage Time, Days Ranking
64 2.
2.
2.
36 2.
2.
4 2.
2.
2.
57
13
14
81
85
62
39
45
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SECTION VII
DISCUSSION
Treatment of High Salt Content Storage Brines
Substantial changes in the values for pH, total acidity, C.O.D. and
color were observed when fresh carbon contacted the brine; the
level of suspended solids followed a random pattern. Increases
in the pH of effluent samples and decreases in total acidity were
found as the brine contacted fresh carbon at low influent volumes.
However, the pH and total acidity were similar in both the influent
and effluent brines as the effluent volume increased (See Tables II,
IV, VII). The retention of the total acidity in the effluent from car-
bon treatment is desirable since the lactic acid (which is the major
contributor to acidity) is a preservative in the brine storage of
olives. The C.O.D. of the effluent brine dropped sharply after
each addition of fresh carbon to the reconditioning unit. The general
trend of the C.O.D. values was to increase up to the influent level
as the volume put through the carbon bed increased (See Tables II
and VIl). The influent storage brine was usually dark yellow-green
or light reddish-orange. The effluent brine ranged in color from
colorless to light greenish-yellow. The values for light transmit-
tance, which provided a more objective measure of color than the
visual estimation, correlated well with the extent of treatment.
The values for light transmittance were high for low effluent vo-
lume : carbon ratios and low for high effluent : carbon ratios (See
Table VIl).
The salt content of storage brines showed little change due to pas-
sage through the carbon bed; the only change was a transitory one
as low volumes of brine contacted freshly exposed carbon (See
Tables II, IV, VII).
Treatment of Low Salt Content Storage Brine
A single experiment on the treatment of low salt, high lactic acid,
storage brine was conducted (See Table III). The carbon treatment
of low salt content brine was effective in removing color and re-
taining lactic acid. The carbon treatment had little effect on C.O.D.
-41-
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The reconditioned brine was stored and observed for a period of six
weeks. The brine did not develop undesirable odors or change sig-
nificantly in color. The reconditioned brine was reused for the
storage of olives with no untoward effect on the quality of the final
product.
Treatment of Salt Free Storage Brine
While not a part of the original project plan, the prospect that a
considerable portion of commercial olive production would use
the salt-free storage system made it of interest to determine the
result of treatment of liquid waste from this type of storage prac-
tice. It was also felt that the used salt-free solution might con-
dition spent carbon and cause it to perform for longer periods in
the treatment of conventional storage brines. The conditioning
of spent carbon might take place due to displacement of adsorbed
organic material from the carbon by the lactic and acetic acids in
the salt-free storage solution. It was also of interest to determine
the fate of the benzoic acid in the salt-free storage solution during
activated carbon treatment. Removal of the benzoic acid would
probably improve the biological degradation of the high B.O.D.
material represented by the liquid waste discharged after use of
salt-free storage solutions. On the other hand, the removal of
benzoic acid by the carbon treatment would detract from the reuse
potential of reconditioned solutions since this acid is one of the
most costly components .
The results of treatment of a salt-free storage solution are sum-
marized in Table V. The activated carbon treatment of a salt-
free storage solution reduces the C.O.D. value markedly at low
effluent volumes (i.e. from 45, 000 to 2 1, 000 mg/1 at 400 gal. of
effluent). The total acidity is also substantially reduced in the
initial effluent volumes. The C.O.D. increases to about 75 per-
cent of the influent level at the point where total acidity values
return to the influent level. The effluent was colorless at all
volumes studied. Ninety percent of the benzoic acid present in
the influent was removed by the carbon treatment.
The passage of the salt-free storage solution through the carbon
bed appeared to have a beneficial effect on carbon efficiency.
-42-
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An additional 4800 gal. of high salt content storage brine was
passed through the carbon and resulted in an effluent with high
light-transmittance readings (See Table Vl).
Treatment of Processing Waters
The carbon treatment of olive brine was originally designed for
high salt content storage brines; it is this application which
would remove most of the sodium chloride from olive cannery
liquid waste discharges. However, if the activated carbon treat-
ment technology were adopted for the reconditioning of high salt
content storage brines, the availability of the equipment in the
cannery may make the treatment of processing waters economi-
cally attractive.
The processing waters are those solutions used for soaking and
washing olives as they are prepared for canning. For the
reasons stated above and in the Introduction, three types of
processing waters were used in brief, exploratory studies of
the effect of activated carbon treatment on the reuse potential.
A lye rinse water of 825 gal. volume was passed through the
carbon bed to explore the potential of reconditioning such pro-
cessing water. The analytical results from this experiment
are tabulated in Table IX. The SS and C.Q.D. content of the
influent were reduced by the carbon treatment; a reduction of
91 percent for the SS content and 62 percent for the C.O. D.
level (on the average) was observed. The concentration of
sodium hydroxide in the effluent returned to nearly the influent
level after one-half of the liquid had passed through the carbon
bed. The reconditioned strong lye rinse water was used as make-
up water in lye curing tanks. The cannery personnel who evalu-
ated this reuse found the practice to be satisfactory.
Results of the treatment of processing water with activated
carbon are summarized in Table X. The major portion of the
carbon within the unit was saturated with sodium hydroxide from
a previous use (See Table IX) and this was partially eluted as
the processing water passed through the carbon bed. The colored
components in the influent were almost completely adsorbed by the
carbon. The high pH of the effluent was due to the previous use of
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the carbon; the effluent had a low salt content. After 640 gal. , the
C.O.D. value for the effluent was 44 percent of the influent value.
The reconditioned processing water was reused in commercial pro-
duction as a soaking solution after a second lye curing of olives.
The cannery personnel evaluating the reuse reported that the flavor
of the olives after the process seemed to be the same as olives having
normal fresh water soaking.
Analytical results of a transport brine reconditioning experiment
are tabulated in Table XI. The salt content of the effluent reached
the influent level after approximately 440 gal. of brine had passed
through the carbon bed. Colored components and SS were almost
completely removed. The reconditioned transport brine was reused
successfully in the commercial operation.
Analytical Indicators of Reconditioned Brine Quality
Five analytical measurements were used to evaluate the quality of
activated carbon treated brines: C.O.D., pH, total acidity, SS,
and light transmittance. It was found that for the major part of
the treated brine, the values of pH and total acidity (as well as
salt content) were relatively constant (See Tables II and VII). The
SS content was variable in a random fashion due to the sporadic
discharge of carbon fines and retained SS (see Tables III and VII).
The only indicators which showed a systematic variation related
to the extent of treatment which the brines received were C.O.D.
and light transmittance. In a majority of the storage brine treat-
ment experiments, considerable color was removed without cor-
responding substantial changes in the C.O.D. values (See Tables
II, III, IV, XIV, and XV). For this reason it was concluded that
brine color was the most sensitive index of reconditioned brine
quality. This conclusion appeared to be substantiated by the fact
that reconditioned brines of high C.O.D. content and medium
light transmittance values were used successfully in the storage
of freshly harvested olives (See Tables II, VII, XIV, XV, and
XVII).
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Flavor of Olives Stored in Reconditioned Brines
The flavor panel testing of canned black ripe olives comparing
samples from storage in activated carbon reconditioned brines
and in freshly prepared brines did not establish any difference
in quality. The samples from the 15 ton scale storage experi-
ment were not significantly different from olives of the same size
and variety stored for the same period in freshly prepared brine.
A confirmation of this result was obtained indirectly by the fact
that the olives stored in reconditioned brine were sold with no
adverse comments received on the quality of the canned product.
The storage experiments on small lots of olives in three different
types of reconditioned brines were evaluated by a laboratory taste
panel. The samples prepared from olives stored in brine having
the lowest extent of treatment and longest storage period before
use were ranked as the best of the four samples presented. The
three samples from the 69- 1 storage conditions (See Table XVIII)
showed values of 2. 13, 2. 14 and 2. 57 . This result suggests that
the quality of the olives from individual storage pails was different.
The two values obtained for the ranking of the commercial control
sample were 2.39 and 2.45. This result indicates the precision
in ranking to be ±0.06. The overall conclusion from the taste
panel results on all the samples from olives stored in reconditioned
brine was that their quality was similar to that of olives stored in
virgin brine.
Use of Regenerated Carbon
All of the results obtained in the evaluation of the performance of
carbon reactivated for reuse indicate that the reactivated carbon
is as efficient as virgin carbon (See Table XVI). A particularly
significant fact is the lack of a requirement for water washing be-
fore activation.
-45-
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Cost Estimates for Brine Reconditioning
The basis for any decision to use the brine reconditioning technology is
its contribution to the wholesale cost of the final product produced for
sale compared to the costs generated by alternative methods of operation.
The alternatives which are available to the industry which will keep their
salt discharges at or within levels which meet the water quality standards
are:
1. Conventional operation with dilution of saline wastes with fresh
water to permissable salt level for discharge.
2. Conversion of operation to complete fresh curing of olives as
harvested.
3. Conventional operation with ponding of saline wastes.
4. Use of salt-free storage systems.
5. Conventional operation with activated carbon reconditioning and
reuse of storage brines and saline processing waters.
6. Combinations of the above methods of operation.
It is beyond the scope of this report to give a detailed cost analysis of
the various alternative methods of operation outlined above. A detailed
cost estimate will be presented on the brine reconditioning approach
based on two options: 1. brine reconditioning at a single site on a 5, 000
tons of olives per year basis with a single use of activated carbon and,
2. brine reconditioning at ten individual plants with a central carbon re-
activation site for a total of 50, 000 tons of olives per year-
The basis for the cost estimate is listed in Table XX. The figures are
derived from the results obtained in this study and are considered con-
servative estimates which allow a safety factor for raw olive variation
and environmental conditions other than those observed during the ex-
perimental period of this project. The critical value of 10 gal.of recondi-
tioned brine for each Ib of carbon is based on the single large scale
storage experiment and alternate cost estimates based on ratios of 15 gal.
and 20 gal. of brine for each Ib of carbon are included for comparison.
-46-
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TABLE XX
BASIS OF CALCULATION OF CARBON COLUMN SIZE, CARBON
INVENTORY AND CARBON REGENERATION REQUIREMENTS
Subject
Value
Annual Weight of Olives Stored
in Brine at A Single Location
Volume of Stored Brine Required
Per Ton of Fresh Olives
Period of Receiving Freshly
Harvested Olives
Storage Period for Recon-
ditioned Brine Before Use
Volume of Brine/Weight of Carbon
(See Tables II, VII, XIV, XV)
Volume of Brine Required Per
Week for 12 Weeks
Annual Carbon Requirement
(Single Use) at 10 gal./lb
Carbon Inventory for Central Regene-
ration Facility Receiving Spent Carbon
from Ten Brine Reconditioning Plants
Olives Harvested for Processing;
Average per year for Period 1961
Through 1968
5000 tons
100 gal.
6 weeks
6 weeks
10-20 gal./lb
41,667 gal.
50,000 Ib
405,000 Ib
37,370 tons
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Assumptions:
Operating Period: 12 weeks; 7 days/week; one 8-hr shift/day, as is
standard practice in the olive processing industry.
Average Flow Through Adsorption System
500,000
12 (7)
- 5, 950 gpd or 12 . 5 gpm
Designed Flow 0.5 gpm/ft2 or 0.025 gpm/ft3
(in pilot unit, best color removal per unit wt of carbon was at 0. 027
gpm/ft3 or 0.75 gpm/1.4 ft2; See Table VIl)
Diameter of Carbon Bed: 5.6 ft
Height of Carbon bed for adequate contact time: 20 ft
Carbon volume: 500 ft / column
Carbon weight: 13, 500 Ibs
Carbon exhausted per day: 595 Ibs
Time to exhaust column: 22. 7,days
Design: Two fixed bed columns in series
OPTION 1
Reconditioned Brine to Act. Carbon Ratio
Capital Cost 10 gal./lb 15 gal./lb 20 gal./lb
2 - 5.6.x 20 ft redwood tanks at $1000 $2,000 2,000 2,000
Screens, distributor plants, etc. 1,000 1,000 1,000
Installation cost 9, 180 9, 180 9, 180
Total capital cost 12, 180 12, 180 12, 180
Amortization, Annual Cost 1,820 1,820 1,820
-48-
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OPTION 1 (Cont'd.)
Operating Costs
Labor (1.6 hrs/day/7 days/week,
12 weeks at 5.00/hr including
fringe benefits)
Reconditioned Brine to Act. Carbon Ratio
10 gal./lb15 gal./lb 20 gal./lb"
$ 672
672
672
Power
Carbon (at $ .31/lb)
Carbon disposal (sanitary land fills
at $ 8.00/ton)
Maintenance
Total Annual Cost
Recovery value of brine components
Water, 500, 000 gal. at $ .20/1000
gal-
Sewer tax (same basis)
Salt at $ 15/ton
Sub -total
Net annual cost -
Cost per ton of olives -
Cost per 1000 gal. of storage brine -
OPTION 2
Capital cost
Installed brine reconditioning units
(12, 180 x 10)
1 - 7 ft I. D. x6ft hearth furnace
60
15, 500
1,200
348
$ 19,600
$ 100
100
1,200
$ 1,400
18,200
3.64
36.40
Reconditioned
10 gal./lb
$ 121, 800
50,000
60
10,333
800
348
14,033
100
100
1,200
1,400
12,633
2.53
25.30
Brine to Act.
15 gal./lb
121,800
50,000
60
7,750
600
348
11,250
100
100
1,200
1,400
9,850
1.97
19.70
Carbon Ratio
20 gal./lb
121, 800
50,000
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OPTION 2 (Cont'd.)
Furnace feed tank
Dewatering screws
Quench tank
Carbon collection tank
Installation of carbon re-
generation plant
Total capital cost
Amortization,*Annual Cost
Carbon inventory
Interest loss on carbon
inventory, Annual
Reconditioned Brine to Act. Carbon Ratio
10 gal./lb 15 gal./lb 20 gal./lb
2,000
7, 000
1,600
2,000
37,800
222,200
33,180
125,600
9,300
2,000
7, 000
1,600
2, 000
37,800
222,200
33, 180
83,600
6,200
2, 000
7,000
1,600
2, 000
37,800
222,200
33,180
62,800
4,650
Operating Costs
Carbon make up
10 plants x 50, 000 Ib/plant
10 percent loss x $0.31/lb
Labor
Power (0.05 kw/lb at
$0.01/kwh)
Fuel (3200 BTU/lb carbon)
Carbon hauling ($0. 10 per ton-
mile, 200 mile round trip
distance)
15,500
3,360
5,000
10,333
2,240
3,750
7,750
1,680
250
400
188
300
125
200
2, 500
*8 percent interest compounded annually for a replacement period of 10 years.
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OPTION 2 (Cont'd.)
Maintenance
Operation of brine reconditioning units
(No carbon costs or disposal costs)
10 plants x $1080 per plant - '
10(672 + 60 + 348)
Reconditioned Brine to Act.Carbon Ratio
10 gal./lb 15 gal./lb 20 gal./lb
250
10,800
250
10,800
250
10,800
Total Annual Cost
$ 78,040
67,241
61, 135
Recovery Value of Brine; water,
salt and sewer tax savings
Net Annual Cost
Net Annual Cost per Cannery
Cost Per Ton of Olives
Cost per 1000 gal. of storage brine
14,000
64,040
6,404
1.28
2.81
14,000
53,241
5,324
1.06
10.64
14,000
47, 135
4,714
0.94
9-42
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SECTION VIII
ACKNOWLEDGMENTS
The advice, counsel and cooperation of the following members of
the Technical Advisory Committee of the California Olive Associ-
ation is gratefully acknowledged:
Orrin Scott Bell Packing Company
Noel Graves California Canners & Growers
J. R. Webster Consolidated Olive Growers
Ralph Fusano Cristo Fusano & Sons
William Perry Early California Foods, Inc.
James Chung Libby, McNeill & Libby
Elton Develter Maywood Packing Company
Marvin Martin Tri-Valley Growers, Oberti Div.
The continued engineering consultation provided by the Engineering
and Development Laboratory, Western Utilization Research and
Development Division, Agricultural Research Service, USDA,
Albany, California, has been most welcome in the planning and im-
plementation of this project.
Financial support for the project provided by the Olive Adminis-
trative Committee and the Olive Advisory Board is gratefully ac-
knowledged.
We welcomed the many suggestions made by Kenneth A. Dostal of
the Pacific Northwest Water Laboratory, WQO, EPA on technical
aspects of the project. We are indebted to William H. Pierce of
Region IX of EPA for advice regarding format, content, and in-
terpretation of results, of this report.
We appreciate the help provided by Bruce Juhola of the Pittsburgh
Activated Carbon Company and G- F. Kroneberger of the BSP Cor-
poration and acknowledge their assistance in preparing cost esti-
mates for full scale commercial installations.
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The following project team was responsible for the operation of the
brine reconditioning unit, the sample collection, and sample analysis:
Walter W. Rose Harry J. Maagdenberg
Jennie Marano Michael Iverson
Valuable contributions to the reporting of the results of the project
were made by:
Edwin S. Doyle Stuart Judd
Walter A. Mercer Jack W. Rails
Project Director Project Coordinator
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SECTION IX
REFERENCES
1. Popper, K., Camirand, W.M., Watters, C.G-, Bouthilet, R.
J. and Boyle, F. P. Food Engineering ^9 (4), 78-80 (1967).
2. Ginnette, L.F. , Forty-Sixth Annual Technical Report of the
California Olive Association, pp 51-57 (1967).
3. Ginnette, L.F. , Forty-Seventh Annual Technical Report of
the California Olive Association, pp 12-17 (1968).
4. Vaughn, R. H. , Martin, M.H., Stevenson, K.E., Johnson, M.
G. and Crampton, V- M. , Food Technology 23^ (6) 832-834
(1969). ~~
5. Jeris, J. S. , A Rapid COD Test, Water and Waste Eng. _4
(5), 87-91 (1967).
6. Diehl, H. and Smith, G- F. , "The Iron Reagents: Bathophenan-
throlene, 2, 4, 6-Tri pyridyl-S-Triazene, Phenyl-2-Pyridyl
Ketoxime, "G. Federick Smith Chemical Company, Columbus,
Ohio 1960, pp. 19-21.
-55-
-------
SECTION X
PATENTS AND PUBLICATIONS
No patents have issued as a result of inventions made during the
course of this project. No patent applications have been made, or
are planned to be made, by the National Canners Association as a
result of work done in this project.
Several presentations of work done in the project have been made
orally during 1968, 1969 and 1970. The first printed account of
results from the project will appear in the proceedings of the Na-
tional Food Processing Waste Symposium, Portland, Oregon,
April 6-8, 1970.
-57-
-------
SECTION XI
APPENDICES
Page No.
A. Analytical Methodology • . . . 60
Volume Measurement . . . • 60
Sampling .-.•...• 60
Sample Storage . • • 60
Chemical Oxygen Demand . • . • 60
Suspended Solids . • 61
Color ......... 61
pH ................ 61
Total Acidity 62
Salt Content 62
Percent-Sodium Hydroxide 62
Iron Determination • 62
Olive Taste Panel. 64
B. Results of Analysis Made on Samples
Collected at Sampling Ports 67
Work at Lindsay 67
Work at Madera 70
C. Salometer Readings On Experimental Olive
Storage Brines . ............... 73
D. Iron Level in Influent and Effluent Salt
Solutions From Activated Carbon Treatment
of Storage Brine • • • 74
-59-
-------
Volume Measurements
A simple measurement, to obtain the flow rate volume from the
carbon tower, was employed using a stop watch and pre-calibrated
plastic container. Tank volumes were either calculated from di-
mensions or from flow rate data. '
Sampling
Grab samples from the influent, effluent and tower port spigots
were obtained at specified intervals of time. Quart glass con-
tainers were used whenever possible to eliminate contamination
of the sample. Each container was clearly labeled by sampling
point, pump rate, date, and time of sampling.
Sample Storage
Samples from the carbon tower were immediately taken to the plant
laboratory refrigerator for temporary storage. After completion
of a regular experiment the samples were gathered and transported
in polystyrene ice chests for the return trip to the Berkeley labora-
tory. At the destination the samples were refrigerated for subse-
quent analysis.
Chemical Oxygen Demand
The Jeris Modified, C.O-D. tests (5) were employed for all analy-
tical data presented in this report. This "rapid" C-O-D. procedure
involves the addition of waste sample to a flask containing mercuric
sulfate. After mixing, 25 ml of dichromate-acid-silver sulfate
misture is added, mixed and placed on a pre-heated hot plate. A
thermometer is inserted in the flask, and the temperature is
checked as the mixture is heated. When 165°C is reached, the
sample is withdrawn and cooled. (Care must be employed in
heating the sample because of the rapid rise in temperature. )
Water is added cautiously, and after further cooling, the solution
is titrated with ferrous ammonium sulfate in the presence of fer-
roin indicator -
-60-
-------
Suspended Solids
A millipore filter apparatus with a 47 mm Type E glass fiber filter
disc is employed in this procedure. The filter disc is dried in an
oven at 103°C for 1 hr, (30 min in a mechanical convection oven)
cooled to room temperature in a desiccator and weighed. The fil-
ter disc is placed in the suction apparatus with tweezers. A volume
of sample to be taken for filtration will depend on the concentration
of the suspended matter in the sample and should be as large as
practical. 100 ml portions are used throughout the report unless
otherwise noted. A well-mixed sample is measured out with a
graduated cylinder and filtered slowly by suction.
Leaving the suction on, with 10 ml distilled water to remove
soluble salts. Dry the filter disc and solids at 103 °C for 1 hr as
previously and allow the disc to cool to room temperature in a
desiccator before weighing.
The suspended solids are calculated in ppm
mg/liter S-S-
R x 106
Sample volume
where R = weight of dried residue.
Color
The color of the waste samples was measured in a Bausch & Lomb
Model 20 Spectrophotometer - The instrument was standardized at
100% transmittance with distilled water at the desired wave lengths
of 425 and 450 mjo,. These wave lengths were selected as those at
which the olive brines showed maximum light absorption. Samples
are read directly in percent transmittance. Aliquots of diluted
samples are necessary if readings fall below 10 percent transmit-
tance .
PH
The measurement of pH of a solution is obtained by the use of a
commercial electrometric portable pH meter- The meter is first
standardized with a buffered pH solution. The appropriate probes
are immersed into the solution under test and the pH determined
by reading the value directly from the meter.
-61-
-------
Total Acidity
In a food plant material, total acidity is a measure of the amount of
acidic substances principally present as organic acids and carbon
dioxide. A 10 ml sample is placed in a 150 ml beaker- Add approxi-
mately 40 ml of distilled water- Using a glass electrode pH meter,
titrate with 0. 1560 N sodium hydroxide with constant stirring to an
end point of pH 8.3. Make sure the tip of the buret is clean and
free from solid alkali. Read the number of ml of sodium hydroxide
used to one-tenth of a ml, and divide by ten. A correction factor
of 1.405 is used to convert the results into percent of acid in terms
of lactic acid.
Salt Content
Pipet 5 mis of an aliquot (5/100 for brine) into a 100 ml beaker-
Add approximately 25 ml of water. Use a PHOTOVOLT Model 115
Electronic pH meter with the silver and calomel electrodes. Im-
merse the electrodes in the solution and set the main switch to
reference. Adjust the pH scale at 7. 0 with the standardizing con-
trol knob. Titrate with -0855 N silver nitrate (do not titrate with
silver nitrate solution that has been exposed to light in the buret
for more than a few hours), with constant stirring until the needle
rests at 11.5. Read the number of ml of silver nitrate used to one-
tenth of a ml and divide by ten. The result is the percent salt.
Percent Sodium Hydroxide
A suitable sample of lye water (less than 25 ml) is titrated with
0. 0908 N H2SO4 with stirring to an end point of pH 7.0. The per-
centage of NaOH in the lye water is given by:
% NaOH = 4 (A* B)
Where: A = volume of acid used
B = normality of the acid
C = size of sample to be titrated, in ml
Iron Determinations
10 ml samples of brine were placed in evaporating dishes and heated
under infrared lamps until the water was removed. The dishes were
-62-
-------
placed in a muffle at 325°C until smoking ceased. The muffle fur-
nace door was closed and the temperature was increased to 550 °C.
The dishes were removed after 1-2 hours and the ash broken up,
wet with water, dried and re-ashed for 1 hour- The residue from
the ashing was dissolved in 2 ml of 1 : 1 hydrochloric acid : water-
The solution was heated for approximately 2 minutes under heat
lamps and then transferred to 25 ml volumetric flasks and diluted
to the mark with distilled water used to rinse the ashed sample dish.
The analytical method was adapted from that of Diehl and Smith (6).
Reagents Bathophe nan thro line, 0.001 M Solution. Prepare a 50 per-
cent ethyl alcohol solution of bathophenanthroline by dissolving
0. 0332 g of 4, 7-diphenyl- 1, 10-phenanthroline (C24H16N2, Mol. wt
332; G- Frederick Smith Chemical Company, Item No. 108) in 50
ml of ethyl alcohol and diluting with 50 ml of iron-free water.
Store this solution in a glass stoppered, reagent bottle.
Hydroxylamine hydrochloride, 10 percent iron-free solution.
Reagent grade hydroxylamine chloride contains appreciable amounts
of iron. Dissolve 10 g of hydroxylamine chloride in 100 ml of water
in a 125 ml separatory funnel. Add 2 ml M bathophenanthroline and
mix well. Add 10 ml of isoamyl alcohol and shake vigorously. Al-
low the liquids to separate and draw off the lower, aqueous layer
into a second separatory, funnel. Add 2 ml of 0. 001 M bathophenan-
throline and repeat the extraction to insure complete removal of
iron. Store iron-free hydroxylamine chloride solution in a glass-
stoppered, reagent bottle. This solution has a pH of 1.5 to 1.75.
It has been shown that all excess bathophenanthroline is extracted
from solutions purified in this manner. The small amount of iso-
amyl alcohol left in the solution is not detrimental.
Sodium Acetate, 20 percent iron-free buffer solution. Dissolve 20
g of sodium acetate in 100 ml of water in a 125 ml separatory funnel.
Add 2 ml of 10 percent hydroxylamine hydrochloride solution to re-
duce the iron present. Add 2 ml of 0.001 M bathophenanthroline and
mix well. Add 10 ml of iso-amyl alcohol and shake vigorously.
Allow the liquids to separate and draw off the lower, aqueous layer
into a second separatory funnel. Repeat the separation to insure
complete removal of iron. Store the solution in a glass-stoppered
reagent bottle.
Iso-amyl alcohol. Reagent grade iso-amyl alcohol may be used
without further purification. Technical grade material must be dis-
tilled before use. N-amyl or n-hexyl alcohol also can be used.
-63-
-------
Standard Iron Solution. 10 and 1.0 ppm Fe. A standard iron solu-
tion may be prepared from primary standard electrolytic iron (G-
Frederick Smith Catalog, Item No. 226, p. 45) by dissolving a
suitable weighed quantity in HC1 and diluting to a known volume.
Five (5) ml of dissolved ash solution (equivalent to 2 ml of olive
brine) was pipetted into a 125 ml separatory funnel containing 10
ml water and 2 ml hydroxylamine solution. The solution was
mixed and allowed to stand for 5 min for all the iron to be reduced
to the ferrous form. After 5 min 2 ml of sodium acetate buffer
solution and 4 ml bathophenanthroline were added and mixed. To
this solution 6 ml of iso-amyl alcohol was added and extracted by
shaking vigorously. The layers were allowed to separate and the
lower, aqueous, layer was discarded. The alcohol layer was run
into one of a matched set of Evelyn colorimeter tubes. The sepa-
ratory funnel was rinsed twice with 5 ml portions of 80 percent
ethanol. The rinsings were added to the Evelyn tube and the solu-
tion diluted with alcohol to 25 ml. A reagent blank was also pre-
pared in the same manner. The transmission was read with a 515
m(o, filter on an Evelyn Photoelectric Colorimeter (Rubicon Co. ,
Philadelphia, Pa. ). A calibration curve can be made with standard
iron solutions extracted as above. The experimental values can be
read from the curve. The ppm Fe in the olive brine was calculated
by applying the appropriate dilution factor -
Olive Taste Panel
A laboratory taste panel room was used for all laboratory taste
tests. The room was furnished with a table, partitioned into eight
booths, and eight folding chairs. The tests were carried out under
conditions of low illumination so that the olives were not judged by
appearance. A triangle presentation of three samples or a series
of four samples were presented for preference ranking. For the
triangle test 3 olives from one can were placed in each of two
paper cubs. The third paper cup held 3 olives of the designated
odd sample. The order of presentation (odd sample in cups marked
L, M, or N) was randomized. The samples were presented in an
aluminum cupcake tray along with a cup of cold water.
For the preference ranking test, 2 olives from each of 4 cans of
samples were placed in four different cups coded L, M, N, and O.
The panelist was asked to complete the scoring sheets shown on
the next two pages.
-64-
-------
CANNED OLIVE FLAVOR
Instructions: Go to a lighted booth. Sit down and taste samples.
Mark results and write initials on scoring sheet. Turn off light.
Take tray of samples and scoring sheet to cutting room.
You are asked to taste three olive samples. Two of the samples
are identical and one is different. Put a check mark (N/ ) after
the two identical samples.
Code
L
M
N
Duplicate Samples
Taster's initials
Date
-65-
-------
OLIVE TASTE PANEL
Please taste and rank samples in order of flavor preference. Take
completed scoring sheets and used sample tray to cutting room.
Code
L
M
N
O
Flavor Ranking
1 = Best; 4 = Worst
Date
Taster's initials
-66-
-------
Work at Lindsay
TABLE XXI
ANALYSIS OF SAMPLES COLLECTED AT SAMPLING PORTS- (Lindsay)
Gallons
of
Date Effluent
10-16-68
rt
11
ii
n
it
it
u
u
ii
it
ii
u
ii
10- 17
ii
ii
u
u
it
n
ii
ii *
n
n
it
n
it
10-18
it
" *
it
ii
n**
270
450
450
630
630
630
900
990
990
990
1350
it
it
ti
2010
n
n
u
2910
11
ii
n
3150
3510
3750
n
3990
n
4660
n
5300
n
n
5625
(See Table II)
Port Flow
Number Rate, gpm
1
1
2
1
2
3
1
2
3
5
1
2
3
5
1
2
3
5
1
2
3
5
5
3
5
3
5
3
5
3
5
2
3
5
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2.5
2.5
2.5
2.5
PH
4.6
4.5
4.7
4.5
4.4
4.5
4.4
4.6
4.4
5.5
4.4
4.4
4.4
4.9
4.4
4.4
4.6
5. 1
4.3
4.4
4.4
4.3
4.3
4.2
4.3
4.3
4.2
4.3
4.2
4.2
4.2
4. 1
4.4
4.2
4.2
Percent
NaCl
5.2
5. 1
5.3
5.4
5.4
5.4
5.5
5.5
5.4
5.5
5.4
5.4
5.5
5.5
5.3
5.4
5.3
5.4
5.5
5.5
5.4
5.5
5.5
5.3
5.5
5.5
5.5
5.5
5.5
5.5
5.5
5.8
5.8
5.8
5.8
C.O.D.,
mg/liter
800
N.M.
N.M.
N.M.
N-M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
9000
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
N.M.
16,500
12,800
16,400
13,600
15,900
15,000
16,700
15,800
15,300
15, 100
-67-
-------
Work at Lindsay (Cont'd. )
ANALYSIS OF SAMPLES COLLECTED AT SAMPLING PORTS (Cont'd)
Gallons
of Port
Date Effluent Number
10- 18
11
ii
10- 19 *
ii
11
" *
ii
1!
II
10-20
ii
" >'f
10-21 *
10-21**
"
6470
6470
7355
7355
7680
7905
8375
8400
8700
9150
9650
9800
10, 985
11, 105
11,345
5
3
5
3
5
5
5
5
5
5
5
5
5
5
3
5
Flow
Rate, gpm
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.0
2.0
2.2
PH
4.2
4.0
4.3
4.2
4.2
4.2
4.5
4.0
4.0
4.0
4.0
4.0
3.9
4.0
4. 1
4.2
Percent
NaCl
5.8
6.0
6.0
6.0
6.2
6.2
6.2
6.2
6.2
6.0
N.M.
N.M.
N.M.
6.0
--
—
C.O.D. ,
mg/liter
15,300
11,400
10,700
15,500
14, 800
16, 800
14, 800
15,400
14,600
17,700
N.M.
N-M.
N.M.
N.M.
--
—
* 60 Ibs fresh carbon added
** Influent Change
TABLE XXII
MEASUREMENT OF SUSPENDED SOLIDS (See Table II)
Effluent Volume, Suspended Solids,
Type of Sample
Influent
Effluent
Effluent
Effluent
Influent *
Influent
Effluent
Gallons
0
1980
3770
7355
7680
8700
9000
mg/1
280
220
220
164
200
286
196
* Change in Influent
-68-
-------
Work at Lindsay (Cont'd.)
TABLE XXIII
MEASUREMENT OF LIGHT TRANSMISSION
AT 450 NANOMETER WAVELENGTH (See Table II)
Type of
Sample
Influent
Port 1
Port 1
Port 2
Port 1
Port 2
Port 3
Effluent
Port 1
Port 2
Port 3
Effluent
Port 2
Port 3
Port 5
Port 1
Port 2
Port 3
Port 5
Port 3
Effluent
Effluent
Effluent
Volume »
Gallons Dilution Factor Transmission, Percent
0
270
450
450
630
630
630
630
900
990
990
1,260
1,350
1,350
1,350
1,980
1,980
1,980
1,980
2, 880
3, 150
3,410
1 : 5
None
None
None
1 : 5
None
None
None
1 : 5
None
None
None
None
None
None
1 : 5
1 : 5
None
None
None
None
None
76
62
65
63
86
67
84
75
88
79
72
92
76
86
84
83
72
52
68
62
96
92
-69-
-------
Work at Madera
— — — — ~— - — - — — — ^— J- " 1 '
ANALYSIS
J-ULI yv^vj. v
OF SAMPLES
COLLECTED AT SAMPLING PORTS - (Made:
(See
Effluent
Volume, Port
Date Gallons Number
4-14-69 160 1
2
3
280 1
2
3
400 1
2
3
520 1
2
3
640 1
2
3
720 1
2
3
4
800 1
2
3
4
1080 1
2
3
4
Table
PH
4.5
6.9
*
4. 1
5.4
*
4.0
4.5
*
4.0
4.5
*
3.9
4.2
*
3.9
4. 1
*
*
3.9
4.0
*
*
3.8
3.9
*
*
IV)
NaCl,
Percent
4.8
4. 1
4.8
5. 1
4.5
5.2
5.6
4.8
5.2
5.6
4.5
5.2
5.5
4.8
5.3
5.4
5.3
4.8
5.3
5.4
5.4
6.3
5.3
5.4
5.5
C.O.D. ,
mg/liter
17,200
7,000
20,800
12,800
22,800
18,400
16,480
22,800
18,400
14,200
23,000
18,700
16,800
22,400
18,200
14, 900
18,700
22,400
18,900
21,000
16,300
36,400
20,200
18, 100
16,600
-70-
-------
Work at Madera (Cont'd. )
ANALYSIS OF SAMPLES
COLLECTED AT SAMPLING PORTS (Cont'd
Effluent
Volume, Port
Date Gallons .Number
4-14 1200 1
2
3
4
4-15 1240 1
2
3
4
1360 1
2
3
4
1480 1
2
3
4
1600 1
2
3
1880 1
2
3
4
2000 1
2
3
4
PH
3.8
3.9
•*
*
3.7
3.7
*
*
3.7
3.6
*
*
3.8
3.6
*
*
3.8
3.6
*
3.7
3.6
*
*
3.7
3.6
*
*
NaCl,
Percent
6.3
5.3
5.4
6.6
6.6
6.5
6.9
6.9
6.3
6.8
6.9
6.9
6.0
6.0
7. 1
6.9
6.0
6.0
6.9
6.3
6.0
7. 1
7.0
6.0
6.8
7. 1
7. 1
C.O.D.,
mg/liter
35,600
19,200
19,500
18,600
34,400
27,200
22,600
22,600
36,600
30,800
26,700
26,400
34,400
31,600
29,800
21,300
34,400
30,400
27,000
22,600
31,200
26,600
26,700
35,200
32,400
28,200
27,700
* Little change from other values, not recorded.
-71-
-------
Work at Madera (Cont'd.)
ANALYSIS OF SAMPLES
COLLECTED AT SAMPLING PORTS
(See
Effluent Sampling
Volume, Port
Date Gallons Number
5-12 160 1
2
3
4
5
400 1
2
3
4
5
800 1
2
3
4
5
5-13 1040 1
2
3
4
5
1160 1
2
3
4
5
Table Vl)
PH
4.2
4.2
4.5
4.7
4.6
4. 1
4.2
4.3
4.4
4.8
4. 1
4. 1
4.3
4.2
4.4
4.0
4.0
4.2
4.2
4. 1
4.0
4.0
4.2
4.2
4.2
Total
Acidity,
g Lactic
per 100 g
0.97
0.96
0.80
0.53
0.37
1.08
0.98
1.00
0.81
0.67
1.08
1.05
1.07
1.03
0.98
1.50
1.42
1.48
1.31
1.03
1.50
1.52
1.50
1.38
1.50
C.O.D.,
mg/liter
39,700
36,300
28,500
28, 500
23,700
40,300
38,400
30,900
30,400
28,000
32, 800
40,500
39,000
34,700
32,300
35,000
36,300
35,000
33,000
31,700
38,700
36, 500
32,800
33, 100
31,200
-72-
-------
Work at Oroville
TABLE XXV
SALOME TER READINGS ON
EXPERIMENTAL OLIVE STORAGE BRINES
Salometer Reading on
Date of Salt Additions
Tank
Number
69-1-A
69-1-B
69-1-C
69-1-D
69-2-A
69-2-B
69-2-C
69-3-A
69-3-B
69-3-C
10-7
69
12
12
12
12
12
12
12
12
12
12
10-14
69
15
14
14.5
13.5
13
13.5
13
14
13
12.5
10-21
69
17
12
15
16
16
15.5
15
17.5
16.5
17
10-28
69
28
28
27.5
25
27
27
27
26.5
26
27
11-4
69
30
29
29
26
27
27
27
26.5
26
27
11-11
69
23
24
22
23
24
23
22
24
22
24
11-25
69
30
28
33
29
28
29
30
26
27
26
12-15
69
28
28
28
29
27
28
28
26
26
26
1-13
70
29
28
29
29
28
28
29
26
26
26
2-9
70
27
26
28
29
28
29
29
25
27
25
-73-
-------
TABLE XXVI
IRON LEVEL IN
INFLUENT AND EFFLUENT SALT SOLUTIONS FROM
ACTIVATED CARBON TREATMENT OF STORAGE BRINE
Date of
Sampling
7-21-69
7-25-69
7-28-69
8-5-69
Table VII
Effluent Gallonage
3030
6060
9615
17,355
Iron Concentration,
ppm
Influent Effluent
9-90
8.80
9.86
14.87
16. 17
13.02
8.42
11.87
-74-
-------
1
5
/tree. ssi on Number
n Subject Fit'ld &. Group
0 5 D
SELECTED WATER RESOURCES ABSTRACTS
INPUT TRANSACTION FORM
Organization
National Canners Association, Berkeley, California 94710
Title
RECONDITIONING OF FOOD PROCESSING BRINES
I Q Authors)
Mercer, W.
16
21
Project Designation
12060 EHU
Note
Rails, J.
22
Citation
Berkeley, California, National Canners Association, 1970, (no. of pages, 76,
(no. of figures, 5), (no. of tables, 26), and (no. of references, 6).
23
Descriptors (Starred First)
*Brines, ^Canneries, #Brine disposal, * Activated carbon, ^'Reclaimed water,
Industrial wastes, Waste treatment
25
Identifiers (Starred First)
*Olive brines
27
Abstract
Storage brines and processing waters from the production of canned ripe
olives and glass packed green olives were treated with activated carbon.
The reuse potential of reconditioned brines was evaluated. Reconditioned
storage brines can be used to store freshly harvested olives for commer-
cially significant periods. Canned samples prepared from olives stored
in reconditioned brine were of good quality. Reconditioned brines of lower
salt content were reused with no detectable effect on the quality of the
final product.
Estimates for commercial application of activated carbon treatment of
storage brines show a cost per ton of olives stored of $3. 64 when capi-
tal costs are amortized over 10 years for a cannery storing 5, 000 tons
of olives annually. Ten olive canneries reconditioning brine and sending
spent carbon to a centrally located reactivation facility would have a cost
of $1.28 per ton of olives stored.
AbKtractor
J. Rails
Institution
National Canners Association, Berkeley, California
WR:<02 (REV JULY 19691
WRSI C
SEND TO: WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT OF THE INTERIOR
WASHINGTON. D. C. 20240
GPO: 196?— 359.330
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