EPA-60Q/2-77-191
September 1977
Environmental Protection Technology Series
COUNTERCURRENT RINSING
ON A HIGH-SPEED HALOGEN
TINPLATING LINE
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental Protection
Agency, have been grouped into five series. These five broad categories were established to
facilitate further development and application of environmental technology. Elimination of
traditional grouping was consciously planned to foster technology transfer and a maximum
interface in related fields. The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
This report has been assigned to the ENVIRONMENTAL PROTECTION TECHNOLOGY
series, this series describes research performed to develop and demonstrate instrumenta-
tion, equipment, and methodology to repair or prevent environmental degradation from point
and non-point sources of pollution. This work provides the new or Improved technology
required for the control and treatment of pollution sources to meet environmental quality
standards.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and approved
for publication. Approval does not signify that the contents necessarily reflect the views and
policy of the Agency, nor does mention of trade names or commercial products constitute
endorsement or recommendation for use.
This document Is available to the public through the National Technical Information Service,
Springfield, Virginia 22161.
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EPA-600/2-77-191
September 1977
COUNTERCURRENT RINSING
ON A HIGH-SPEED HALOGEN
TINPLATING LINE
by
D.A. Pengidore
National Steel Corporation
Weirton Steel Division
Weirton, West Virginia 26062
Grant No. S801989
ROAP No. 21ADT-003
Program Element No. 1BB610
EPA Project Officer: Robert C. McCrillis
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, N.C. 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, D.C. 20460
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ABSTRACT
Countercurrent rinsing, as applied to high speed strip plating
lines, involves the use of a compartmentized rinsing tank. The
objective of the use of this method of rinsing is to reduce the amount
of water required so as to have a volume of liquid more easily handled
to recover the chemicals.
This report covers the first use of this type of rinsing on a high
speed plating line. The first unknown to be studied was the operating
performance of the multistage rinse system to determine whether or not
the basic principles of countercurrent rinsing would hold for a high
speed strip plating operation. Secondly, the best manner for recovering
the chemicals in the concentrated stream from this rinse system had to
be determined.
Efforts to recycle the concentrated rinse back into the main plating
system and the problems which were encountered are also described in this
report. New technology for solving these problems is described as well
as an alternate method involving indirect recycling by means of the
Detinning Plant.
This report was submitted in fulfillment of Grant S801989 received
by the National Steel Corporation, Weirton Steel Division from the
Environmental Protection Agency.
ii
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CONTENDS
PAGE
Abstract ii
List of Figures v
List of Tables vi
Acknowledgment
SECTIONS
I Introduction 1
II Conclusions 4
III Recommendations 5
IV Description of Plating Process 6
V Theory and Description of the Countercurrent Rinse
Prucsss °
VI Design and Installation of Countercurrent Rinse
Equipment 1°
VII Operational Results
A. Operating Practices and Experience 20
3. Rinsing Performance 21
C. First Problem of Chloride Buildup 23
D. Snonoraio Study for One Year of Operation 25
E. Problems Generated 27
VIII Solutions to Problems Generated
A. Use of Hydrofluoric Acid 29
B. Use of An Alkalinity Removal Unit 32
C. Indirect Recycle Via Detinning Plant 34
iii
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PAGE
IX Environmental Aspects
*
A. General Information 36
B. Background Survey (Phase I) 42
C. Evaluation of Countercttrrent Rinsing (Phase III) 47
D. Discussion of Results 49
X Bibliography 52
XI Appendices 53
iv
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LIST OF FIGURES
NO.
1 Reclaim Rinse 7
2 Horizontal Pass Acid KLectrotinning Line Configuration
(Halogen Process) 7
3 Math Model 10
4 Rinse Tank Equilibrium Concentration Two Tank System 13
5 Rinse Tank Equilibrium Concentration Three Tank System 14
6 Rinse Tank Equilibrium Concentration Four Tank System 15
7 Multistage Spray Rinse Tank Piping Schematic 19
8 Chloride Concentration vs Time 24
9 Rate of Monthly Consumption - No. 6 Electro-Line 26
10 Amotint of Chlorides in System
November 1974 - November 1975 28
11 Proposed Hydrofluoric Tank 30
12 Distribution System For Strong Acid Using Neither
Pumps or Carboy 31
12A Flow Chart of the Pet inning and Tin Recovery Process 35
13 Background Rinsing System
Phase I Sample Points 37
14 Countercurrent Rinsing System
Phase III Sample Points 38
15 Photograph - Recovery Tank 39
16 Photograph - Spray Wash 40
17 Photograph - Hot Rinse ' 41
18 Sampling Diagram 43
19 Water Sampler 44
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LIST OF TABLES
NO. PAGE
1 Concentrations of Stannous Tin in Each Stage 22
2 Phase I - Background Effluent Loadings 46
3 Phase III - Countercurrent Rinsing Effluent Loadings 48
4 Phase III - Comparison of Background vs Countercurrent
Rinsing Effluent Loadings 51
vi
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ACKNOWLEDGMENTS
The following personnel and organizations are recognized for their
contributions and assistance in preparation of this report:
National Steel Corporation:
Weirton Steel Division:
Mr. A. J. Lamantia - Assistant Project Director
Mr. G. Current - Assistant Project Director
Mr. J. T. Gilmore - Engineering
Mr. D. Montgomery - Environmental Control
Research and Development Division:
Mr. L. W. Austin - Technical Director
Mr. J. R. Suitlas - Environmental Control
Mr. C. V. DeCaria - Environmental Control
E. I. DuPont De Nemours and Company:
Dr. D. A. Swalheim
Environmental Protection Agency:
Mr. R. C. McCrillis - Project Officer
Metallurgical Processes Branch
Industrial Processes Division
vii
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I-INTRODUCTION
Weirton Steel Division of National Steel Corporation has completed
research on the project "Demonstration and Evaluation of Countercurrent
Rinsing for Reducing Pollution from a Halogen Tin Plating Line". This
research was sponsored in part by the U.S. Environmental Protection
Agency.
This project was designed to demonstrate that the use of counter-
current rinsing is a viable approach to reducing pollution from this
type of plating operation and to conserving valuable materials. This
demonstration according to Environmental Protection Agency is an essential
prerequisite to the industry-wide acceptance of this process because of the
complexity of the electrolytic solutions used and the high speed at which
the plating lines are operated. Any increase in the concentration of
either the ionic constituents of the plating bath or the solid (sludge)
material contained therein caused by the return of the concentrated effluent
from the first rinse tank to the main electrolyte could result in either
the production of poor quality or unsaleable tinplate or the frequent
disposal of the expensive plating solution or both.
The demonstration and eventual application of countercurrent rinsing
systems on halogen tin plating operations could have a significant impact
on the amount of pollutants discharged from tin plating operations as
approximately fifty percent of the tinplate in the United States is produced
by the halogen process. In view of the above the project was initiated and
completed in 36 months.
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Technical Background
In the halogen tinplating process, a steel strip is cleaned in an
alkaline solution, pickled and passed through a series of electrolytic
cells containing a tin bearing solution. Following the actual plating
operation the strip must be rinsed before being processed further. Typically
the rinsing takes place in three stages; the dragout recovery, the spray
wash and the hot rinse. In the dragout recovery tank the strip is dipped
into the rinsing solution (water contaminated with plating solution)
and is further rinsed by a set of sprays followed by wringer or squeegee
rolls. The solution which is sprayed onto and wiped off of the strip flows
into the recovery tank. Solution not fed back into the main system is
discharged to the sewer. This discharge is the most contaminated effluent
from the halogen plating process and is made up of the same constituents
as the plating solution but is in a form too dilute to reuse. The major
pollutants in this stream are tin, cyanides, fluorides and suspended solids.
Several concepts for treating this primary dragout rinse had been
proposed. These processes included ozonation and alkaline chlorination
for destruction of cyanide wastes, calcium precipitation for the removal
of fluorides, tin hydroxide formation and ion exchange for the removal of
tin and thickening for removal of suspended solids. It appears that these
processes may be workable; however, in most cases, the capital and operating
costs for these systems are high and the space requirements for these
processes preclude their installation in existing plating shops. Also,
none of these processes is easily adaptable to the concept of zero waste
discharge.
The use of countercurrent rinsing was suggested by personnel at
National Steel Corporation as being a process which could achieve a zero
discharge at minimal capital and operating expense as well as being a
system which would not require excessive space. The process involves the
use of countercurrent rinsing to concentrate the dragout wastes sufficiently
so that they may be returned to the plating solution storage tank and reused.
Computer simulations were run on the system and it was found that the number
of countercurrent rinsing tanks required to achieve the necessary concentration
in the first rinse tca:k was not excessive and could be retrofitted into an
existing plating line. The main problem anticipated with the system was the
buildup of sludge at an excessive rate in the plating solution. It was felt
that this sludge buildup could be controlled via a chemical identified as
AA40. This chemical, developed by National Steel Corporation in conjunction
with E.I. DuPont DeNemours and Company, Inc., minimizes the formation of
this sludge in the plating process.
General Objective
The general objective of this project was threefold:
1. To successfully design and to install a countercurrent rinsing system
on an existing halogen tinplating line,
2. To demonstrate that over a long period of time the recycle of the
primary dragout rinse could be achieved without loss of product
quality or frequent solution changes,
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3. To demonstrate that the system would significantly reduce the amount
of pollutants discharged from a halogen tin plating process, perhaps
even to achieve zero discharge.
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II-CONCLUSIONS
A countercurrent rinse system was designed and installed on the
Weirton Steel Division No. 6 Electrotin Line. A four stage system was
designed for the recovery of the dragout electrolyte.
Mo design problems were encountered mechanically in the four stage
rinse unit. Equivalent or improved rinsing of the strip resulted from
the use of this new system. No problems with sludge buildup were
encountered.
Problems resulted due to buildup of chlorides in the main electrolyte
upon recycle of the concentrated rinse stream containing the recovered
dragout. Methods to solve this problem are being investigated to enable
recycle of the rinse water back to the main plating system. An alternate
method for recovering the chemical values of the recovered dragout is also
a definite possibility.
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III-RECOMMENDATIONS
It is recommended that a second phase be instigated to evaluate
both the recycle of the concentrated rinse into the main (on line) bath
and indirect recycle involving the Detinning Plant.
The problems uncovered in the direct recycle of the concentrated
rinse from countercurrent rinse system may be solved by a new technique
in removing sodium ions from the rinse stream or the main bath. Another
system was also investigated.
Plans are under way to recover immediately the tin values from the
dragout recovery system by sending the rinse solution to the Detinning
Plant. Full recovery of the fluorides and other constituents at the
Detinning Plant is also under investigation. This method for recovery
may be the most desirable after all the test results are evaluated.
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IV-DESCRIPTION OF PLATING PROCESS
The Halogen Tin Process is designed to plate tin at high current
densities and to produce high-quality tin deposits required for
continuous electrotinning of strip steel. The process was introduced
commercially in 1942.
The halogen tin bath, as the name implies, is formulated with halogen
salts. The bath is operated with a relatively high chloride concentration
to obtain maximum conductivity. Fluoride functions largely as a ccmplexing
ion in stabilizing the stannous tin. It combines with the tin to form a
sodium fluostannite complex salt, the composition of which may be expressed
as Na/^SnF^. In the absence of fluoride, stannous chloride hydrolyzes
in the pH range 2-4 to form precipitated hydroxy salts.
The halogen bath is subject to oxidation when operated under highly
aerated conditions such as are encountered in high speed strip plating lines.
The presence of small amounts of iron or copper salts in the halogen bath
acts as an accelerator in promoting the oxidation. Without an inhibitor,
substantial amounts of stannic tin are formed in the bath through oxidation.
In addition to depleting the stannous tin, oxidation causes a significant
fluoride loss from the electrolyte since each mole of stannic tin combines
with six moles of fluoride to form sodium fluostannate (NagSnFfc). In
contrast to the high solubility of the sodium fluostannite salt (
the sodium fluostannate is relatively insoluble in the electrolyte and
separates as a sludge. Addition agents are added to the bath in order to
deposit the fine grain type of tin required for continuous electrotinning
of strip steel. Without additives, the tin deposit is nonadherent and
spongy.
With the high cost of tin and tin salts along with the costs of the
fluoride and addition agents, each gallon of electrolyte represents over
one dollar in value.
The halogen bath is used in a horizontal type process configuration
(see Figure l). This design comprises a succession of small horizontal
cells. The plating solution is circulated continuously through each cell.
Electrical contact is made to the strip by the rolls at each end of the
cell. The tin anodes are positioned close to the strip travel path,
which is just under the solution level, and rest on a center contact
support and end support within each cell.
After passing through the plating cell, the strip is passed through a
reclaim rinse (see Figure 2) in which the residual plating solution may be
removed. The bright, lustrous finish of electrolytic tinplate is obtained
by fusing and quenching the matte tin coating resulting from the plating
process.
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RECL/MM RINSE
COUNTER, CURRENT
R\NSE SYSTEM
SPRAY RVMSE
HOT
SECTlOM
F^ure 1. Reclaim rinse.
DRYER
-
PL.A.TER
TR.AVEI
Figure 2. Horizontal pass acid electrotinning configuration (halogen process).
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V-THEORY AND DESCRIPTION OF COUNTERCURRENT RINSE PROCESS
In the production of tinplate, it is essential that after the strip
leaves the last plating cell the electrolyte be rinsed completely from the
surface of the tin-plated strip. It has been the practice in the mill to
employ ample quantities of rinse water to effect this removal and to
insure the cleanliness of the final product. However, with this practice
c-u.]y a small amount of the electrolyte removed from the last plating cell
on the surface of the strip can be recovered and reused in the plating
system. Rinse water that is put into the plating system is limited to
only the amount needed to maintain volume. The bulk of the rinse water
goes into the sewer and is a contributor to stream pollution. In order
to effect & higher percentage of recovery of dragout, the volume of rinse
water must be decreased and the concentration of electrolyte increased.
A method that can do this is countercurrent rinsing.
As its name implies, the flow of rinse water is counter to the flow
of the strip. The main advantage of this type of rinsing is the ability
of a much smaller quantity of water to effect the same degree of dragout
removal from the strip. This insures the same cleanliness of the strip
after rinsing and results in a smaller volume of rinse water that can
all be used as makeup back in the main system. This volume has a high
concentration of electrolyte salts and effects almost total recovery of
dragout.
ADAPTATION TO MILL USE
Figure 2 shows the outline of a typical reclaim rinse tank into which
the strip passes immediately after the last plating cell. The dotted line
shows the present path of the strip through the reclaim tank. The strip
is deflected down into the rinse water around sink roll (JQ) from the wringer
rolls (Ko and K]j . The strip emerges from the tank from sink roll "J]_"
into wringers "!]_" and "I2-" From this set of wringer rolls, the strip
is further wasvod in tho hot rinse tank.
To employ the principles of countorcurrent rinsing, the tank now in
place, or a new tank to replace the existing tank, must be divided into
compartments. A four-stage system is shown in Figure 3. The flow of
rinse water must be opposite to the direction of strip travel. The flow
proceeds through each compartment by the proper positioning of overflow
weirs. The level of rinse water is lower in each succeeding compartment
or stage. The same rinse water flows through each stage. There are two
ways in which the strip may be contacted with the water in each compartment.
Sink rolls could be placed below the solution level in each compartment.
The strip would thus be diverted down into each compartment and would exit
through wringer rolls located between compartments. The second method, would
be to pass the strip directly across the top of the compartments as shown
in the sketch. The solution in each compartment would be sprayed onto the
strip from pumps as indicated. The solution would drain back into each
individual compartment at the entrances of the wringer rolls, such as
and (IQ-II)• In the opinion of the operating
8 .
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people, this method would have advantages. All sink rolls would be eliminated.
These rolls are sources of trouble since their positions make them difficult
to clean. Also strip breaks at these locations would entail more down time.
It is believed that with the proper size pumps and good spraying
practice, the mixing of solution in each stage with the drag through films
can be as good, or better, than with the design involving sink rolls. One
control is required on the feed water at point A. When the line is not
running this valve must be closed to prevent dilution of the system. The
flow of the rinse water is A to B to C to D to E.
With a three or four stage system the mathematics indicate the
possibility of recovering over 90 percent of the dragout electrolyte.
Good mixing of the solution in each stage with the film on the strip is
required in approaching the theoretical performance. Cost savings should
be considerable especially when all the electrotin lines are considered
on a yearly basis.
Using the math model shown in Figure 3, the equilibrium concentrations
in each rinse tank of a countercurrent system having "M" tanks can be found
by solving "M" simultaneous material balance equations. One equation is
written for each tank. A typical equation for the nth tank is:
,! - (D + R) X
n
= 0
where
Xn =
D =
R =
the equilibrium concentration in the nth rinse
tank - ounces/gal
dragout flow rate - GEM
countercurrent flow rate - GPM
K0 = the cell concentration (a constant) ounces/gal
If K = 6, the countercurrent flow ratio, is substituted, the typical
equation becomes:
X
n_l- (1 + K) Xn + K X I = 0
n
After solving sets of these equations for 2, 3 and 4 tank systems,
it was found that the solution for the equilibrium concentration in the
nth tank of a system of "M" tanks could be generalized as follows:
r~
' i = M - n
I (Ki)
i = o
\n
Kr
i = M
I
1=0
L_
(Ki) I
I
I
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CELL
f
^ ^
.,
"X. ^
^
" r- 1 " 'J
TANK NO 1
TANK NO 2
TANK n
'-I
T
TANK M
KO
D
R
K
M
n
PLATING CELL CONCENTRATION, ml/1 (oz/gal.)
= DRAG OUT RATE, l/min (gpm)
= COUNTERCURRENT FLOW RATE, l/min (gpm)
= R/D COUNTERCURRENT FLOW RATIO
X2 XM = EQUILIBRIUM RINSE TANK
CONCENTRATIONS, ml/I (oz/gal.)
= NUMBER OF RINSE TANKS
= NUMBER OF RINSE TANK BEING
CONSIDERED
Figure 3. Math model.
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As an example, the equilibriim concentration of the 2nd tank in a
4. tank system with a count ere u ."rent flow ratio of 2, may be found by
setting n = 2, M - 4., and X = 2.
2
(21)
21 + 22
2° + 21 f 22
11
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The results for 2, 3 and 4 tank systems are given in Figures 4 to
6. As an example, in a two stage system the concentrations of the rinse
water in either tank can be found from the graph in Figure 3. If the
ratio of water flew to dragout from the last plating cell into the
rinse system is two, the equilibrium concentration in stage #1 is 44
percent of the concentration of the electrolyte in the cells. The
equilibrium concentration in the second or last stage is 14 percent
cf the bath composition. If the ratio of rinse water to dragout increases
the equilibrium compositions will decrease according tc the graph.
A four stage system was chosen for this installation for several
reasons. Space was a primary consideration. The graph for a four stage
system, Figure 6, indicated low concentrations could be obtained for the
final rinse and high concentrations in the first rinse. Thus product
quality could be maintained or improved plus a concentrated stream would
be generated for closed loop recycling or use in a recovery system. A
five stage system would be harder to maintain and no big advantage over
a four stage system. A three stage system would not give enough difference
between the first and last tanks.
12
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100
90
80
o
i 70
i—
LLJ 60
3 50
Sj 40
u_
o
»*; 30
20
10
J_
2
K=R/D
R=Counter Current Flow (gpm)
D=Drag Out Flow (gpm)
3
Figure 4. Rinse tank equilibrium concentration as percent of cell concentration (two tank system).
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100 r
90
80
o 70
<:
8;
60' •
50
§ 40
LU ,
oj 30
20 •
10 -
1
2
K=R/D
R=Counter Current Flow (gpm)
D=Drag Out Flow (gpm)
Figure 5. Rinse tank equilibrium concentrations as percent of plating cell concentration
(three tank system).
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100
90
80
I 70
8 60
o
= 50
Q>
•S 40
30
20
10
0
.5
tanktfl
R=Counter Current Flow (gpm)
D=Drag Out Flow (gpm)
1
1.5
K=R/D
Figure 6. Rinse tank equilibrium concentrations as a percentage of cell concentration
(four tank system).
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VI-DESIGN AND INSTALLATION OF GPUNTERCURREM1 RINSE EQUIPMENT
The No. 6 Electrolytic Tinning Line was designed in 1964.. The
line was built to produce tin plate coils as follows:
LINE SPECIFICATIONS
Maximum Coil Weight 60,000 Ib.
Minimum Strip Thickness 0.003 in.
Maximum Strip Thickness 0.036 in.
Minimum Strip Width 16 in.
Maximum 3trip Width 4-5 in.
LINE SPEED
Entry End loOO fpm at 24.0 volts
24.00 fpm at over voltage
Center Section 2600 fpm at 240 volts
2000 fpm at over voltage
Exit End 1600 fpm at 24.0 volts
2400 fpm at over voltage
The line is 492'-6" long. The plater cells are located in the
center section. The reclain tank is located immediately after the
last plater cell on the third deck of the plater structure. The original
tank was equipped with an entry end and exit dunk roll to submerge the
strip for 25'-0" in the reclaim water rinse.
Specifications were drafted for the replacement of the existing
dunk-type reclaim tank section with a cascade, wringer roll type rinse tank.
The scope of trork included removal of the reclaim tank, modifying the
adjacent tank;.-,, alterations to the structural supports and installation
of the new equipment.
The new reclaim rinse tank has four compartments for circulating rinse
solution. Fresh demlrieralized water is added to the No. 4- or last compart-
ment. Each compartment overflows in a countercurrent direction from compart-
ment No. 4 t-> compartment No. 1. The individual compartments have a pump
suction line .-.'or the &pra;r pumps- rlhe No. 1 compartment is furnished with
an overflow line.
The spray pumps take solution from the individual tank compartments
and pump to the spray headers in the same tank compartment. Each compartment
is also furnished with a hopper for addition of chemicals.
16
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NEW EQUIPMENT SPECIFICATIONS;
Tank - Fabricated of 5/8" thick mild steel,
1/4" rubber lined and 3/16" rubber
covered.
Cover _ Fabricated 1/4" thick mild, steel 14"
rubber lined.
Drive Bases - Fabricated 5/8" thick mild steel.
Pump Bases - Fabricated 5/8" thick mild steel.
Rolls - Nine (9)-10" diameter and 54" face
steel, rubber covered.
One (1)-15-1/2" diameter by 54" face
steel, rubber covered.
Roll Drives - Ten (10)-single reduction gear type
with steel housing.
Roll Drive Motors - Nine (9)-3 Horsepower, 1150/2300 rpm
One (l)-5 Horsepower, 1150/2300 rpm
Couplings - Gear Type
Bearings - Pillow Block Roller Bearing Type
Pumps - Four (4)-100 gpm at 50 psi
Pump Motors - Four (4)-15 Horsepower, 1750 rpm
Spray Headers - Eight (8) -316L Stainless Steel
The tank, drive bases, and pump bases were mounted to a common drip
pan. The rinse tank being on the third level of the structure, the drip
pan was installed to prevent any spillage from dropping on the structure
and/or equipment on the two levels below. The drip pan also served as a
unitized sub-base for the equipment. After all equipment was mounted to
the pan it was then possible to fabricate and install all piping and
apparatus at an off-site location.
The plating line operation was shut down for four (4) days to install
the countercurrent rinse tank. The installation was possible in such a
short time because of the pre-assembly of equipment and piping. The old
reclaim tank was removed, and the new rinse section dropped into place in
two (2) lifts of an overhead crane. The balance of the installation time
was used to join the new tank section to the existing equipment and connect
the piping and electrical terminations.
17
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A schematic of the piping system is shown in Figure 7 . The
incoming water flows through a rotometer, rated 0 to 5 gpm. This water
flows in compartment No. 4. The overflow from compartment No. 1 flows
through a rotometer on the way to the main plating system.
The value on the incoming water line is controlled by a solenoid
which closes the valve whenever the speed of the line reaches zero.
This protects against dilution of the equilibrium concentrations during
shut down periods.
18
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LEVEL ALARM SWITCH
MOTOR JOHP
1800 RPM
STORAGE TANK OR
RECOVERY TANK
OTD5GPI
Figure 7. Multistage spray rinse tank piping system.
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VII-OPERATIONAL RESULTS
A. OPERATING PRACTICES AND EXPERIENCE
Production with this new unit began on November 26, 1974-. Problems
that were anticipated during start-up such as buildup on the rolls and
drying out of salts on the strip did not occur.
Sodium bifluoride was added in the No. L, compartment. This chemical
maintains an acid rinse so that the tin in the solution does not
hydrolyze and stain the strip. It vjas found that one pound per hour
maintains a pH of 3.5 to 3.8 which is about the same as the plating
solution.
After the initial week, the spray nozzles were found to be corroding.
These were replaced with stainless steel nozzles and no major problems
have occurred with the spray nozzlas as long as they were cleaned on
a weekly basis.
The rolls need only occasional sandirg to remove salt buildup. The
solution of the No. 1 compartment has a pH of 3.5 to 3.8 and the total
tin concentration ranges from 0.5 to 1.0 ounces per gallon. The No. 4
compartment ranges from 0.1.0 to 0.15 ounces per gallon. The demineralized
water is put into the iTo. 4 jompartment at a rate of 3 to 3-5 gallons per
minute.
On start-up of the countercurrent rinse tank, it was found that the
quality of the tinplate was as good as, or better than, before. The
tinplate strip is brighter because the countercurrent rinse tank
affords better rinsing of the strip. It is only natural that a cleaner
water is used to rinse the strip with the countercurrent rinse system
versus the old method of immersion rinsing. Since the strip is rinsed
better before ?t goes into the scrubber and the hot rinse tank, there
are less salt.c left on (:he strir ihi^h allow for a brighter strip when
tin is melted in the reflow
Eight sets of spray headers are used, two sets in each tank. Each
header has eight stainless steel V-jet sprays. The sprays are located
five inches apart.
20
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B. RINSING PERFORMANCE
In Table 1 the results of the chemical analyses for stannous tin
are given. It required three days or 72 hours to reach equilibrium
concentrations. Calculations had indicated at least 48 hours would
be required. Once equilibrium was reached, the differences in
concentrations of the four stages were as expected.
Because of the high flow required to maintain volume in the main
plating system, the concentrations in the various stages have not
reached the higher levels expected. This, however, is a big
advantage because the concentration of the last stage (No. 4) can
be kept at a very low level. This means minimum loss of chemicals
to the spray and hot rinse sections. It was somewhat surprising to
find that a flow rate of 4- to 5 gpm into the countercurrent rinse
could be used without a buildup of volume in the main plating system.
Apparently the evaporation losses are considerable.
The concentration of the tin in the last stage is about one tenth of
the concentration found in the reclaim tank during the base period
investigation. Therefore losses to the spray rinse and hot rinse
sections have been reduced by around 90 percent. This figure will
be checked in future repeat testing by Environmental Control of the
effluents from these rinses. This reduction is in addition to the
elimination of the losses which occurred from the flow which used to
enter the sewer from the reclaim tank.
Sodium bifluoride is being added to the last stage of the countercurrent
rinse system to control pH and prevent hydrolysis of tin salts on the
strip. Operators have noted that the strip looks cleaner than it did
when the old system was in use.
21
-------
STAGE (oz/gal (SN++
Date
11-26-74
11-27-74
1 1-28-74
11-29-74
11-30-74
12-2-74
12-4-74
12-6-74
12-9-74
12-11-74
12-13-74
12-20-74
12-27-74
1-31-75
2-38-75
3-14-75
4-10-75
9-8-75
9-19-75
9-25-75
No. 1
0.18
0.118
0.37
0.49
0.^.6
0.43
0.49
0.49
0.31
0.59
0.46
0.43
0.46
0.65
1.08
0.65
O.h2
0.92
0.86
0.68
No. 2
0.09
0.09
0.22
0.30
NR
0.22
0.24
0.15
0.15
0.31
0.21
0.21
0.24
0.34
0.55
0.30
0.31
0.33
0.37
0.31
TIM)-)
No. 3
0.06
0.06
0.12
0.12
NR
0.09
0.12
0.12
0.09
0.15
0.12
0.12
0.12
0.15
0.27
0.15
0.15
0.12
0.15
0.12
No. 4
-
-
0.03
0.06
0.06
0.03
0.06
0.06
0.03
0.09
0.06
0.06
.06
0.09
0.15
0.09
0.06
.04
.05
0.06
* Values should be multiplied by factor 1.2 for total tin,
22
-------
?IH3T F-iOBLM OF CHLORIDE BUILDUP
Throughout December of 1974 a rise in the chloride content of the
electrolyte was noted. A plot of the chloride content is shown in
Figure 8. As can be seen by the graph the chloride level
prior to the start-up of the countercurrent rinse system was between
4.0 and 4.6 ounces per gallon. After the start-up of the new rinse
system on November 26, the chloride content started to rise. A level
of 5 ounces per gallon was reached on December 13 j a level of 6 ounces
per gallon was reached on December 22 and finally a level of 7 ounces
per gallon was reached shortly after the first of the new year.
The levels of tin and fluoride did not increase. The reasons for the
increase in chloride have become obvious. Chemical additions were
reduced for several components which normally supply hydrogen ions to
the plating bath. Both stannous chloride and sodium bifluoride are
acid salts . With a cut back in the additions of these chemicals rr.ore
hydrochloric acid was added to control pH.
The desired pH range is 3.3 to 3.5. The pH will gradually rise due
to the electrode reactions at the cathode (strip) and also due to
the formation of sludge. According to the DuPont Manual, one of the
major causes for change in pH during operations is the difference in
anode and cathode efficiency. Hydrogen ions are consumed in the
formation of hydrogen at the cathode. Another cause for increase
in pH according to the DuPont Manual is the oxidation reaction. This
can be expressed as follows:
2Sn+2 + 02 + 4H"1" -? 2Sn+if and 2H20
Since the reaction removes hydrogen ions, the pH increases.
To counteract this rise in pH, hydrochloric acid was added. During
the rise of chlorides in December, it was hoped that an equilibrium
concentration would be reached before salting out occurred. This is
a condition which occurs when the total salt content rises too high
and crystallization develops in the plating system, especially on
rolls, causing denting of the surface of the strip. When the chloride
content exceeded 7.0 oz/gal, the dent problem developed and corrective
action had to be taken. Steps were taken which included running part
of the effluent from the countercurrent rinsing system to the sewer
rather than back into the plating system.
23
-------
8.0
7.0
6.0
5.0
1
' 4.0
c
V
(J
•S! 3.0
O I
CO ;
2.0
1.0
O
D A A*
Q
A chloride
n floride
tin, total
AA
A
0
D
AA
00
no
AA
0 20 25 30
Nov 1974
5 10 15 20 25 30
Dec 1974
4 9 14
Jan 1975
Figure 8. Bath concentration vs. time.
24
-------
D. ECONOMIC STUDY FOR ONE YEAR OF OPERATION
In Figure 9 a graph shows the consumption of stannous chloride and
hydrochloric acid for the year (1974) prior to the installation of
countercurrent rinsing and the first year of its use (1975)• The
amounts are given as the chlorides of each of the two chemicals.
Taking an average for each twelve month period, see Figure 8, the
amounts used per month were -
1274 19-75
(Cl) 6,000 Ibs 3,000 Ibs.
HC1 (Cl) 1,000 Ibs 2,200 Ibs
As the consumption of stannous chloride was reduced the use of
hydrochloric acid had to be increased to obtain the acidity required
to maintain the pH within the desired range (3-4 to 3.7).
The line was operated at a slightly higher pH in order to control
the level of chlorides below a level where salting out would occur.
This (jill be discussed in more detail later. However, with certain
slight changes in operation the tin plating line was able to operate
without denting problems at least until November 1975.
The 3,000 pound difference in chlorides from the reduction in the
rate of consumption of stannous chloride is equivalent to 3_000 or
0.63"
4,762 pounds per month of stannous chloride. Taking a cost of stannous
chloride at $2.60 per pound this represented a savings of $12,380 per
month. From this must be subtracted the increased cost in the use of
hydrochloric acid. The 1,200 pounds per month increase amounted to
$60 per month based on a cost of $32 per ton of 32$ acid. The net
savings was thus $12,380 - $60 or $12,320 per month or $147,840 per
year. There were other changes made during the year by Operations
which may have assisted in this cost reduction. Additions were made
more often which insured more complete dissolution of the chemicals.
This change was made in the summer of 1975.
25
-------
to
10,000
-° 8,000
a
s
a>
6,000 -
4,000 •
2,000 •
J F M A M J J A S 0 N D J F M A M J J A S 0 N
"l974 1975
Figure 9. Rate of monthly consumption—No. 6 electro-line.
-------
E. PROBLEMS GENERATED
After one year of operation an evaluation has been made of the new
rinse system. Some problems have developed not due to the mechanical
performance of the equipment but due to the peculiarities of the
Halogen Tin plating Process. It was anticipated prior to the
installation that this might be the case and some modification of the
process or operation would be required to obtain maximum benefit
from dragout recovery.
Since oxidation of tin in the halogen electrolyte occurs continuously,
sludge is produced also continuously. Sludge contains sodium, tin
and fluoride but very little chloride. There is, therefore, a
continuous need for additions of sodium, fluoride and tin to replace
the amounts lost in sludge formation. While part of the tin may be
supplied by the differences in electrode efficiencies the other
elements must be added by periodic chemical additions.
The electrolyte also becomes more basic with coulombic input due to
the generation of hydroxide ions at the cathode and with the consumption
of hydrogen ions in sludge formation. Therefore, regular additions of
either stannous chloride or hydrochloric acid must be made for control
of the pH at a fixed value.
Another pecularity of the halogen electrolyte is the need to keep the
sodium chloride content below the level where salting out, or saturation
occurs. Sodium chloride formation within the bath will lead to denting of
the strip due to buildup on rolls. The anions, particularly fluorides
and chlorides, must be held within a certain range to avoid this problem.
In Figure 10, the amount of chlorides in the system is shown. After the
initial surge of buildup in January the levels were reduced by operating
the electrolyte at a slightly high pH thus reducing the additions of
hydrochloric acid. Operating personnel have contended that the denting
problem has been greater than normal even during the best periods. In
November 1975, the denting problem became severe. The blame was given
to countercurrent rinsing and the flow was diverted to the sewer from
the first stage.
It has been found that the use of countercurrent rinsing along with
dragout recovery and reuse has affected to some extent two aspects
of the halogen process; (l) the control of pH and (2) the level of
chlorides.
27
-------
CO
00
12
11
10
9
8
7
6
5
4
3
o
o_
O
><
N
X-sludge periods
Nov Dec Jan Feb Mar Apr June July Aug Sept Oct
1974 1975
Figure 10. Amount of chlorides in system.
-------
Vin-SOLUTIONS TO PROBLEMS GENERATED
A. USE OF HYDROFLUORIC ACID
As previously mentioned the problem of chloride buildup resulted
because additions of hydrochloric acid were still required for pH
control after recovery of dragout was instituted. Since chlorides
are not removed from the system in the formation of sludge, the
elimination of losses due to dragout results in an increasing
concentration of chlorides in the electrolyte. A solution to this
problem, as suggested by Dr. D. A. Swalheim of DuPont, is to
substitute hydrofluoric acid (HF) in place of hydrochloric. Fluorides
are removed from the system in sludge formation.
This possibility has been studied and is still under consideration.
However, the problem with using hydrofluoric acid is the hazardous
nature of this chemical. Burns due to hydrofluoric acid are extremely
serious. Nevertheless this acid is used in many plants where proper
safety precautions are employed.
In efforts to counter the reluctance of operating personnel to consider
the use of hydrofluoric acid, the Environmental Department of R & D
has designed a system for minimizing the hazards involved in unloading,
transporting, and emptying containers of HF. This system consists of
a portable heavy steel tank with a double valve control. A sketch of
this system is shown in Figure 11. All the employee in charge of
adding the HF has to do is open the air vent and turn the long stemmed
valve on or off. When the container is empty, as indicated by a floating
ball type, liquid level instrument, the nozzle is rinsed out via a
special water connection and removed.
Another method for handling HF is shown in Figure 12 . This method
appeared in the January 17, 1977 issue of Chemical Engineering. Air
pressure is used to fill and transport to the user tank a predetermined
amount of the acid. No pumps or carboys are required. With the storage
tank located outside the building, the time that the acid is in the plant
at full strength is limited to just a few minutes.
29
-------
106.68 cm
(3.5ft)
WATER CONNECTION
Figure 11. Proposed HF tank.
30
-------
GO
•gT , '' „- "8 in drilled orifice
rO
in pipe
Check valve ""
1 in drain valve
•
side
•nt
fety •
.»f
ssure
ssel
?)-
-^
//
X
3/4 in
pipe
•«• ^
Pressure-:
vessel r~^
"
i i" i
5
)
Sulphuric
storage
tank
Shut-off valves
^/
1
User tank
nitric
v-v
f
1
User tank
sulphuric
,3/4 in pipe
/;
(A }
7 Pressure (safety) valve (0 50 psi)--^V"
i — ^-r\i — 1 i
, supply
\
T 1 Pressure regulator- —(»)
-ft-* (& I
>-*
I
User
\ t
\ in shut-off
Manual shut-off ~~
Figure 12. Distribution system for strong acid using neither pumps nor carboy.
"^Chemical Engineering, 1/17/77, page 150; used with permission.)
-------
B. USE OF AN ALKALINITY REMOVAL UNIT
Recent advances in technology has extended the use of electrodialysis
cells from laboratory curiosities to commercial use. These cells
employ perm-selective membranes, which have ion exchange properties.
New fields for use of these cells include continuous ion exchange.
In this process, one ion is exchanged for another, in the same
manner as an ion exchanger, with the exception that in this process
the resin (the membrane) is regenerated continuously by electrical
energy, rather than cyclical, by chemical regeneration.
In the halogen bath there is a continued need to add acid to counter
the buildup of sodium ions due to the oxidation of the tin and to the
generation of hydroxyl ions at the Cathode. As a result sodium
hydroxide is produced. The concentrated rinse from the countercurrent
rinse system can be made to pass between two cationic membranes
wherein the sodium is migrated from the bath through the cation
membrane to the cathode compartment forming sodium hydroxide. At
the same time hydrogen is passed from the acid in the anode compartment
into the concentrated rinse water. A diagram of the process follows:
Anode
Cation j
Membranes -
\
H+
Sulfuric Acid
Solution
Nan-
Rinse from Countercurrent
System
n Cathode
Caustic
Solution
Acidified Rinse
to Plater System
32
-------
Alkalinity is removed from the stream and acid is generated thus
reducing or eliminating the acid requirements. In this manner,
an alkalinity removal unit might permit operation of a closed
loop system. If more removal of alkalinity is required to balance
the system, electrolyte from the plating cells could be passed
through the unit.
The only by-product from the unit is a solution of caustic soda.
This material has wide usage for acid neutralization. The purity
should be sufficient to permit use in processes requiring solutions
of caustic soda.
33
-------
C. INDIRECT RECYCLE VIA DETIMING PLANT
Located at the Weirton Steel Division is a Detinning Plant, which
was designed primarily for the recovery of tin from scrap tinplate.
However, this plant also processes sludge from the plating lines.
A flow sheet of the process is shown in Figure 12A . The sludge enters
the system at the point where sodium stannate filter cake is fed to
the dissolving tank. When sludge is being processed the sludge
replaces the filter cake in the system. The concentrated rinse
from the countercurrent rinse system is now being sent to this plant
for recovery of the tin values. The rinse solution replaces part of
the water used to dissolve the sludge.
The chemical principles on which the entire operation is based are
generally well known. Metallic tin will dissolve in a hot solution
of sodium hydroxide to form soluble hydrated sodium stannate. Once the
alkaline solution has become saturated with sodium stannate, precipitation
occurs and the crystalline solid is periodically removed and separated
from the detinning solution. It is then dissolved in water in a
suitable tank. This is the same tank or point in the process where
sludge or concentrated rinse solution is added. The stannate solution
is transferred to a second tank where it is converted to stannic
hydroxide by controlled additions of sulfuric acid. The tin hydroxide
thus formed appears as a white insoluble compound. Sodium sulfate, the
other product of the conversion, remains dissolved in solution as well
i.j ..::e fluorides from the sludge and recovered rinse. The tin hydroxide
is next filtered and washed. The wet filter cake is then dried and
mixed with anthracite coal. When this mixture of hydrated tin oxide
and carbon is heated to about 2200°F, the oxide is reduced to metallic
tin.
-------
DETINNED SCRAP RINSED SCRAP TO
SULfUBIC ACID
SOPIUM STANKMTC [""WATER
»«UTLA*0 f«.TCH
COAL
WET STANNIC
HYDROXIDE
msoLuout SUIOGC
TO WAJTC
HYDROXDC SLURRY
MCTALLIC TIN
Figure 12A. Flow chart of the detinning and tin recovery process.
((c)lron and Steel Engineer Year Book, 1953, page 207;
used with permission.)
35
-------
DC-ENVIRQMMENTAL ASPECTS
A. GENERAL INFORMATION
The most important environmental aspect of countercurrent rinsing
is that the eff] icnt from the countercurrent rinse tank has been
concentrated to ^iich an extent that direct or indirect recovery
methods can be *:orployed. Recovery of the effluent from the
court ereiarrent rir ae tanks can permit significant reductions in
the loauings of the key pollutants such as tin, chlorides,
fliK'ri.ios, cyanides, suspended solids, etc., to the receiving stream.
3ir.ee the nost convenient method of recovery was the re-use of this
'j.'Tluer.t, in the •?] ocj.r-lytic process,, this environmental study was
accomplished with th 2 affluent froi; the countercurrent rinse tanks
recycled to the electrolytic plating solution tank.
It was the expressed intent of Weirten Steel Division to gather
sufficient environmental background , ata on the original rinse system
(see Figure 13) as to have a sulid basis for comparison with the
countercurrent rinse system (s e Figure 14.). In this regard, the
environmental survey was designed to establish the existing average
background loadings of key pollutants prior to the installation of
the countercurrent rinsing system. These averages were then compared
with the average loading- of trie same parameters which were being
diverted to the sewer after the installation of the countercurrent
rinsing system. The Uu-kgrotmd survey and the subsequent installation
of the system shall be referred to as Phase I of the project in this
report. Th start-up ar I optimization of the system shall be referred
to as Phasf- II and the "valuation of the system shall be referred to
as Phase II.i of this project. During Phase I of the project, effluents
from the recovery tank (Figures 13 and 15), spray wash (Figures 13
and 16), and hot rinse (Figures 13 and 17), were diverted to the
sewer. During Phase III of the project only the effluents from the
spray wash and the hot rinse were diverted to the sewer since the
effluent from the countercurrent rinse tank was recycled to the plating
solution tv.j k.
-------
/ / /\
xCtv x^s J^V O
RE. c. o v e. R v
HOT
Figure 13. Bacl^round rinsing system, phase I sample points.
-------
00
00
To COUUTE.RC.OBLgL%; VAT
Figure U. Countercurrent rinsing system, phase III sample points.
-------
GO
Figure 15. Recovery tank.
-------
Figure 16. Spray wash.
-------
Figure 17. Hot rinse.
41
-------
B. BACKGROUND SURVEf (PHASE I) General Description
A total of seventeen samples was taken during the period of
approximtely one month (August 5 to September 6, 1974) to provide
base' line data with which to compare data obtained from the ensuing
countercurrent rinse system. Figure 13 shows the basic rinse system
and identifies the three sample locations. The recovery tank
(Sample Point No. 1) was merely a dunk tank with an average incoming
fresh water supply of approximately five gallons per minute. Ths
spray wash (Sample Point No. 2) rinse section was composed of a
series of sprays above and below the strip with an average flow of
about fifty gallons per minute. The hot rinse (Sample Point No. 3)
section was composed of a dunk tank which was occupied with hot
water (180°F.) with a make-up flow of forty gallons per minute. The
overflow or drains of each of the three rinse sections were channeled
to the sewer during the base line period.
Figure 18 is a schematic of the basic sampling facilities. A flow
meter was installed at each sampling location to measure the amount
of fresh water coining into each rinse section. The summation of
these flows was representative of the total effluent from the plating
process, including dragout and evaporation. The effluent from each
rinse was channeled into a polypropylene sampling box. Two representative
samples of the effluent were collected from each polypropylene box
utilizing the refrigerated pressure operating sampler described in
Figure 19. One sample was treated with sodiun hydroxide to preserve
cyanides and the other sample was left untreated for the remainder
of the analyses. The background samples were then analyzed for the
following parameters:
Temperature Suspended Solids
pH Cadmium
Acidity or Alkalinity Chromium
Chlorides Iron
Chemical Oxygen Demand Nickel
Free Cyanides Phosphates
Total Cyanides Potassium
Fluorides Sodium
Sulfates Tin
All samples analyzed were collected as 24-hour composites.
Flow Rates
During the background survey all flows were obtained by setting the
make-up water to the desired level using calibrated flow meters. These
flow meters provided an instantaneous read-out and also provided an
electronic signal to the integrators which totalized the flows. Due to
problems encountered with the integrators, the instantaneous read-out
was checked periodically and the daily flow calculated from the direct
read-out. The flow meters were calibrated periodically using the
stopwatch and bucket technique.
42
-------
Fuow
CO
PCI.VPROP v
To Stiw E:
Figure 18. Sampling diagram (essentially the same for: recovery tank, spray wash, hot rinse).
-------
PRESSURE
SUPPLY
5-200 PSIG
On-Off
SWITCH
PRESSURE
GAUGE
PRESSURE
REGULATOR
SAMPLING
INTERVAL
TIMER
2 Seconds-
60 Minutes
SAMPLING
DURATION
TINER
1.2 Seconds-
50 Seconds
1. A pressure supply of from 5 to 200 PSI is connected to
the sampler. This supply pressure is controlled by the
sampler's On-Off switch.
2. With the switch in the On position, the pressure regu-
lator is adjusted to indicate a pressure of from 5 to
140 PSI on the pressure gauge. The 140 PSI pressure is
the maximum operating pressure of the sampler's timing
circuits. The pressure should be set to allow one pound
of pressure for every two feet of vertical lift.
3. Pressure is now applied to the sampling interval timer.
This timer controls the length of time between samples.
The interval timer is continuously adjustable from 2
seconds to 60 minutes between samples.
4. When the interval timer completes its time cycle it ap-
plies pressure to the sampling duration timer. This tim-
er controls the length of time that the sampler releases
pressure to the sampling probe. The greater the vertical
lift or the longer the horizontal run, the longer the
period of time that is required to purge the sample from
the sample tubing.
5. Upon completion of the duration timer's time cycle, the
applied pressure is released and enters connection "P"
on the sampling probe. The sampling probe is a gravity-
fill unit and holds a sample of 50 ml. Pressure is exert-
ed upon the liquid contained in the probe and forces it
to exit through the fitting "S" located on the side of
the probe. The liquid travels through the connecting tub-
ing and into the sample container. The sample container
may be located at any point from several feet to over
200 feet from the sampling probe. iNormally the container
is located in the sampler's case or refrigerator.
NOTE: Only the sampling probe is submerged in the liquid
to be sampled. The liquid never enters the sampler's con-
trol circuits.
SAMPLING
PROBE
When the sample is deposited in the sample contain-
er, the pressure in the lines is vented through the
'V connection on the sample container. In the event
that the total composite sample taken over a period
of time should exceed the container's capacity, it
will be discharged through the "V" connection on the
container.
After the sampling lines are purged of all sample,
the timing circuits must reset themselves automatic-
ally. During this reset period which occurs immedi-
ately after the sample is taken, the timers must
vent their timing valves. The vent pressure from the
timing valve on the interval timer is connected to
the sampling probe through connection "F". This vent
pressure is used to purge the probe's inlet screen
of any foreign matter.
The sampler requires a pressure supply of from 5 to
200 PSI. R-12, nitrogen or compressed air can be
used to power the sampler. Since the sampler is op-
erated on pressure only, it is explosion-proof.
Figure 19. Schematic, pressure operated sampler.
-------
Chemical Analysis
The analyses were performed using procedures found in one of these
three sources:
1. Standard Methods for the Examination of Water and Wastewater,
13th Edition.
2. ASTM Standards. Part 23, Water; Atmospheric Analysis. .
3. E.P.A. Manual of Methods for Chemical Analysis of Water and
Wastes.
The only exception of the above statement pertains to the analysis of
free cyanides. Since an approved method has not been published, an
American Iron and Steel Institute's method was used. A summary of
each procedure used for each parameter is listed in Appendix I
(4, 5. 6)- All metals were analyzed on a Perkin-Elmer Model 306 Atomic
Absorption Spectrophotometer.
Results
Table 2 indicates the average daily loading in oourv?i3 for each rinse
rank over the seventeen-day sampling duration. A daily tabulation
of the results can be found in Appendix II.
-------
TABLE II
PHASE I - BACKGROUND EFFLUEWT LOADING
RECOiTSKT TANK
Average
Effluent Loading
Flow 5 gprn - 7200 gpd
Temperature 1129F.
pH 4.46
Alkalinity Acidity/7.99 Lbs/Day
Chlorides
C.O.D.
Free Cyanides
Total Cyanides
Fluorides
Sulfates
Suspended Solids
Chromium
Iron
Nickel
Potassium
Sodium
Tin
153
121
.032
2.35
281
17.5
21.6
0.051
3.86
0.044
0.47
260
203
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
Lbs/Day
SPRAY WASH
Average
Effluent Loading
HOT RINSE
Average
Effluent Loading
53.53 gpm - 77,082 gpd 40 gpm - 57,600 gpd
93°F.
Acidity/22.1 Lbs/Day
32.9 Lbs/Day
27.2 Lbs/Day
0.16 Lbs/Day
0.66 Lbs/Day
59.6 Lbs/Day
110 Lbs/Day
56.9 Lbs/Day
0.015 Lbs/Day
1.40 Lbs/Day
-------
C. EVALUATION OF COUNTERCI3RRENT RINSING (PHASE III)
General Description
After the start-up and optimization of the system (Phase II), a
series of eleven samples were taken over a period of six weeks
August 26 to October 3, 1973) to evaluate the improvement in
pollutant loadings coming from the new rinse system featuring a
countercu-ient rinse tank as the primary rinse.(See Figure 14
for a schematic of the countercurrent rinsing system.) As can be
seen from Figure 14, the spray wash and the hot rinse were being
used as make-up for the plating solution. The identical sample
points (Figure 14) and sampling facilities (Figure 18) were used
for both Phase I (Background) and Phase III (Countercurrent Evaluation)
sampling programs. Sampling of the countercurrent system was delayed
several times due to equilibrium problems in the plating process.
Flow Rates
Due to problems which developed with the flow meters, the flows which
were obtained during the countercurrent rinsing system evaluation
were arrived at by the stopwatch and bucket technique. The flows
were set before each test interval and re-checked at the end of the
24-nour testing period to insure their reliability/.
Chemical Analysis
The chemical analyses of the effluents from the spray wash and the
hot rinse were analyzed by the same procedures as previously outlined.
Summaries of the analytical methods may be found in Appendix I.
Results
Table III indicates the average daily loading, in pounds, of the eleven
samples taken for the countercurrent rinse system evaluation. A
complete day-by-day tabulation of the analysis may be found in
Appendix III.
47
-------
TABLE III
PHASE III - nonMTERCURflENT RINSING EFFLUENT LOADING
Flow
Temperature
pH
Acidity/Alkalinity
Chlorides
C.O.D.
Free Cyanides
Total Cyanides
Fluorides
Sulfates
Suspended Solids
Chromium
Iron
Nickel
Potassium
Sodium
Tin
SPRAY WASH
Average
Effluent Loading
27,027 g.p.d.
88.3 Deg. F.
5.3
1.28 Lbs. Alkalinity
10.7 Lbs
3.31 Lbs.
0.034 Lbs.
0.040 Lbs.
7.45 Lbs.
27.0 Lbs.
10.1 Lbs.
^Detectable Limit
0.16 Lbs.
^Detectable Limit
1.05 Lbs.
11.6 Lbs.
11.0 Lbs.
HOT RINSE
Average
Effluent Loading
46,172 g.p.d.
172.2 Deg. F.
7.5
7.41 Lbs. Alkalinity
22.3 Lbs.
2.38 Lbs.
0.035 Lbs.
0.065 Lbs.
0.99 Lbs.
42.8 Lbs.
7.80 Lbs.
<. Detectable Limit
0.33 Lbs.
^Detectable Limit
1.64 Lbs.
5.81 Lbs.
2.52 Lbs.
48
-------
D. DISCUSSION OF RESULTS
Table IV illustrates the magnitude of reduction of the major
pollutants that can be achieved by one hundred percent recycle of the
effluent from a countercurrent rinsing system on a high speed electrolytic
tin plating operation. Total recovery of the countercurrent rinsing
effluent occurred during the two months preceeding the evaluation
until approximately six weeks after the termination of the evaluation.
An analysis of the analytical results from this survey indicates the
following reduction in daily loadings of key pollutant from an electro-
lytic tin plating operation when a countercurrent rinsing recovery
system is employed:
Tin 95/6 Reduction
Total Cyanides 91% Reduction
Fluorides 98$ Reduction
Chlorides BB% Reduction
Sodium 95/6 Reduction
During this period in which the effluent from the countercurrent rinse
tank was completely re-used as make-up for the plating solution the
possible environmental improvements were demonstrated. However, as
indicated in Section VII of this report, product quality problems
prevented the continued operation of the electrolytic plating line
utilizing this concept. In this regard, three alternatives have
been proposed in Section VIII of this report, which could eliminate
the product quality problems previously described. The environmental
aspects of each alternative is discussed below:
1. Use of Hydrofluoric Acid - Section VIII-A describes the
mechanism by which this alternative should eliminate product
quality problems. The utilization of hydrofluoric acid as
a source for fluoride and to control pH should permit the
continuous recycle of one hundred percent of the countercurrent
rinsing effluent into the plating solution tank, thus achieving
the reductions in pollutant discharges indicated above.
However, a potential safety hazard exists in the handling of
hydrofluoric acid, and the acceptance of this alternative is
questionable even if the safety precautions described in
Section VIII-A are adopted.
-------
2. Use of an Alkalinity Removal Unit - A description of the
operating principles of an alkalinity removal unit and its
ability to eliminate the product quality problems associated
with this project is documented in Section VIII-B. This
unit would treat the countercurrent rinse tank effluent,
utilizing electrodinalysis principles, and it should permit
the recycle of one hundred percent of the countercurrent
rinsing effluent into the plating solution tank, thus
achieving the pollutant reductions previously cited. A
small quantity of sodium hydroxide would be produced as a
by-product from the alkalinity removal treatment process.
This material would be utilized in a wastewater neutralization
treatment system serving the Tin Mill operations.
3. Indirect Recycle Via Detinning Plant - As stated in Section
VIII-C, Weirton Steel Division has a unique advantage in that
the company operates a Detinning Plant which has the capa-
bility to remove the tin from the countercurrent tank effluent.
By storing the effluent which cannot be directly re-used and
transporting it to the Detinning Plant, a significant amount
of the pollutants from the tin plating operations can be
recovered and thus preventing their return to the environment.
If zero discharge from the tin plating system cannot be
achieved, then tests should be conducted to find out exactly
how much blowdown must be removed from the system to prevent
the accumulation of materials in untenable amounts. If, for
example, it can be demonstrated that the system will work
satisfactorily with a 70 percent recycle, the remaining 30
percent could be transported to the Detinning Plant for
recovery. This alternative should also achieve the reduction
in pollutant loadings previously documented.
This project has shown that significant environmental benefits can be
derived by the direct or indirect recovery of the countercurrent rinsing
effluent. The adoption of any one of the three proposed alternative
solutions for the product quality problem should accomplish the desired
environmental benefits. The selection of the alternative to be utilized,
therefore, becomes one of economic, process, and safety considerations.
50
-------
TABLE IV
COMPARISON OF BACKGROUND VS COUNTKiCIRaEflT RINSING EFFLUENT LOADINGS
Flow
Temperature
PH
Acidity/Alkalinity
Chlorides
C.O.D.
Free Cyanides
Total Cyanides
Fluorides
Sulfates
Suspended Solids
Chromium
Iron
Nickel
Pota'ssium
Sodium
Tin
Background
Evaluation
Total Average
Affluent Loading
28.2 Lbs. Acidity
271.6 Lbs.
165.9 Lbs.
0.237 Lbs.
3.15 Lbs.
350.6 Lbs.
202.8 Lbs.
93.5 Lbs.
0.066 Lbs.
5.53 Lbs.
0.044 Lbs.
5.53 Lbs.
371.3 Lbs.
270 Lbs.
C ouate rcurrent
Rinsing
Evaluation
Total Average
Effluent Loading
8.69 Lbs Alkalinity
33.0 Lbs.
6.19 Lbs.
.069 Lbs.
.105 Lbs.
8.44 Lbs.
69.8 Lbs.
17.9 Lbs.
< Detectable Limit
.49 Lbs.
-------
X-BIBLIOGRAPHY
1. Graham, A. K., Electroplating Engineering Handbook, 2nd Edition,
Reinhold Publishing Corporation, New York, 1962, Chapter 34,
Rinsing, p. 705.
2. U.S. Patent 3,907,653, R. E. Horn to P. H. Metals, Process for
Recovering Tin Salts from a Halogen Tin Plate Source.
3. Kromblolz, A. J., "Recovery of Tin from Scrap Tinplate," Iron
and Steel Engineer Yearbook, 1953, p. 206.
4. 1974 Manual and Methods for Chemical Analysis of Water and
Wastes, U.S. Environmental Protection Agency, p. 239-
5. Standard Methods for the Examination of Water and Wastewater,
13th Edition, p. 495, Method 220 (1971).
6. ASTM Standards, Part 28, Water; Atmospheric Analysis, p. 273,
Method 512-67, Reteree Method A (1973).
52
-------
APPENDIX NO. 1
ACIDITY
ALKALINITY
ANALYTICAL METHODS
All pH measurements were made on a Beckman Zeromatic II
using glass electrode with a saturated calomel electrode
used as the reference potential as specified in the
1974 Manual of Methods for Chemical Analysis of Water
and Wastes. U.S Environmental Protection Agency; Page
239. The instrument was calibrated daily with buffer
solutions.
All acidity analyses were performed as outlined by the
procedure listed in Standard Methods for the Examination
of Water and Wastewater, 13th Edition, Page 50, Method
101 (1071).
All acidity analyses were performed by titrating an
unaltered sample to a pH of 4-. 5 using standardized
sodium hydroxide as the titrant.
All alkalinity analyses were performed as outlined by
procedure listed in Standard Methods for the Examination
of Water and Wastewater, 13th Edition, Page 52, Method
102 (1971).
All alkalinity analyses were performed by titrating an
unaltered sample to a determined end point of pH A-.5 using
standardized sulfuric acid as a titrant.
CHEMICAL OXYGEN
DEMAND (0.0.0.)
CHLORIDES
1 -
2 -
All C.O.D. analyses were performed as outlined by the
procedure listed in Standard Methods for the Examina-
tion of Water and Wastewater. 13th Edition, Page 495,
Method 220 (1971).A proper aliquot of sample is mixed
with sulfuric acid, mercuric sulfate, silver sulfate, and
standard potassium dichromate and the excess potassium
dichromate in the cooled mixture is titrated with standard
ferrous ammonium sulfate to the endpoint indicated by
ferroin.
For the Spray Wash and Hot Rinse Locations - all chloride
analyses for the above locations were performed according
to the procedure outlined in the ASTM Standards. Part 23,
Water; Atmospheric Analysis. Page 273, Method 512-67,
Referee Method A (1973).According to this method, an
acidified sample is titrated with a dilute mercuric
nitrate solution to a blue-violet endpoint shown by a
mixed diphenylcarbazone-bromophenol blue indicator.
For the Recovery Tank and the Countercurrent Tank Locations
because of interferences shown when using the above
method, pre-treatment steps, as outlined in Standard
Methods for the Examination of Water and Waatewater.
53
-------
CHLORIDES - 13th Edition, Page 379, Method 203C, 4B (1971) were
(cont'd) followed. This pre-treatment involves boiling the
acidified sample to remove volatile compounds and
then oxidizing the sample with h7drogen peroxide.
After the pre-treatment, the standard mercuric nitrate
procedure (as outlined in the preceding paragraph) is
followed.
CYANIDES 1 - Total - all total cyanide analyses were performed as
outlined in Methods for Chemical Analysis of Water and
Wastes. U.S. Environmental Protection Agency, Page 40
(1974). All samples were collected by a refrigerated
sampler and split into a treated and untreated plastic
bottles. The treated bottles contained sodium hydroxide
to prevent significant losses in cyanide.
The cyanide as hydrocyanic acid (HCN) is released from
cyanide complexes by means of a reflux system of mineral
acid in the presence of mercuric chloride and magnesium
chloride and a distillation operation where the HCN is
then collected in a scrubber containing sodium hydroxide
solution. The pH of the scrubber solution is adjusted
to a pH of 7.0 and reacted with chloramine - T. Proper
sample aliquots were used in order that all samples could
be determined colorimetrically at a wave length of
620 nm.
2 - Free - all free cyanide analyses were performed by the
same procedure as that listed for total cyanides except
that bhe catalysts (mercuric and magnesium chlorides)
were not added, thus preventing the breakdown of the
iron-cyanide complexes. The samples were also preserved
by both refrigeration and by the addition of sodium
hydroxide.
^FLUORIDES - all the fluoride analyses ware determined potentio-
metrically using a selective ion fluoride electrode in
conjunction with a standard single junction sleeve-type
rsference electrode and a pH meter having an expanded
millivolt scale. The procedure used is contained in
manual of Methods for Chemical Analysis of Water and
Wastes. Page 65 (1974), published by the Environmental
Protection Agency. The method involves adjusting the
pH of the sample by means of a buffer solution and
chelating the polyvalent cations which could interfere.
PHOSPHORUS^ - all phosphorus analyses were performed according to the
method outlined in a manual of Methods for Chemical
Analysis of Water and Wastes, U.S Environmental
Protection Agency, Page 249. Amaonium molybdate and
antimony potassium tartrate react in an acid medium
with dilute solutions of phosphorus to form an
antimony-phospho-:aolybdate complex. This complex is
reduced to an '.ntensely blue-colored complex by ascorbic
acid. The color is proportional to the phosphorus
concentration.
-------
. - all sulfate analyses were performed as outlined in
Standard Methods for the Examination of Water and
Wastewater. 13th Edition, Page 334, Method 156C
1971). Sulfate ion is converted to a barium sulfate
suspension under controlled conditions. The resulting
turbidity is determined by a spectrophotometer and
compared to a curve prepared from standard sulfate
so?.utions.
METALS - (Cadmium, chromium, iron, nickel, potassium, sodium
and tin) all the metals were treated and analyzed as
outlined in the manual of Methods for Chemical Analysis
of Water and Wastes, Environmental Protection Agency
Metals (Atomic Absorption), Page 78. All metal samples
were preserved with HNC>3. All analyses were performed
on a Perkin-Elrner Model 306 Atomic Absorption Spectro-
photometer. The samples were prepared by taking an
appropriate aliquot to which HNC>3 had been added and
evaporating carefully to dryness. Repeated HN03
additions were made until the removal of organic
material was completed. The samples were then re-
dissolved and analyzed using the atomic absorption
spectrophotometer equipped with hollow cathode lamps.
55
-------
APPENDIX II
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 8/5 to 8/6/74
FLOW TO SEWER
TEMPERATURE
Tfl
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5gpm - 7,200 gpd
110° F
4.5
Oppm - 0 Ibs
1800 ppm - 108. lbs/Day
892 ppm - 53.6 lbs/Day
1.44 ppm - .09 lbs/Day
54 ppm - 3.24 lbs/Day
4,200 ppm - 252 lbs/Day
250 ppm - 15.0 lbs/Day
694 ppm - 41.7 lbs/Day
0.80 ppm - .048 lbs/Day
144.5 ppm - 8.68 lbs/Day
1.25 ppm - .075 lbs/Day
7.0 ppm - 0.42 lbs/Day
3517 ppm - 211 lbs/Day
3180 ppm - 191 lbs/Day
SPRAY WASH ..
35 gpm - 50,400 gpd
93°F
4.0
Acidity
140 ppm - 58.41bs/Da3
33 ppm - 139. lbs/Day
.54 ppm - .23 lbs/Day
rtX _.„_ o£ • • . /_
OO uuui ~ JO.i- ' I..Q/ JjflV
166 ppm - 69.8 Ibs/Daj
138 ppm - 580 .0 Ibgfoay
0.03 ppm - .013 Ibs/Da
2.4 ppm - 1.01 lbs/Day
*
4.78 ppm - 2.01 Ibs/Da
132 ppm - 55.5 lbs/D$
'94 ppm - 39.5 lbs/Day
HOT RINSE
40 gpm - 57,600 gpd
181°F
3.8
Acidity
8.0 pm - 3.84 Ibs
114 ppm - 54.8 lbs/Day
41 ppm - 19.71 lbs/Day
.038 ppm - .018 lbs/nn,T
46 ppm - 22 . Ibs /Day
166 ppm - 79.7 lbs/Day
18 ppm - 8.65 lbs/Day
7*
.40 ppm - .19 lbs/Dav
*
jr4.0 ppm - 1.92 lbs/Day
23.3 ppm - 11.2 lbs/Day
18.0 ppm - 8.6 lbs/Da
*
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 8/6 to 8/7/74
vr.ru TO SEWER
TEMPERATURE
A rrroiTY/ALKALINITI
mr-QRIDES
1WIEE CYANIDES
'.YVTAL CYANIDES
FLUORIDES
STILFAtES
CHROMIUM
IRON
HTCKEL
POTASSIUM
SODIDM
TIN
RECOVERY TANK
5 gpm - 7200 gpd
120° F
4.4
Acidity
20 pom - 1.20 Ibs/Dav
2250 ppm - 135 Ibs/Day
1235 ppm - 74.2 Ibs/Day
0.40 ppm - .024 Ibs/Day
137 ppm - 8.23 Ibs/Day
5500 ppm - 330 Ibs/Day
312 ppm - 18.7 Ibs/Day
625 ppm - 37.5 Ibs/Day
0.95 ppm -.057 Ibs/Day
89.5 ppm - 5.37 Ibs/Day
0.80 ppm - .048 Ibs /Day
7.25 ppm -.44 Ibs/Day
4350 ppm - 261 Ibs/Day
3775 ppm - 227 Ibs/Day
SPRAY WASH ..
35gpm - 50,400 gpd
92°F
4.2
Acidity
12 pom -5.04 Iba'Dav
85 ppm - 35.7 Ibs/Day
27 ppm - 11.3 Ibs/Day
0.84 ppm - .35 lbs/)ay
3.52 ppm - 1.48 Ibs^
56.0 ppm - 23.5 Ibs/Da
166 ppm - 69.8 Ibs /Da}
98 ppm - 41.2 Ibs/Day
*
1.6 ppm - 0.67 Ibs/Dqj
*
4.26 ppm - 1.79 Ibs^
86 ppm - 36. 1 Ibs/^y
52 ppm - 21.9 Ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
185°F
4.6
Alkalinity
2.0 pom - 0.96 Ibs /Day
72 ppm - 34.6 Ibs/Day
46 ppm - 22.1 Ibs/Day
.16 ppm - .077 Ibs/Day
>r56 ppm - 26. 9 Ibs/Day
158 ppra - 75.9 Ibs/Day
11 ppm - 5.28 Ibs/Day
K
0.40 ppm - .19 lbs/Day
*
3.71 ppm - 1.78 lbs/Day
24.4 ppm -11.7 lbs/Day
9 ppm - 4-32 Ibs, /pay
*
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 8/7 to 8/8/74
FLOW TO SEWER
TEMPERATURE
nH
ACIDITY/ALKALINITT
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
1110F
4.65
Alkalinity ,
296 ppm - 17.8 Ibs/Day
2200 ppm - 132 Ibs/Day
1390 ppm - 83.5 Ibs/Day
0.41 ppm - .025 Ibs/Day
120 ppm - 7.21 Ibs/Day
5000 ppm - 300 Ibs/Day
287 ppm - 17.2 Ibs/Day
649 ppm - 39.0 Ibs/Day
0.85 ppm - 0.05 Ibs/Day
74.5 ppm - 4.47 Ibs/Day
0.65 ppm - .039 Ibs/Day
7.7 ppm - 0.46 Ibs/Day
4150 ppm - 249 Ibs/Day
3785 ppm - 227 Ibs /Day
SPRAY WASH ..
35 gpm - 50,400 gpd
930 F
4.2
Acidity
12.0 ppm -5.04 Ibs/Daj
185 ppm - 77.8 Ibs/Daj
42.5 ppm -17.9 Ibs/fetf
0.94 ppm - .40]bs/Day
2.4 ppm - 1.01 lbs/Da
115 ppm - 48.3 lbs/Da:
170 ppm - 71.5 Ibs/Day
181 ppm - 76.1 lbs/Da
.02 ppm - .01 Ibs/Day
2.5 ppm - 1.05 Ibs/Day
*
4.5 ppm - 1.89 Ibs^aj
161 ppm - 67.7 Ibs/ife3
'83 ppm - 34.9 Ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
182° F
4.15
Acidity
4.0 ppm - 1.92 Ibs/Day
154ppm - 74.0 Ibs/Day
39 ppm - 18.7 Ibs
««____
fO.21 ppm - 0.10 Ibs /DS v
'50 ppm - 24.0 Ibs/Day
146 ppra - 70.14 Ibs/Day
r!4 ppm - 6.73 Ibs/Day
*
0.39 ppm - .19 Ibs/Day
*
3.72 ppm - 1.75 Ibs/Day
24.4 ppm - 11.7 Ibs /Day
11 ppm - 5.28 Ibs/Day
*
-------
COONTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSE
*r.rw TO SEWER"
TEMPERATURE
rw
AP.TOITY/ALKALINITY
nm.nRlDES
ram
mm CYANIDES
TYEAL CYANIDES
JLUCRIDES
STITJ-ATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
107°F
4.5
Oppra - 0 Ibs/Day
1540 ppm - 92.5 Ibs/Day
10,108 ppm - 607 Ibs/Day
.84 ppm - .05 Ibs/Day
5.32 ppm - .32 Ibs/Day
3500 ppm - 210 Ibs/Day
233 ppm - 14.0 Ibs/Day
1238 ppm - 74.3 Ibs/Day
0.90 ppm - .054 Ibs/Day
100 ppm - 6.00 Ibs/Day
0.95 ppm - .057 Ibs/Day
6.5 ppm - 0.39 Ibs/Day
3150 ppm - 189 Ibs/^y
2500 ppm - 150 Ibs/Day
SPRAY WASH ..
35 gpm - 50,400 gpd
95°F
4.0
Acidity
18 ppm - 7.57 Ibs/bay
165 ppm -69.4 Ibs/baj
49 ppm - 20.6 Ibs/jay
. 566 ppm - . Z^. . Ibs/Da;
88 ppm - 37.0 Ibtfoey
130 ppm -75,7 Ibs/Day
178 ppm -52.11bs/Ba3
.05 ppm -.013 Ibs/Dqy
3.7 ppm -1.351bs/Da2
*
4.84 ppm -1.981bs/D<
147 ppm -87.9 Ibs/Cty
1 87 ppm -39.1 Ibsytey
HOT RINSE
40 gpm - 57,600 gpd
176°F
4.1
Acidity
4.0 ppm - 1.92 Ibs/Day
94 ppm - 45.2 Ibs/Day
64 ppm - 30.7 Ibs/Day
.100 ppm - .05 Ibs/Day
• .277 ppm - .13 Ibs/Day
14 ppm - 6.73 Ibs/Day
154 ppm - 74-0 Ibs/Day
31 ppm - 14.9 Ibs/Day
#
0.33 ppm - .16 Ibs/Day
*
y4.09 ppm - 1.96 Ibs/Day
32.2 Ibs - 15.5 Ibs/Day
15 Ibs - 7.21 Ibs/Day
*
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 8/13 to 4/14/74
FLOW TO SEWER
TEMPERATURE
txH
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SDLFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
113°F
4.5
0.0 ppm - 0 Ibs/Day
2900 ppm - 174 Ibs /Day
1588 ppm - 95.4 Ibs/Day
.54 ppm - .032 Ib^Day
2.48 ppm - .15 Ibs/Day
7000 ppm - 420 Ibs/Day
______
238 ppm - 14.29 Ibs/Day
1.0 ppm - .06 Ibs/Day
72 ppm - 4.32 Ibs/Day
.95 ppm - .057 Ibs/Day
8.65 ppm - .52 Ibs/Day
5900 ppm - 354 Ibs/Day
4345 ppm - 261 Ibs/Day
SPRAY WASH ..
35 gpm - 50,400 gpd
91°F
4.2
Acidity
96 ppm - 40.4 Ibs/Day
240 ppm - 101 Ibs/Day
93 ppm - 39.1 Ibs/Day
.42 ppm - .18 Ibs/bay
155 ppm -65.. 2 Ib3/r&2
180 ppm - 75-7 Ibs/bsy
124 ppm - 52.1 IbgDaj
.03 ppm - .013 Ibs/baj
3.2 ppm - 1.35 Ibsyfoy
#
4.71ppra- 1.98 Ibs/Dgy
209 ppm - 87.9 Ibafa
' 93 ppm - 39.1 Ibs/ttey
HOT RINSE
40 gpm - 57,600 gpd
180°F
5.4
Alkalinity
4.0 ppm - 1.92 Ibs /Day
72 ppm - 34-6 Ibs /Day
32 ppm - 15.4 Ibs/^y
.06 ppm - .029 Ibs /Day
.099 ppm - .048 Ibs/Day
15 ppm - 7.21 Ibs/Day
150 ppm - 72.1 Ibs/Day
21 ppm - 10 . 1 Ibs /Day
#
.37 ppm - 0.18 Ibs/Day
*
3.93 ppm - 1.89 Ibs/Day
36.7 ppm - 17.6 Ibs/Day
13 ppm - 6.24 Ibs/Day
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSE
DATE 8/14. to 8/15/74
FLOW TO SEWER
TEMPERATDRE
i>H
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM •
TIN
RECOVERY. TANK
'5 gpm - 7200 gpd
111°F
4.6
Alkalinity
142 ppm - 8.53 Ibs /Day
3130 ppm - 191 Ibs/Day
H45 ppm - 86.8 Ibs/Day
1.34 ppm - .08 Ibs/Day
7.0 ppm - .42 Ibs/Day
9400 ppm - 564 Ibs/Day
184 ppm -11.0 Ibs/Day
193 ppm - 11.6 Ibs/Day
.75 ppm - .045 Ibs/Day
81.5 ppm - 4.89 Ibs/Day
1.00 ppm - .06 Ibs/Day
10.45 ppm - .63 Ibs/Day
4500 ppm - 270 Ibs/Day
4795 ppm - 288 Ibs/Day
SPRAY WASH .
35 gpm - 50,400 gpd
9C°F
3.7
Acidity
84 ppm - 35.3 Ibs
20- oppm -35.3 ibs/Day
80 ppm - 33.6 Ibs /Day
155 ppm -65.2 Ibs/Daj
166 ppm -69.8 Ibs/Day
175 ppm -73.6 Ibs/Day
.05 ppm -.02 ibs/Day
3.5 ppm -1>47 ibs/Day
*
4.89 ppm -2.06lbs/Daj
205 ppm -86.2 Ibs/Day
'150 ppm -63.1 Ibs/Day
HOT RINSE .
40 gpm - 57,600 gpd
186°F
4.2
Acidity
4.0 DDm - 1.92 Ibs/Day
79 ppm - 38.0 Ibs/Day
19 ppm - 9.13 Ibs/Day
.113 ppm - .05 Ibs/Day
.413 ppm - .20 Ibs/Day
28 ppm - 13.5 Ibs/Day
150 ppm - 72.1 Ibs/Day
26 ppm - 12.5 Ibs/Day
*
0.5 ppm - .24 Ibs/Day
*
4.12 ppm - 1.98 Ibs /Da
48.9 ppm - 23.5 Ibs/Day
22 ppm - 10.6 Ibs/Day
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSIS
DATE 8/19 to 8/20/74
FLCW TO SEWER
TEMPERATURE
r>H
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SI]LFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
109°F
4-4
Acidity
248 ppm - 14.9 Ibs/Day
3300 ppm - 198 Ibs /Day
1417 ppm - 85.1' Ibs /Day
.68 ppm - .041 Ibs/Day
15 ppm - .90 Ibs/Day
3800 ppm - 228 Ibs/Day
357 ppm - 21.4 Ibs/Day
384 ppm - 231.1 Ibs/Day
.85 ppm - .051 Ibs/Day
75.5 ppm - 4-53 Ibs/Day
.85 ppm - .051 Ibs/Day
8.55 ppm - .51 Ibs/Day
5400 ppia - 324. Ibs/Day
3520 ppm - 211 Ibs/Day
SPRAY WASH ..
35 gpm - 50,400 gpd
91°F
3.6
Acidity
150 ppm -63.1 Ibs/Day
80 ppm - 33-6 Ibs/Day
83 ppm - 34-9 Ibs/Day
.31 ppm -.13 Ibs/Day
.51 ppm -.21 Ibs/Day
260 ppm -109 Ibs/Day
190 ppm -79.9 Ibs/Day
149 ppm -62.6 Ibs/Day
.03 ppm -.013 Ibs/Day
5.3 ppm -2.23 Ibs/Dav
*
5.36 ppm -2.25 Ibs/Da:
372 ppm - 156 Ibs/Day
287 ppm - 121 Ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
183°F
3.7
Acidity
12 ppm - 5.76 Ibs /Day
78 ppm - 37.5 Ibs/Day
28 ppm -13.5 Ibs/Day
.15 ppm - .075 Ibs/Dav
.29 ppm - .14 Ibs/Day
29 ppm -13.9 Ibs/Day
122 ppm - 58. 6 Ibs/Dav
49 ppia - 23.5 Ibs/Day
#
0.72 ppm - .35 Ibs/Dav
#
•4.13 ppm - 1.98 Ibs/Day
46.7 ppm - 22.4 Ibs/Dav
31 ppm - 14.9 Ibs/Day
*
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 8/20 to 8/;.j/?/
FLOW TO SEWER
TEMPERATURE
ifl
ACIDITY/ALKALINITY
CHLORIDES
COD
T?RTi!F PYflWTnFQ
infiCi LilAIM J.JJJ-O
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY TANK
5 gpm - 7200 gpd
113°F
4.5
Oppm - 0 Ibs /Day
2700 ppm - 162 Ibs /Day
1533 ppm - 92.1 Ibs /Day
32 ppm - 1.92 Ibs/Day
5800 ppm - 348 Ibs/Day
330 ppm - 19.8 Ibs/Day
227 ppm - 13.6 Ibs/Day
0.80 ppm - .04.8 Ibs/Day
63.5 ppm - 3.81 Ibs /Day
0.85 ppm - 0.051 Ibs/Day
8.7 ppm - 0.52 Ibs/Day
5200 ppm - 312 Ibs/Day
3675 ppm - 221 Ibs/Day
SPRAY WASH ..
35 gpm - 50,400 gpd
93°F
3.9
Acidity
138 ppm -58.0 Ibs/Da;
384 ppm -161 Ibs/Day
100 ppm -42.0 Ibs/Da-
8.0 ppm -3.36 Ibs/Da-
245 ppm -103 Ibs/Day
174 ppm -73. libs/Day
119 ppm -50.01bs,Day
.02 ppm -.008 Ibs/Day
3.4 ppm -1.431bs/Dav
*
5.28 ppm -2 . 22 Ibs/Da
321 ppm -135 Ibs/Day
'228 ppm -95. g ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
184°F
4.5
Oppm - 0 Ibs/Day
59 ppm - 28.3 Ibs/Day
12 ppm - 5.76 Ibs/Day
2.4 ppm - 1.15 Ibs/Day
29 ppm - 13.9 Ibs/Day
154 ppm - 74.0 Ibs /Da 5
39 ppm - 18.7 Ibs/Day
#
0.68 ppm - .33 Ibs/Daj
*
r4.22 ppm - 2.03 Ibs/Dt
4.8.9 ppm - 23.5 Ibs/Df
25 ppm - 12.0 Ibs/Day
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 8/21 to 8/22/74
FLCW TO SEWER
TEMPERATURE
uH
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
110°F
4-4
Acidity
116 ppm -6.97 Ibs/Day '
4800 ppm - 288 Ibs/Day
6238 ppm - 375 Ibs /Day
.633 ppm - .038 lbs/Day
2.5 ppm - .15 Ibs /Day
5000 ppm - 300 Ibs /Day
287 ppm - 17.2 lbs/Day
271 ppm - 16.3 lbs/Day
.85 ppm - .051 lbs/Day
67 ppm - 4.02 lbs/Day
.90 ppm - .054 lbs/Day
8.85 ppm - .53 lbs/Day
6350 ppm - 381 lbs/Day
4455 ppm - 268 lbs/Day
SPRAY WASH ..
35 gpm - 50,400 gpd
92 °F
3.9
Acidity
132 Dm -55.5 lbs/Day
440 ppm -185 lbs/Da;y
106 ppm -u>6 lbs/Day
.273 PP^ -.^its/Day
M Ppm - .27 Ibs/Dav
225 PI« -94.6lbs/Da,
162 ppm -68.1 lbs/Day
203 ppm -85.3 Lbs/Day
#
5.2 ppm -2.19 lbs/Day
*
5.39 ppm -2.27 Ibs/Da;
331 ppm -^ lbs/Day.
'271 pprn -^ lbg/Day
HOT RINSE
40 gpm - 57,600 gpd
183°F
4.3
Acidity
JUJ.rmm -. R-6^ Tha/Ttaw
144ppm - 69.. 2 lbs/Day
46 ppm - 22.1 lbs/Day
.087 ppm - .042 Ibs/Day
.124 ppm - .060 Ibs/Day
33 ppm - 15.9 lbs/Day
150 ppm - 72.1 Ibs /Dav
81 ppm - 38.9 Ibs/Day
ik
.74 ppm - .36 lbs/Day
%
7-4.30 ppm - 2.07 Ibs/Da-y
55.6 ppm - 26.7 lbs/Day
36 ppm - 17.3 lbs/Day
*
-------
COONTERCUKRENT RINSING
PHAS.K I - CHEMICAL ANALYSTS
DATE 8/22 to 8/23/?A
FLOW TO SEWER
TEMPERATURE
I?
ACIDITY/ALKALINITY
CHLORIDES
COD
J'KlSE ClANID.no
TOTAL CYANIDES
ILUORIDES
SHLFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
ITICKEL
POTASSIUM
SODIUM
TIN „,.
RECOVERY . TANK
5 gpm - 7200 gpd
115°?
4.5
0. Oppm - 0 Ibs/Day
4600 ppm - 276 Ibs/Day
1303 ppm - 78.2 Ibs/Day
17.6 ppm - 1.06 Ibs/Day
6000 ppm - 360 Ibs/Day
384 ppm - 23.1 Ibs/Day
2^9 ppm - 15.0 Ibs/Day
.90 ppm - .054 Ibs/Day
71 ppm - 4.26 Ibs/Day
.55 ppm - .033 Ibs/Day
9.1 ppm - .55 Ibs/Day
6500 ppm - 390 Ibs/Day
4930 ppm - 296 Ibs/Day
SPRAY WASH ..
35 gpm - 50,400 gpd
95°F
3.65
Acidity .
164 ppm -68.9 Ibs/Daj
544 ppm -229 Ibs/Day
84 ppm -35.3 Ibs/Day
tt"| 9 nrttn _ Oy T \^f* /n**.
• o±j ppm -04 -Los/Day
2.3 ppm -.97 Ibs/Day
320 ppm -^ ibs/Day
166 ppm -69. 8 Ibs/Day
170 ppm -71. 5 ibs/Day
.02 PPni-.oo8lbs/Dav
5-5 ppm -2.3Hbs/Itey
*
5.53 ppm -2.321bs/Ety
418 ppm - 176 ibs/Day
'347 ppm-u6 ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
178°F
4.0
Acidity .
10 ppm - 4.80 Ibs/Day
96 ppm - 4-6.1 Ibs/Day
54 ppm - 25.9 Ibs/Day
.167 ppm - .08 Ibs/Day
33 ppm - 15.9 Ibs/Day
150 ppm - 72.1 Ibs/Day
81 ppm - 38.9 lbs/D9y
#
.72 ppm - .35 Ibs/Day
*
4.17 ppm - 2.00 Ibs/Day
62.2 ppm - 29.9 Ibs/Day
37 ppm - 17.8 Ibs/bay
*
-------
COONTERCURRENT RINSING
PHASE I _ CHEMICAL ANALYSES
DATE 8/26 to 8/27/74
FLOW TO SEWER
TEMPERATURE
pH
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
112°F
4.3
Acidity
485 ppm - 29.1 iWDay '
2200 ppm - 132 Ibs/Day
1944 ppm - 117 Ibs/Day
10.8 ppm - .65 Ibs/Day
2850 ppm - 171 Ibs/Day
295 ppm - 17.7 Ibs/Day
261 ppm - 15.7 Ibs/Day
.75 ppm - .045 Ibs/Day
32.5 ppm - 1.95 Ibs/Day
.45 ppm - .027 Ibs/Day
6.15 ppa - .37 Ibs/Day
3150 ppm - 189 Ibs/Day
2500 ppm - 150 Ibs/Day
SPRAY WASH ..
80 gpm - 115,200 gpd
94°F
4.2
Acidity
2 . 0 ppm -1 . 92 Ibs/Day
50 ppm -48.0 Ibs/Day
19.4 ppm -IS^lbSj/tb-s
.6 ppm -.58 Ibs/Day
47 ppm -54-2 Ibs/Day
170 ppm -163 Ibs/Day
48 ppm -46,1 Ibs/Day
* \
1.5 ppm -^44 ibs/Day
*
4.91 ppm -4.721bs/tby
109 ppm -105 Ibs/Day
'62 ppm - 59.6 ibs/Daj
HOT RINSE
40 gpm - 57,600 gpd
180°F
6.5
Alkalinity
18.0 ppm - 865 Ibs/Day
46 ppm - 22.1 Ibs/Dav
43 ppm - 20.7 Ibs/Day
1 —
.10 ppm - .048 Ibs/Day
.112 ppm - .054 Ibs/Day
5.2 ppm - 2.50 Ibs/Day
174 ppm - 83.6 Ibs/Day
36 ppm - 17.3 Ibs/Day
*
.80 ppm - .38 Ibs/Day
*
4-31 ppm - 2.07 Ibs/Day
27.8 ppm - 13.4 Ibs/Day
14 ppm - 6.73 Ibs/Day
* ^Detectable Limit
Analysis Not Performed
66
-------
CODNT.ERCURRENT RINSING
PHASE I - CHEMTCAL ANALYSES
DATE 8/27 to 8/28/74
l?T.oy TO SEVER
TEMPERATURE
r"
arrmiTY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SITUATES
SUSPENDED SC3LIDS
CHROMIUM
•moN
WTCKEL
POTASSIUM
SODIUM
TDL
RECOVERY . TANK
5 gpm - 7200 gpd
112 OF
4.5
Oppm - 0 Ibs/Day
2000 ppm - 120 Ibs/Day
1012 ppm - 60.8 Ibs/Day
,
.007 ppm - .0004 Ibs/Day
4.0 ppm - .24 Ibs/Day
3250 ppm - 195 Ibs/Day
295 ppm - 17.7 lb£/Day
195 ppm - 11.7 Ibs/Day
.85 ppm - .051 Ibs/bay
35 ppm - 2.10 Ibs/Day
.55 ppm - .033 Ibs/bay
7.25 ppm - .44 Ibs^ay
3250 ppm - 195 Ibs/Day
2480 ppm - 149 Ibs/Day
SPRAY WASH ..
80 gpm - 11,200 gpd
95°F
5.0
Alkalinity
10 ppm - 9.61 Ibs/Day
35 ppm -33.6 Ibs/Day
35 ppm -33.6 Ibs/Day
nnm r,^m Ibs/
.0001 ppnu.oooi Day
.45 ppm -.43 ibs/Day
36 ppm - 34.6 ibg/Day
174 ppm - 167 Ibs/Day
45 ppm -43.2 Ibs/Daji
.02 ppm -019 ibs/Daj;
1.3 ppm --L 25 lbg/Da:s
*
4.89 ppm -4..70]bs/Da
73 ppm -vo.l Ibs/Day
' 25 ppm -24^ ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
181°F
6.3
28 ppm - 13.5 Ibs/Day
58 ppm - 27.9 Ibs/Day
58 ppm - 27.9 Ibs/Day
.05 ppm - .024 Ibs/Day
2.6 ppm - 1.25 Ibs/Day
180 ppm - 86.5 Ibs/Day
30 ppm - 14.4 Ibs/Day
*
.61 ppm - .29 Ibs/Day
*
4.40 ppm - 2.11 Ibs/Day
27.8 ppm - 13.4 Ibs/Day
9 ppm - 4-32 Ibs/Day
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 8/28/ to 8/29/74
FLOW TO SEWER
TEMPERATURE
PH
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
STJLFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
112°F
4-5
Oppm - 0 Ibs /Day
2100 ppra - 126 Ibs /Day
1166 ppm - 70.0 Ibs/ Day
.0001 ppm - 0 Ibs/ Day
24 ppra - 1.44 Ibs/ Day
4300 ppm -258 Ibs /Day
295 ppm - 17.7 Ibs /Day
74 ppm - 4.44 Ibs /Day
.90 ppm - .054 Ibs/ Day
39. ppm - 2.34 Ibs /Day
.50 ppm - .03 Ibs /Day
9.1 ppm - .55 Ibs /Day
4150 ppm - 249 Ibs /Day
2780 ppm - 167 Ibs/Day
SPRAY WASH ..
80 gpm - 115,200 gpd
95°F
4.0
Acidity
16.0 ppm -15.4 Ibs/Bay
50 ppm -48.0 Ibs/Day
31 ppm -29.8 Ibs/Day
.028 ppm -.027 Ibs/Dss
.38 ppm -.37 Ibs/Day
51 ppm -49.0 Ibs/Day
166 ppm - 159 Ibs/Day
40 ppm -38.4 Ibs/Day
*
-, ^ lts/
1.10 ppm -l-.Ob pay. ..
#
4.95 ppm -4.76 D?^
96 ppm -92.2 Ibs/Day
42 ppm -/.0.4 Ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
184°F
8.2
Alkalinity
18.0 ppm - 8.65 Ibs/Dav
36 ppm - 17.3 Ibs/Day
12 ppm - 5.76 Ibs/Dav
.0002 ppm - 0 Ibs/Dav
.10 ppm - .05 Ibs/Dav
3.6 ppm - 1.73 Ibs/Dav
170 ppm - 81.7 Ibs/Day
5.0 ppm - 2.40 Ibs/iw,
*
.53 ppm - .25 Ibs/Dav
#
4-34 ppm - 2.08 Ibs/Ttay
27.3 ppm - 13.4 Ibs/Dav
10 ppm - 4.80 lb£/Day
-------
CODNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 3/^9 to 8/:35 xbg/Qj
#
5.25 ppm -5.041bs/fotf
92 ppm -88.4 lbs/Day
' 47 ppm -45.2 lbs/Day
HOT RINSE
40 gpm - 57,600 gpr?
134° ff
8.3
Alkalinity
22.0 ppm - 10.6 Ibj/Day
16 ppm - 7.69 lbs/Day
.02 ppm - .01 lbs/Day
.172 ppm - .083 lbs/Day
2.1 ppm - 1.01 lbs/Day
158 ppm - 75.9 lbs/Day
19 ppm - 9.13 lb£/Day
#
.57 ppm .27 Ibs/Day
*
4.68 ppm - 2.25 lbs/Day
27.8 ppm - 13.4 Ibi/Day
7 ppm - 3.36 Ibn/Day
*
-------
CODNTERCDRRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 9/3/ to 9/4/74
FLOV/ TO SEWER
TEMPERATURE
Ttf
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
112°F
4.3
Acidity
812 ppm - 43.8 Ibs/Day
1620 ppm - 97.3 Ibs/Day
894 ppm - 53.7 Ibs/Day
______
16.5 ppm - .99 Ibs/Day
3250 ppm - 195 Ibs/Day
303 ppm - 18.2 Ibs/Day
195 ppm - 11.7 Ibs/Day
.95 ppm - .057 Ibs/Day
31 ppm - 1.86 Ibs/Day
.65 p?m - .039 Ibs/Day
6.7 ppm - .40 Ibs/Day
3400 ppm - 204 Ibs/Day
2435 ppm - 146 Ibs/Day
SPRAY WASH ..
80 gpm - 115,200 gpd
92°F
4.3
Acidity
6.0 ppm -5.76 Ibs/Day
50 ppm - 48.0 Ibs/Day
20 ppm - 19.2 Ibs/Day
.175 ppTi -.17 Ibs/Day
.183 ppm -.176 Ibs/Day
39 ppm - 33-5 Ibs/Day
180 ppm J-73 Ibs/Day
18 ppm - 17.3 Ibs/Day
.04 ppm -.038 Ibs/Day
1.0 ppm -.96 ibs/Day
*
4.34 ppm -4.17lbs/fcy
69 ppm - 66.3 Ibs/Day
26 ppm - 25.0 Ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
178°F
7.0
Alkalinity —
8.0 ppm - 3.84 Ibs/Dav
24 ppm - 11.5 Ibs/Day
41 ppm - 19.7 Ibs/Day
______
.12 ppm - .058 Ibs/Dav
3.2 ppm - 1.54 Ibs/Dav
162 ppm - 77.8 Ibs/Dav
20 ppm - 9.61 Ibs/Day
#
.59 ppm - 028 Ibs/Day
#
3.97 ppm - 1.91 Ibs/Day
27.8 ppm - 13.6 Ibs/Day
13 ppa - 6.24 Ibs/Day
*
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSES
DATE 9/4/ to 9/5/74
TPT.CW TO SEWER
TEMPERATURE
r?
A nlDITY/ALKALINITr
nHLORIDES
nan
TOEE CYANIDES
•jfOTAL CYANIDES
KHORI0KS
SpLFATES
SUSPENDED SOLIDS
CplCMTDM
man
NICKEL
POTASSIUM
SCB5IDM
T™
RECOVERY TANK
5 gpm - 7200 gpd
114°F
Acidity
36D ppm - 21.6 Its/Day
1860 ppm - 112 Its/Day
884 ppm - 53.1 las/Day
__
152 ppm - 9.13 Ibs/Day
3400 ppm - 204 Ibs/Day
295 ppm - 17.7 Ibs/Day
210 ppm - 12.6 Ibs/Day
.80 ppm - .048 Ibs/Day
35 ppm - 2.10 Ibs/Day
.50 ppm - .03 Ibs/Day
6.45 ppm - .39 Ibs/Day
3400 ppm - 204 Ibs/Day
2735 ppm - 164 Ibs/Day. . .
SPRAY WASH ..
80 gpm - 115,200 gpd
89°F
4.8
Alkalinity
2.0 ppm -1,92 Ibs/Day
60 ppm -57.6 Ibs/Day
16 ppm -15.4 Ibs/Day
Ibs/
.002 ppm -.002 Day •
.88 ppm - .85 Ibs/Day
35 ppm - 33.6 Ibs/Day
186 ppm - 179 ibs/Dav
45TOm - 43.2 Ibs/Day
.03 ppm - .03 Ibs/Day
1.2 ppm -1.15 Ibs/Day
#
4.27 ppm -4.101bs/Day
72 ppm - 69.2 Ibs/Day
30 ppm - 28.8 Ibs/Day
HOT RINSE
40 gpm - 57,600 gpd
186° F
5.3
Alkalinity
12.0 .ppm - 5.76 Ibs/Day
36 ppm - 17.3 Ibs/Day
32 ppm - 15.4 Ibs/Day
.25 ppm - .12 Ibs/Day
2.46 ppm - 1.18 Ibs/Day
166 ppm - 79.7 Ibs/Day
25 ppm - 12.0 Ibs/Day
*
.57 ppm - .27 Ibs/Day
*
3.77 ppm - 1.81 Ibs/Day
25.6 ppm - 12.3 Ibs/Day
11 ppm - 5.28 Ibs/Day
*
-------
COUNTERCURRENT RINSING
PHASE I - CHEMICAL ANALYSE
DATE 9/5 to 9/6/74
FLOW TO SEWER
TEMPERATURE
r>H
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
RECOVERY . TANK
5 gpm - 7200 gpd
110°F
4.3
Acidity
660 ppm - 39.6 Ibs/Day
1900 ppm - 114 Ibs/Day
160 ppm - 9.61 Ibs/Day
.125 ppm - .008 Ibs/Day
60 ppm - 3.60 Ibs/Day
3700 ppm - 222 Ibs/Day
272 ppm - 16.3 Ibs/Day
245 ppm - 14-7 Ibs/Day
.60 ppm - .04 Ibs/Day
45 ppm - 2.70 Ibs/Day
.45 ppm - .027 Ibs/Day
6.8 ppm - .41 Ibs/Day
3700 ppm - 222 Ibs/Day
2700 ppm - 162 Ibs/Day
SPRAY WASH ..
80 gpm - 115,260 gpd
91°F
4.5
Oppm - 0 Ibs/Day
65 ppm -62.4 Ibs/Day
8 ppm -7.69 Ibs/Day
.1 ppm -.096 Ibs/Day
.3 ppm -029 Ibs/Dav
48 ppm -46.1 ibs/Dav
166 ppm - 159 Ibs/Day
90 ppm -86>5 lbs/Da^
.03 ppm - /
1.4 ppm -1.35 Ibs/Day
*
4.43 ppm -£. 26 Ibs/Day
117 ppai -112 ibs/Day
64 ppm -61>5 ibs/Da;v
HOT RINSE
40 gpm - 57,600 gpd
135°F
5.9
Alkalinity —
16 ppm - 7.69 Ibs/Day
26 ppm - 12 . 5 Ibs/Day
44 ppm - 21.1 Ibs/Day
.126 ppm - .061 Ibs/Dav
2.56 ppm - 1.23 Ibs/Day
154 ppm - 74.0 Ibs/Day
25 ppm - 12.0 Ibs/Day
.61 ppm - .29 Ibs/Day
*
3.72 ppm - 1.79 Ibs/Dav
28.9 ppm - 13.9 Ibs/Day
11 ppm - 5.28 Ibs/Day
*
-------
Appangi in
COUNTERCURRENT RINSING
PHASE III _ CHEMICAL ANALYS&3
DATE 8/26/75
ffr.rTJ TO SEWER
TEMPERATDRE
COUNTERCURRENT TANK
0 gal/min - 0 gal/day
SPRAY WASH ..
24,000 gal/day
87° F.
HOT RINSE
43,200 gal/day
175° F.
CHLORIDES.
COD
4-3
7.3
Acidity
6.0 ppm - 1,20 Ibs/Da:
Alkalinity ,
U.0 ppm - 5.04 Ibs/Day
80 ppm -16.0 Ibs/Day
50 ppm - 18.0 Ibs/Day
TTREE CYANIDES
.176 ppm -0.35 Day
.119 ppm - .043 Ibs/Day
CYANIDES
.231 ppm - .05 Day
.202 ppm - .073 Ibs/Day
FLUORIDES
40 ppm -8.01 Lbs/Da;
3.6 ppm - 1.29 Ibs/Day
SULFATffS
SUSPENDED SOLIDS
Ibs
153.6 ppm -30.7 Day
1 Kd /
"IBs/
6.0 ppm -1.20 Day .
149.6 ppm - 53.9 Ibs/Day
12.0 ppm - 4.32 Ibs/Day
CEEOMTOM
IRON
0.35 ppm -.07 Ibs/De yO.37 ppm - .13 Ibs/Day
NICKEL
PQTASSIT1M
Ibs/
4.73 ppm -.95 Day
4-31 ppm - 1.55 Ibs/Day
SODIDH_
89 ppm -17.8 Ibs/Da
22 ppm - 7.93 Ibs/Day
65 ppm -13.0 Ibs/Da,
9 ppm - 3.24 Ibs/Day
*le Limit
-Analysis not performed.
73
-------
COUNTERCURRENT RINSING
PHASE III - CHEMICAL ANALYSES
DATE 8/29/75
FLOW TO SEWER
TEMPERATURE
pH
ACIDITY/ALKALINITY
j
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
COUNTERCURRENT TANK
0 gal
.
_
_
_
_
—
—
_
.
_
SPRAY WASH ..
24,000 gpd
85° F.
4.1
Acidity Ibs./
10 ppm -2.00 Day
75 ppm -15.0 Ibs /Day
_
Ibs/
.170 ppm -,034 Day •
.170 ppm -.Q34lbs/Da;
44 ppm - 8.81 Ibs/lter
149.6 ppm - 29.9 Day
Ibs/
11 ppm - 2.20 day.
*
0.52 ppm -.10 Ibs /Da
*
Ibs/
4.62 ppm -.92 Day
87 ppm -17.51bs/Day
65 ppm -13..01bs/Day
HOT RINSE
43,200 £pd
177° F.
6.9
Alkalinity
12.0 ppm - 4-32 lbs./Dav
300 ppm - 108 Ibs. /Day
— _
.280 ppm - .10 Ibs. /Day
r .345 ppm - .12 lbs./Dav
8.0 ppm - 2.88 Ibs ./Day
, 142.8 ppm - 51-5 Ibs. /Da-,
22.0 ppm - 7.93 lbs./Dav
#
r 0.53 ppm - .19 ibs./foav
*
4-28 ppm - 1.54 lbs./Dav
28 ppm - 10.1 lbs./Dav
12 ppm - 4-32 Ibs /Day
*
-------
CODNTERCDRRKNT RINSING
PHASE III _ CHEMICAL ANALYSIS
DATE 9/2/75
w/if TO SEWER
nueuPEaATPRE
COP
COPNTERCURRENT TANK
0 gal
SPRAY WASH ..
24,000 gpd
84° F.
5.4
Alkalinity Lbs/
6.0 ppm -1.2 Day
32.5 ppm -6.5
bs/
Ibs/
10.2 ppm -2.04 Pav
HOT RINSE
43,200 gpd
173° F.
8.0
Alkalinity
22 ppm - 7.93 Ibs/Day
20 ppm - 7.21 Ibs/Day
6.8 ppm - 2.45 Ibs/Day
CYANIDES
lbs/
.360 ppm - .072 pay •
.162 ppm - .058 Ibs/Day
TYVPAT. CYANIDES
.360 ppm - .07.2
Ibs/
.244 ppm - .088 Ibs/Day
FLUORIDES^
28 ppm - 5.60 Ibs/Da;
3.4 ppm - 1.22
121 ppm - 43.6 Ibs ./bay
STILFATES
oo r,
114.8 ppm -23.0
Ibs/
47 ppm - 9.41 Day
lbS/
SnSPEHPED SOLIDS
CHROMIIJM
14 ppm - $.04 Ibs/Day
mow
-, ,«
1.49 ppm -.30
lbs/
2.35 ppm - .85 Ibs/Day
NICKEL
POTASSIUM
SODIDM
4.82 ppm -.96]bs/Day
4.32 ppm - 1.56 lbs ./Day
42 ppm -e.41 Ibs/Day
18 ppm - 6.49 lbs ./Day
TIN
25 ppm -5.00 Ibs/Day
4 ppm - 1.44 lbs ./Day
* -
-------
COUNTERCUKRENT RINSING
PHASE III - CHEMICAL ANALYSES
DATE
FLCW TO SEWER
TEMPERATURE
pH
ACIDITY/ALKALINITY
/
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SDLFATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
COUNTERCURRENT TANK
0 gal
^
_
_
_
_
_
_
_
_
_
—
—
-
-
-
SPRAY WASH ..
24,000 gpd
89° F.
4.5
0.0 ppm -
80 ppm -16.0 Its/Day
Ibs/
27.2 ppm -5. 44 Day .
Ibs/
.176 ppm -.035 Day
Ibs/
.330 ppm -.066 Day .
64 ppm -12.8 Lbs/Day
Ibs/
112 ppm -22.4 Day .
75 ppm -15.0 Ibs/Day
,x.
0.76 ppm -j. 5 Ibs/Day
#
4.61 ppm -.92 Ibs/Day
74 ppm -14.8 Ibs/Day
52 ppm -10.4 Ibs/Day
HOT RINSE
43,200 gpd
175° F.
8.0
Alkalinity
12.0ppm - 4-32 Ibs./Dav
61 ppm - 22.0 Ibs. /Day
6.8 ppm - 2.45 Ibs./Dav
.09 ppm - .032 Ibs. /Day
.148 ppm - .054 Ibs./Dav
1.7 ppm - .61 Ibs. /Day
100 ppm - 36.0 Ibs./Dav
17 ppm - 6.12 Ibs./Dav
#
0.66 ppm - .24 Ibs./Dav
#
4.22 ppm - 1.52 Ibs./Dav
14 ppm - 5-04 Ibs. /Day
4 ppm - 1.44 Ibs. /Day
*
-------
COOHTERCDRRENT RINSING
PHASE III - CHEMICAL ANALYSIS
DATE 9/11/75
pr.ru TO SEWER
n
ACIDITY/ALKALINITY
/
rnrrtRIDES
mn
mm r^TANlDES
WMT. CYANIDES
Ff.nrRTDES
SULFATES
SDSPBSDED SOLIDS
CWlpMTTjw
IRON
NICKEL
POTASSIUM
snmTUM
TIM
COUNTERCURRENT TANK
0 gal
_
_
-
_
-
-
-
-
-
-
-
-
-
-
-
-
SPRAY WASH ..
23,826 gpd
91° F.
4.4
Acidity Ibs/
2.0 ppm -.AQ n«3r
50 ppm -9.94 Ibs/Da-v
17 ppm -3.38 Ibs/Day
IBs/
.176 ppm -.035 Day .
ItsT]
.176 ppm -.035 Day
Ibs/
56.0 ppm -11.1 Day
IDS/
142.8 ppm -28.4 Day
Ibs/
47.0 ppm -9.34 Day
*
Ibs/
0.26 ppm -.052 Day
*
Ibs/
4.52 ppm -.090 Day
50 ppm -9.94 Ibs/Day
50 ppm -9.94 Ibs/Day
HOT RINSE
43,200 gpd
175° F.
8.1
Alkalinity
22 ppm - 7.93 Ibs. /Day
67.5 ppm - 24.3 Ibs./Ds
6.8 ppm - 2.45 Ibs./Daj
.032 ppm - .012 lbs./DE
.191 ppm - .069 Ibs. Ate
2.0 ppm - .72 Ibs. /Day
. 121.2 ppm - 43.7 Ibs. A
20.0 ppm - 7.21 Ibs./Di
%
0.59 ppm - 0.21 Ibs./Df
#
4.20 ppm - 1.51 lbs./I>
13 ppm - 4.68 Ibs. /Day
6 ppm - 2.16 Ibs. /Day
*
-------
CODNTERCDRRENT RINSING
PHASE III , CHEMICAL ANALYSIS
DATE 9/12/75
FLOW TO SEVER
TEMPERATURE
rH
ACIDITY/ALKALINITY
/
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULPATES
SUSPENDED SOLIDS
CHROMIUM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
COUNTERCDRRENT TANK
0 Gal
_
_
-
-
_
-
—
-
-
-
-
-
-
-
-
'
SPRAY WASH ..
23,826 gpd
90° F.
4.6
Alkalinity
2.0 ppm -.AOlbg'Dav
.65 ppm -12.9 Ibs/Day
_
Ibs/
. 162 ppm - . 032 Day .
Ibs/
.162 ppm -.032 Dav •
48 ppm -9.54 Ibs/Ba-y
146 ppm -29.0]bs/Day
55 ppm -10.9 Ibs/Day
#
0.50 ppm-. 10 Ibs/Day
#
4.70 ppm -.93]bs/Day
53 ppm -10.5 Ibs/Day
125 ppm -24.8I>s/Day
HOT RINSE
43,200 gpd
180° F.
7.0
Alkalinity
18.0 ppm - 6.49 Ibs. /Dav
18. 5 ppm - 6.. 67 Ibs. /Day
^
.082 ppm - .030 Ibs. /Dav
.220 ppm -.079 Ibs. /Day
1.24 ppm - .45 Ibs. /Day
135.6 ppm - 48.9 Ibs. /Dav
38 ppm - 13-7 Ibs. /Day
#
0.71 ppm - .26 Ibs. /Day
#
4.25 ppm - 1.53 Ibs. /Day
12 ppm - 4-32 Ibs. /Day
6 ppm - 2.16 Ibs. /Day
*
-------
COUNTERCURRENT RINSING
PHASE III - CHEMICAL ANALYSIS
DATE 9/18/75
PLOL
TO SEWER
TEMPERATURE
a r.TPlTY/ALFALINI'n:
COUNTERCURRENT TANK
0 gal
SPRAY WASH ..
36,000 gpd
93° F.
6.7
Alkalinity
18 ppm -5.4 Ibs/Day
20 ppm-6.0 Ibs/Day
HOT RINSE
25,488 gpd
o
178 F
7.5
Alkalinity
20 ppm - 4.25 Ibs./Day
54 ppm - 11.5
COD
11.9 ppm-3.6 Ibs/Day
ppm - 1.08 Ibs./Dav
TORE CYANIDES
.096 ppm-.029 Ibs/Da
r .066 ppm - .014 Ibs./Dav
. CYANIDES
Ibs/
.096 ppm -.029 Dav
.066 ppm - .Ol/, Ibs./Dav
ILPQRIDES
14 ppm -4-20 Ibs/Da;
1.6 ppm - .34 Ibs./Day
SPLFATES
114.8 ppm-34..5
97.2 ppm - 20.7 Ibs./Day
SflSPEHDED SOLIDS
32 ppm-9.6l Ibs/Day
26
-5.53 Ibs./Day
CHROMIUM
.72 ppm—.22 Ibs/Da:
0.93 ppm - 0.20 Ibs./Day
HICKEL
POTASSIUM
4.63 ppm-1.39 Ibs/Da
T 4.27 ppm - 0.91 Ibs./Day
SODIUM
30 ppm _9.oi
14 ppm - 2.98 Ibs./Day
TIN
26 ppm -7.81 Ibs/Da
12 ppm - 2.55 Ibs./Day
*
-------
COONTERCURRENT RINSING
PHASE III - CHEMICAL ANALYSIS
DATE 9/19/75
FLOy TO SEWER
TEMPERATURE
cH
ACIDITY/ALKALINITY
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
ntronMrmr
IRON
NICKEL
POTASSIUM
SODIUM
TIN
COUNTERCURRENT TANK
0 gal
—
—
_
_
_
^
_
.
_
LM
_
_
_
_
-
-
SPRAY WASH ..
36,000 gpd
87° F.
6.2
Alkalinity
10 ppm-3.00 Ibs/Day
35 ppm-10.5 Ibs/Day
10.2 ppm-3.06 l"bs/Da
.066 ppm-.020 Ibs/Da:
.066 ppm-.020 Ibs/fey
Ibs/
22.64 ppm-6.80 Dav
Ibs/
1U. 8 ppm-34.5 Dav
54 ppm-l6.2 Ibs/Day
X
0.83 ppm-. 25 Ibs/Day
K-
4.68 ppm-1.14 Ibs/Aaj
23 ppm_6.91 Ibs/Day.
16 ppm-4.80 Ibs/Day
HOT RINSE
25,488 gpd
177° F.
7.3
Aixaiinity
20 ppm - 4-25 Ibs. /Day
16.0 ppm - 3*4 Ibs. /Day
r 8.5 ppm - 1.81 Ibs. /Day
.066 ppm - .014 Ibs. /Day
.238 ppm - .051 Ibs. /Day
3.3 ppm - 0.70 Ibs. /Day
97.2 ppm - 20.7 Ibs. /Day
33 ppm - 7.01 Ibs. /Day
*
1.27 ppm - 0.27 Ibs. /Day
*
4.33 ppm - .092 Ibs. /Day
15 ppm - 3-19 Ibs. /Day
3 ppm - .64 Ibs. /Day
* ^Detectable Limit
Analysis Not Performed
80
-------
COONTERCORRENT RINSING
PHASE III - CHEMICAL ANALYSIS
DATE 9/26/75
vr.cfj TO SEWER
•fEMPERATURE
i?
ACIDITY/ALKALINITI
t
CHLORIDES
r/ffi
™EE CYANIDES
jnpvi. CYANIDES
W.TTCRIDES
RnrFAfES
snsPfEMDED SOLIDS
nmoMUM
7*0*
WTHKEL
POTASSIUM
flnmnM
Tffi
CODNTERCURRENT TANK
0 gal
-
-
—
—
-
- '~ • ..
-
-
-
-
-
-
_
-
-
-
SPRAY WASH ..
22,320 gpd
85° F.
8.1
Alkalinity
28 ppm- 5. 21 Ibs/Day
54 ppm-10.1 Ibs/Day
Ibs/
20.4 ppm-3.80 Day
.104 ppm-.02 Ibs/Day
.104 ppm-.02 Ibs/Day
35.2 ppa-e.ssijs/Day
Ibs/
124.8 ppm_23.2 Day
64 ppm-ii,9 Ibs/Day
*
0.85 ppm_.i6 Ibs/Da^
#
4.70 ppm_o.87 ibs/Da
41 ppm-7.63 Ibs/Day
' 40 ppm-7.45 Ibs/Day
HOT RINSE
39,312 gpd
175° F.
6.5 .
Alkalinity
12.00 ppm - 3.93 Ibs. /Day
30 ppm - 9.84 Ibs. /Day
6.8 jppm - 2.23 Ibs. /Day
.046 ppm - .015 Ibs. A^
.135 ppm - .044 Iba./Day
2.0 ppm - 0.66 Ibs. /Day
102.8 ppm - 33.7 Ibs. /bay
21 ppri -^6.89 Ibs./Day
*
0.93 ppm - 0.30 ibs./Day
#
' 4.19 ppm - 1.37 Ibs./Day
14 ppm - 4.59 Ibs./Day
6 ppm - 1.97 Ibs./Day
*
-------
COUNTERCURRENT RINSING
PHASE III - CHEMICAL ANALYSES
DATE 9/30/75
yLOT TO SEWER
TEMPERA TORE
nH
ACIDITY/ALKALINITY
/
CHLORIDES
COD
FREE CYANIDES
TOTAL CYANIDES
FLUORIDES
SULFATES
SUSPENDED SOLIDS
CERCMTOM
IRON
NICKEL
POTASSIUM
SODIUM
TIN
COUNTERGURRENT TANK
0 Gal
_
-
-
_
_
_
_
_
_
_
_
-
-
-
SPRAY WASH ..
27,792 gpd
89° F.
4.7
Alkalinity
L.Q ppm -°- 93 Ibs/Daj
32 ppm -7. 42 Ibs/Dry
Ibs./
24.08 ppin-5.58 Day.
Ibs/
.131 ppm -.030 Day
Ibs/
.176 ppm -.041 Day •
22 ppm-5.10 Ibs/Dav
Ibs/
89.2 ppm-20.7 Day .
49 ppm-11.4 lbs/^)ay
*
0.83 ppm-.19 Ibs/Day
»
4-59 ppm -1.06 Ibs/Dav
70 ppm-16.2 Ibs/Day
73 ppm_i6.9 Ibs/Dav
HOT RINSE
72,000 gpd
176° F.
7.8
Alkalinity
2L ppm - 1L.L 1 b.=| . /Day
22 ppm - 13.2 Ibs. /Day
r 6.88 Dpm - 4.13 Ibs. /n«>r
.054 pprn - .032 Ibs./Dav
.122 ppm - .073 Ibs./Dav
2.0 ppm - 1.20 Ibs./Dav
86.8 ppm - 52.1 Ibs./^y
15 ppm - 9.01 Ibs. /Day
#
• 0.68 ppm - .4.1 Ibs./Ttey
*
4.25 ppm,- 2.55 Ibs./Dav
11 ppm - 6.6l Ibs. /Day
7 ppm - 4.20 Ibs. /Day
*
-------
COTNTERCORRENT RINSING
PHASE III _ CHEMICAL ANALYSIS
DATE 10/3/75
•^^•••^•MiMMMHMMMHHMBMM^B^^^BMH^
TJT/W TO SEWER
•TEMPERATURE
if
A fiTDITY/ALKALINITI
rHLORIDES
rnn
vt'KE CYANIDES
WVPAT. CYANIDES
SmJITES
nUDTMTTTM
THflff
M1UKJ8L
jprmSSIDM
5flDlOM
TTW
MMM^^BB^M«MMMi^MIMMB^^BBBMMH«««^^^^Hi«i«MM^
CODNTERCDRRENT TANK
0 gal
^ ,
_
-
_
.
_
—
_
—
—
-
-
-
-
••^•^•••••^••^••^^•^•^•••^•••••••••••^••^H
SPRAY WASH .
31,536 gpd
91° F.
5.3
Al k»l inity
6 T3tm-1.5'8 Ibs/day
28 ppm-7.36 Iba/Dav
Ibs/
13.6 'PIBI='^ - ^ Tip y
Ibs/
Ibs/
.140 ppm-. Q37 Dav •
Ibs/
TO f^ u'jun T>
Ibs^
77.2 ppm-20.5 Day ..
*
0.58 ppnu.15 Ibs/Day
*
4.63 ppm-1.22 Day
35 ppm_9.2i Ibs/Dav
i
31 ppm-a.i5 Ibs/Day
HOT RINSE
86,400 gpd
177° F.
8.0
Alkalinity
26 nnm _ 18.7 11^. /Day
29 ppm - 20.9 Ibs. /Day
3. L rmm - 2./.'5 Ihs./Dev
.073 ppm - .053 Ibs. /Dav
1.2 HOT - 0.86 Ibs. /Day
92 ppm - 66.3 Ibs. /Day
' 18 ctm - 13.0 Ibs.Atev
' * / . .
0.84 ppm - .61 Ibs. /Day
u
4.20 ppm - 3.03 Ibs. /Day
11 ppm - 7.93 Ibs. /bay
5 ppm - 3.60 Ibs. /Day
*
-------
TECHNICAL REPORT
(Please read Ins&uctions on the reverse
DATA
before completing)
1. REPORT NO.
EPA-600/2-77-191
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Countercurrent Rinsing on a High-speed Halogen
Tinplating Line
5. REPORT DATE
September 1977
6. PERFORMING ORGANIZATION CODE
7. AUTHORlS)
8. PERFORMING ORGANIZATION REPORT NO.
D. A. Pengidore
9. PERFORMING ORGANIZATION NAME AND ADDRESS
National Steel Corporation
Weirton Steel Division
Weirton, West Virginia 26062
10. PROGRAM ELEMENT NO.
1BB610; ROAP 21ADT-003
11. CONTRACT/GRANT NO.
Grant S801989
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Final; 2/73-5/76
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES jERL-RTP project officer for this report is Robert C. McCrillis,
Mail Drop 62, 919/541-2733.
16. ABSTRACT
The report describes the results of the first use of countercurrent rinsing
(involving the use of a compartmentized rinse tank) in high-speed strip plating lines.
The objective of using this rinse method is to reduce the amount of water required
so as to have a volume of liquid more easily handled in recovering chemicals. The
first unknown studied was the operating performance of the multistage rinse system
to determine if the basic principles of coantercurrent rinsing would hold for a high-
speed strip plating operation. Second was the best way to recover the chemicals in
the concentrated stream from this rinse system. The report also describes problems
encountered in recycling the concentrated rinse into the main plating system. It also
describes new technology for solving these problems and an alternate method involving
indirect recycling using the detinning plant.
7.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Rinsing
Plating
Tin Coatings
Halogens
Circulation
Pollution Control
Stationary Sources
Countercurrent Rinsing
Tinplating
Chemical Recovery
Detinning
13B
13H,07A
11C
07B
3. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
91
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
84
------- |