US 20060226023A1

(19) United States

(12) Patent Application Publication (10) Pub. No.: US 2006/0226023 A1
Nanjundiah et al. (43) Pub. Date: Oct. 12, 2006
(54) NEUTRALIZATION SYSTEM FOR Publication Classification
ELECTROCHEMICAL CHLORINE DOXDE
GENERATORS (51) Int. Cl.
C25B I/26 (2006.01)
(76) Inventors: Chenniah Nanjundiah, San Diego, CA (52) U.S. Cl. .............................................................. 205/556
(US); Larry L. Hawn, Laguna Niguel,
CA (US)
(57) ABSTRACT
Correspondence Address:
MCANDREWS HELD & MALLOY, LTD
SOO WEST MAIDSON STREET An electrochemical chlorine dioxide generator with a neu
SUTE 34OO tralization system includes a pH treatment tank for receiving
CHICAGO, IL 60661 waste products from the electrochemical generation process
Such as anolyte and catholyte wastes. A neutralization solu
(21) Appl. No.: 11/418,741 tion tank is fluidly connected to the pH treatment tank. A
neutralization feed pump transfers a neutralization Solution
(22) Filed: May 4, 2006 to the pH treatment tank. A recirculation pump for mixing
the waste products is fluidly connected to the pH treatment
Related U.S. Application Data tank. An effluent holding tank is fluidly connected to the pH
treatment tank. A transfer pump transfers the neutralized
(63) Continuation-in-part of application No. 10/902,681, waste products from the pH treatment tank to the effluent
filed on Jul. 29, 2004. holding tank.

A 500
ANOLYTE
LOOP

DILUTION WATER

NEUTRALIZATION EFFLUENT
SOLUTION HOLDING
TANK Y-560 Qir TANK

PHTREATMENT
ANK
510
Patent Application Publication Oct. 12, 2006 Sheet 1 of 5 US 2006/0226023 A1

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US 2006/0226023 A1
NEUTRALIZATION SYSTEM FOR
ELECTROCHEMICAL CHLORINE DOXDE
GENERATORS
CROSS-REFERENCE TO RELATED
APPLICATION(S)
0001. This application is a continuation-in-part of U.S.
patent application Ser. No. 10/902,681 filed on Jul. 29, 2004,
entitled “Chlorine Dioxide Solution Generator.” This appli
cation is also related to U.S. patent application Ser. No.
11/145,398 filed on Jun. 3, 2005, entitled “Chlorine Dioxide
Solution Generator With Temperature Control Capability”,
which is, in turn, a continuation-in-part of the 681 appli
cation. This application is also related to U.S. patent appli
cation Ser. No. 11/289,813 filed on Nov. 30, 2005, entitled
“High-Capacity Chlorine Dioxide Generator', which is also
a continuation-in-part of the 398 application. The 681,
398 and 813 applications are each hereby incorporated by
reference herein in their entirety.
FIELD OF THE INVENTION
0002 The present invention relates generally to chlorine
dioxide generators and to the use of Such generators in water
treatment systems. More particularly, the present invention
relates to an electrochemical chlorine dioxide generator,
with a neutralization system for waste products from chlo
rine dioxide production.
BACKGROUND OF THE INVENTION
0003 Chlorine dioxide (CIO) has many industrial and
municipal uses. When produced and handled properly, CIO
is an effective and powerful biocide, disinfectant and oxi
dizer.
0004 CIO is also used extensively in the pulp and paper
industry as a bleaching agent, but is gaining further Support
in Such areas as disinfection in municipal water treatment.
Other end-uses can include as a disinfectant in the food and
beverage industries, wastewater treatment, industrial water
treatment, cleaning and disinfections of medical wastes,
textile bleaching, odor control for the rendering industry,
circuit board cleansing in the electronics industry and uses
in the oil and gas industries.
0005. In water treatment applications, CIO is primarily
used as a disinfectant for Surface waters with odor and taste
problems. It is an effective biocide at low concentrations and
over a wide pH range. CIO, is desirable because when it
reacts with an organism in water, chlorite results, which
studies to date have shown does not pose a significant
adverse risk to human health at chlorite concentrations less
than 0.8 parts per million (ppm). The use of chlorine, on the
other hand, can result in the creation of chlorinated organic
compounds when treating water. Such chlorinated organic
compounds are suspected to increase cancer risk.
0006 Producing ClO gas for use in a CIO water treat
ment process is desirable because there is greater assurance
of CIO purity when CIO is in the gas phase. CIO is,
however, unstable in the gas phase and will readily undergo
decomposition into chlorine gas (Cl), oxygen gas (O) and
heat. The high reactivity of CIO generally requires that it be
produced and used at the same location. CIO is, however,
soluble and stable in an aqueous solution.
Oct. 12, 2006
0007. The production of CIO can be accomplished both
by electrochemical and reactor-based chemical methods.
Electrochemical methods have an advantage of relatively
safer operation compared to reactor-based chemical meth
ods. In this regard, electrochemical methods employ single
precursor, namely, a chlorite solution, unlike the multiple
precursors employed in reactor-based chemical methods.
Moreover, in reactor-based chemical methods, the use of
concentrated acids and chlorine gas can pose safety con
CS.
0008 Electrochemical cells are capable of carrying out a
selective oxidation reaction of chlorite to ClO. The selec
tive oxidation reaction product is a solution containing
CIO. To further purify a CIO gas stream, the gas stream is
typically separated from the solution using a stripper col
umn. In the stripper column, air is passed from the bottom
of the column to the top while the CIO solution travels from
top to the bottom. Pure ClO is exchanged from solution to
the air. Suction of air is usually accomplished using an
eductor, as described in copending and co-owned applica
tion Ser. No. 10/902,681, of which the present application is
a continuation-in-part.
0009. As described in the 681 application, CIO can be
prepared a number of ways, generally via a reaction involv
ing either chlorite (CIO) or chlorate (CIO) solutions. The
CIO created through such a reaction is often refined to
generate CIO gas for use in the water treatment process.
The CIO gas is then educed into the water selected for
treatment. Eduction occurs where the CIO gas, in combi
nation with air, is mixed with the water selected for treat
ment.
0010 While electrochemical generators are suited for
generating chlorine dioxide, Such generators produce unde
sirable waste products. These waste products are produced
both in the anolyte and catholyte loops of the electrochemi
cal generator. Anolyte waste products typically result from
residual reactants, side reaction products, and chlorine diox
ide that remains unstripped from the stripper column. Other
anolyte impurities can include Sodium chlorite, sodium
chlorate, sodium chloride, Sodium Sulfate, hypochlorous
acid and chlorine dioxide. The operation of the catholyte
loop in an electrochemical chlorine dioxide generator also
produces caustic soda (that is, Sodium hydroxide). Although
Sodium hydroxide can be used in other reactions, when
catholyte production is low it can be more economical to
dispose of it. The present apparatus and method effectively
neutralize waste products from the anolyte and catholyte
loops of electrochemical chlorine dioxide generators.
SUMMARY OF THE INVENTION
0011. An electrochemical chlorine dioxide generator
comprises an anolyte loop fluidly connected to a neutraliza
tion system. A catholyte loop is fluidly connected the neu
tralization system and the neutralization system treats (that
is, neutralizes) waste products from the anolyte loop and/or
the catholyte loop. In a preferred embodiment, an absorption
loop is fluidly connected to the anolyte loop.
0012. In an embodiment, the electrochemical chlorine
dioxide generator has a stripper column within the anolyte
loop that is fluidly connected to the neutralization system. In
a further embodiment, a probe monitors the pH of the waste
products in the neutralization system. In another embodi
US 2006/0226023 A1
ment, at least one of the electrochemical chlorine dioxide
generator and the neutralization system is controlled by a
programmable logic controller (PLC).
0013 In a preferred embodiment, the neutralization sys
tem comprises a pH treatment tank for receiving waste
products that is fluidly connected to at least one of the
anolyte loop and the catholyte loop. The neutralization
system can further comprise a neutralization Solution tank
fluidly connected to the pH treatment tank. In a further
embodiment, a recirculation pump is fluidly connected to the
pH treatment tank, and the recirculation pump mixes the
waste products in the pH treatment tank.
0014. In a preferred embodiment, the electrochemical
chlorine dioxide generator further comprises an effluent
holding tank fluidly connected to the pH treatment tank. The
effluent holding tank receives neutralized waste products.
The electrochemical chlorine dioxide generator can further
comprise a transfer pump for transferring the neutralized
waste products to the effluent holding tank. A diverting valve
controls the fluid connection between the pH treatment tank
and the effluent holding tank.
0015. In a preferred embodiment, an acidic solution is
contained in the neutralization solution tank and is used to
neutralize the waste products in the pH treatment tank. The
acidic solution can comprise hydrochloric acid. The acidic
Solution can further comprise a chlorite neutralizing com
pound. In a further embodiment, the chlorite neutralizing
compound is selected from the group of ferrous chloride
tetra hydrate, sodium sulfite, sodium metabisulfite, and
Sodium thiosulfate pentahydrate.
0016 A method for neutralizing waste products from an
electrochemical chlorine dioxide generator comprises col
lecting waste products from the electrochemical generator in
a pH treatment tank. A neutralizing Solution is added to the
waste product in the pH treatment tank. The waste products
are recirculated to achieve at least one of the removal of
substantially all chlorite and a pH between 4 and 10. The
waste products are transferred from the pH treatment tank
for storage and/or disposal. A preferred embodiment further
comprises controlling the neutralizing of waste products
with a PLC.
BRIEF DESCRIPTION OF THE DRAWINGS
0017 FIG. 1 is a process flow diagram of a CIO,
generator of the type described in application Ser. No.
10/902,681 that includes a neutralization system for waste
products from the electrochemical generator.
0018 FIG. 2 is a process flow diagram of an anolyte loop
of a CIO generator of the type described in the 681
application.
0.019 FIG. 3 is a process flow diagram of a catholyte
loop of a CIO generator of the type described in the 681
application.
0020 FIG. 4 is a process flow diagram of an absorption
loop of a CIO generator of the type described in the 681
application.
0021 FIG. 5 is a process flow diagram of a neutralization
system for waste products from an electrochemical ClO.
generator.
Oct. 12, 2006
0022. These and other features of the apparatus and
method disclosed herein will become more readily apparent
to those having ordinary skill in the art from the following
detailed description of the preferred embodiments taken in
conjunction with the drawings.
DETAILED DESCRIPTION OF PREFERRED
EMBODIMENT(S)
0023 FIG. 1 illustrates a process flow diagram of an
embodiment of a chlorine dioxide solution generator 100 of
the type described in application Ser. No. 10/902,681. The
process flow of FIG. 1 can consist of three sub-processes
including an anolyte loop 102, a catholyte loop 104 and an
absorption loop 106. The purpose of anolyte loop 102 is to
produce a CIO, gas by oxidation of chlorite, and the process
can, along with the catholyte loop process 104, be referred
to as a CIO gas generator loop. The CIO gas generator loop
is essentially a CIO gas source. Various sources of CIO are
available and known in the water treatment field. Catholyte
loop 104 of the CIO gas generator loop produces Sodium
hydroxide and hydrogen gas by reduction of water. Once the
CIO gas is produced in the CIO gas generator loop, the
CIO, gas can be transferred to an absorption loop 106 where
the gas can be further conditioned for water treatment
end-uses. The anolyte loop 102 and catholyte loop 104 can
be fluidly connected to a neutralization system 500 that can
process wastes produced by the anolyte loop 102 and
catholyte loop 104. The process can be operated at least
partially through a PLC-based system that can include visual
and/or audible displays.
0024. In this application, the term “absorb refers to the
process of dissolving or infusing a gaseous constituent into
a liquid, optionally using pressure to effect the dissolution or
infusion. Here, CIO gas, which is produced in the CIO gas
generator loop, is “absorbed' (that is, dissolved or infused)
into an aqueous liquid stream directed through absorption
loop 106. The neutralization system 500 can process wastes
for electrochemical CIO generators that produce CIO gas
(for example, without an absorption loop) or CIO solution
(for example, with an adsorption loop).
0.025 FIG. 2 illustrates an anolyte loop 102 in an
embodiment of chlorine dioxide solution generator 100 of
the type described in the 681 application. The contribution
of anolyte loop 102 to the CIO, solution generator is to
produce a CIO gas that is directed to absorption loop 106
for further processing. The anolyte loop embodiment of
FIG. 2 is for a CIO gas produced using a reactant feedstock
202. In a preferred embodiment, a 25 percent by weight
sodium chlorite (NaClO) solution can be used as reactant
feedstock 202. However, feedstock concentrations ranging
from 0 percent to a maximum solubility (40 percent at 17°
C. in the embodiment involving NaClO), or other suitable
method of injecting Suitable electrolytes, can be employed.
0026. The reactant feedstock 202 can be connected to a
chemical metering pump 204, which delivers the reactant
feedstock 202 to a recirculating connection 206 in the
anolyte loop. Recirculating connection 206 in anolyte loop
connects a stripper column 208 to an electrochemical cell
210. The delivery of the reactant feedstock 202 can be
controlled using PLC system 108. PLC system 108 can be
used to activate chemical metering pump 204 according to
signals received from a pH sensor 212. pH sensor 212 is
US 2006/0226023 A1
generally located along recirculating connection 206. A pH
set point can be established in PLC system 108, and once the
set point is reached, the delivery of reactant feedstock 202
can either start or stop.
0027. Reactant feedstock 202 can be delivered to a posi
tive end 214 of electrochemical cell 210 where the reactant
feedstock is oxidized to form a CIO gas, which is then
dissolved in an electrolyte solution along with other side
products. The CIO, solution with the side products is
directed away from electrochemical cell 210 to the top of
stripper column 208 where a pure CIO, is stripped off in a
gaseous form from the other side products. Side products or
byproducts can include chlorine, chlorates, chlorites and/or
oxygen. The pure CIO gas is then removed from Stripper
column 208 under a vacuum induced by gas transfer pump
216, or analogous gas or fluid transfer device (Such as, for
example, a vacuum-based device), where it is delivered to an
adsorption loop. The remaining solution is collected at the
base of stripper column 208 and recirculated back across the
pH sensor 212 where additional reactant feedstock 202 can
be added. The process with the reactant feedstock and/or
recirculation solution being delivered into positive end 214
of electrochemical cell 210 is then repeated.
0028. As described in the 681 application, modifications
to the anolyte loop process can be made that achieve similar
results. As an example, an anolyte hold tank can be used in
place of a stripper column. In Such a case, an inert gas or air
can be blown over the surface or through the solution to
separate the CIO gas from the anolyte. As another example,
chlorate can be reduced to produce CIO, in a cathode loop
instead of chlorite. The CIO gas would then similarly be
transferred to the absorption loop. In a further example,
CIO, can be generated by purely chemical generators and
transferred to an absorption loop for further processing.
0029 FIG. 3 illustrates a catholyte loop 104 in an
embodiment of a chlorine dioxide solution generator 100 of
the type described in the 681 application. Catholyte loop
104 contributes to the chlorine dioxide solution generator
100 by handling byproducts produced from the electro
chemical reaction of reactant feedstock 202 solution in
anolyte loop 102. As an example, where a sodium chlorite
(NaClO) solution is used as reactant feedstock 202, sodium
ions from the anolyte loop 102 migrate to catholyte loop
through a cationic membrane 302, in electrochemical cell
210, to maintain charge neutrality. Water in the catholyte is
reduced to produce hydroxide and hydrogen (H) gas. The
resulting byproducts in catholyte loop, in the example of a
NaClO reactant feedstock, are sodium hydroxide (NaOH)
and hydrogen gas. The byproducts are directed to a byprod
uct tank 304.
0030. In an embodiment of catholyte loop in the example
of a NaClO reactant feedstock, a soft (that is, demineral
ized) water source 306 can be used to dilute the byproduct
NaOH using a solenoid valve 308 connected between soft
water source 306 and the byproduct tank 304. Solenoid
valve 308 can be controlled with PLC system 108. In a
preferred embodiment, PLC system 108 can use a timing
routine that maintains the NaOH concentration in a range of
5 percent to 20 percent. When byproduct tank 304 reaches
a predetermined level above the base of byproduct tank 304,
the diluted NaOH byproduct above that level is removed
from catholyte loop.
Oct. 12, 2006
0031. In the example of a NaClO reactant feedstock, the
catholyte loop self-circulates using the lifting properties of
the H2 byproduct gas formed during the electrochemical
process and forced water feed from soft water source 306.
The H gas rises up in byproduct tank 304 where there is a
hydrogen disengager 310. The H gas can be diluted with air
in hydrogen disengager 310 to a concentration of less than
0.5 percent. The diluted H gas can be discharged from
catholyte loop 104 and chlorine dioxide solution generator
100 using a blower 312.
0032. As described in the 681 application, in another
embodiment, dilute sodium hydroxide can be fed instead of
water to produce concentrated Sodium hydroxide. Oxygen or
air can also be used as a reductant instead of water to reduce
overall operation Voltage since oxygen reduces at lower
Voltage than water.
0033. The reaction of anolyte loop 102 and catholyte loop
104 in the embodiment illustrated in FIGS. 2 and 3 is
represented by the following net chemical equation:
2NaClO2+2H2O >2CIO2a+2NaOHa!-H2 as
The NaClO is provided by reactant feedstock 202 of
anolyte loop 102. The NaOH and H gas are byproducts of
the reaction in catholyte loop 104. The CIO, solution along
with the starting unreacted NaClO and other side products
are directed to the stripper column for separating into ClO.
gas as part of anolyte loop 102 process. Chlorite salts other
than NaClO can be used in anolyte loop 102.
0034 FIG. 4 illustrates an absorption loop 106 of an
embodiment of a chlorine dioxide solution generator 100 of
the type described in the 681 application. The absorption
loop processes the CIO gas from anolyte loop 102 into a
CIO, solution that is ready to be directed to the water selected
for treatment.
0035 CIO gas is removed from stripper column 208 of
anolyte loop 102 using gas transfer pump 216. In a preferred
embodiment, a gas transfer pump 216 can be used that is “V”
rated at 75 Torr (10 kPa) with a discharge rate of 34 liters per
minute. The vacuum and delivery rate of gas transfer pump
216 can vary depending upon the free space in stripper
column 208 and desired delivery rate of CIO solution.
0036) The CIO gas removed from stripper column 208
using gas transfer pump 216 is directed to an absorber tank
402 of the absorption loop. In a preferred embodiment,
discharge side 404 of gas transfer pump 216 delivers ClO.
gas into a 0.5-inch (13-mm) poly(vinyl chloride) (PVC)
injection line 406 external to absorber tank 402. Injection
line 406 is an external bypass for fluid between the lower to
the upper portions of the absorber tank 402. A gas injection
line can be connected to injection line 406 using a T-con
nection 408. Before CIO gas is directed to absorber tank
402, the tank 402 is filled with water to approximately 0.5
inch (13 mm) below a main level control 410. Main level
control 410 can be located below where injection line 406
connects to the upper portion of absorber tank 402. Intro
ducing CIO gas into injection line 406 can cause a liquid lift
that pushes newly absorbed CIO solution up past a forward
only flow switch 412 and into absorber tank 402. Flow
switch 412 controls the amount of liquid delivered to
absorber tank 402. Absorber tank 402 has a main control
level 410 to maintain a proper tank level. In addition to main
control level 410, safety control levels can be employed to
US 2006/0226023 A1
maintain a high level 414 and low level 416 of liquid where
main control level 410 fails. A process delivery pump 418
feeds CIO solution from absorber tank 402 to the end
process without including air or other gases. Process deliv
ery pump 418 is sized to deliver a desired amount of water
per minute. The amount of CIO gas delivered to absorber
tank 402 is set by the vacuum and delivery rate set by gas
transfer pump 216.
0037 PLC system 108 can provide a visual interface for
the operator to operate the chlorine dioxide Solution gen
erator 100. PLC system 108 can automatically control the
continuous operation and safety of the production of CIO
solution. PLC system 108 can set flow rates for anolyte loop
102 and catholyte loop 104. The safety levels of absorber
tank 402 can also be enforced by PLC system 108. PLC
system 108 can also control the power for achieving a
desired current in an embodiment using an electrochemical
cell 210. In a preferred embodiment, the current ranges from
0 to 100 amperes, although currents higher than this average
are possible. The amount of current determines the amount
of CIO gas that is produced in anolyte loop 102. The current
of the power supply can be determined by the amount of
CIO, that is to be produced. PLC system 108 can also be used
to monitor the voltage of electrochemical cell 210. In a
preferred embodiment, electrochemical cell 210 can be shut
down when the Voltage exceeds a safe Voltage level. In
another preferred embodiment, 5 volts can be considered a
safe voltage level.
0038. As described in the 681 application, another
operation that can be monitored with PLC system 108 is the
temperature of electrochemical cell 210. If overheating
occurs, PLC system 108 shuts down electrochemical cell
210. PLC system 108 can also monitor the pH of the anolyte
using a pH sensor 212 (shown in FIG. 2). During operation
of electrochemical cell 210, the pH of the solution circulat
ing in anolyte loop decreases as hydrogen ions are gener
ated. In the exemplary embodiment of the NaClO reactant
feedstock, when the pH goes below 5, additional reactant
feedstock is added using PLC system 108. Control of pH can
also be handled by adding a reactant that decreases the pH
when the pH is too high.
0039. In another embodiment, the transfer line from gas
transfer pump 216 can be connected to absorber tank 402
directly without injection line 406, and can allow for
increasing the pump transfer rate. Other embodiments can
include a different method of monitoring the liquid level in
absorber tank 402. For example, an oxidation and reduction
potential (ORP) can be dipped in absorber tank 402. ORP
can be used to monitor the concentration of CIO in the
solution in absorber tank 402. PLC system 108 can be used
to set a concentration level for the CIO as monitored by
ORP, which provides an equivalent method of controlling
the liquid level in absorber tank 402. Optical techniques
Such as photometers can also be used to control the liquid
level in absorber tank 402. Absorption loop 106 can be a part
of the chlorine dioxide solution generator or it can be
installed as a separate unit outside of the chlorine dioxide
Solution generator. In another embodiment, process water
can be fed directly in absorber tank 402 and treated water
can be removed from the absorber tank 402. The process
water can include a demineralized, or soft, water source 420
and the process water feed can be controlled using a Solenoid
valve 422.
Oct. 12, 2006
0040 FIG. 5 is a process flow diagram of an embodiment
of a neutralization system 500 for waste products from an
electrochemical CIO generator 100, such as the generator
described in the 681 application. As illustrated in FIG. 1,
wastes from the anolyte loop 102 can be fluidly connected
to the neutralization system 500 by way of a connection
from the stripper column. Another embodiment illustrates
the wastes from the catholyte loop 104 fluidly connected to
the neutralization system 500 by way of a connection from
a byproduct tank. Hydrogen byproduct wastes from the
catholyte loop typically exit the byproduct tank by way of
the blower 312 as shown in FIG. 3, where the hydrogen can
be diluted with air and discharged into the atmosphere at a
preferred concentration of less than 0.1 percent hydrogen.
Caustic soda or sodium hydroxide from the catholyte loop is
also typically collected in the byproduct tank 304, such as,
for example, where a chlorite reactant feedstock is used in
the anolyte loop 102.
0041 FIG. 5 illustrates anolyte waste and catholyte
waste directed into a pH treatment tank 510. In a preferred
embodiment, both waste streams are combined into the same
tank. The pH treatment tank 510 is fluidly connected to a
number of pumps including a recirculation and transfer
pump 520 and a neutralization feed pump 530. A single
pump can perform one or more functions. For example, the
recirculation and transfer pump 520 can perform both recir
culation and transfer operations or two separate pumps can
be used to individually perform each separate operation. The
neutralization feed pump 530 can allow uninterrupted flow
to the pH treatment tank 510 using a pH control system 540
that can continuously modulate the neutralization feed pump
530. The recirculation and transfer pump 520 can serve a
dual function of treating (that is, mixing or neutralizing)
waste products in the pH treatment tank 510 and transferring
or discharging the treated waste products to an effluent
holding tank 5.50, which can have a drain 555 to remove
waste products. The effluent holding tank can also accept
dilution water.
0042. A waste product that can result in the anolyte loop
102 process is unseparated CIO, from the stripper column
operation. In one embodiment, a typical concentration range
of a chlorine dioxide waste product from the anolyte loop is
700 ppm to 1500 ppm. For a CIO, concentration at this level,
it is difficult to tolerate the odor and the overall effects can
be toxic, thus making neutralization of the toxic effects of
the chlorine dioxide waste a desired outcome. Since the
waste from the catholyte loop of an electrochemical chlorine
dioxide generator includes sodium hydroxide, the catholyte
waste can neutralize the chlorine dioxide waste produced
from the anolyte loop, as represented by the following
chemical equation:
0043. The quantity of chlorine dioxide waste that is
produced in the electrochemical reaction is typically much
less that the quantity of sodium hydroxide. As the anolyte
and catholyte waste streams enter the pH treatment tank 510
and combine, the overall mixture is typically alkaline in
nature where the pH can range from approximately 12 to 13.
This high pH range is due to the larger quantity of catholyte
waste compared to the anolyte waste.
US 2006/0226023 A1
0044) In consideration of various disposal options, the
waste products can be neutralized with acid prior to disposal.
In a preferred embodiment, hydrochloric acid or muriatic
acid, Such as that which is commercially available for use in
Swimming pools, can be used as a neutralizing agent. By
way of the neutralization solution tank 520, hydrochloric
acid can be added to the pH treatment tank 510. The addition
of the hydrochloric acid to the combined anolyte and
catholyte wastes in the pH treatment tank is preferably done
with sufficient mixing to limit the formation of chlorine
dioxide, which can occur when the pH in the treatment tank
510 decreases to less than approximately 4. In a preferred
embodiment, the neutralization system 500 illustrated in
FIG. 5 can have the pH control system 540 monitor the pH
so that the addition of acid is stopped when the pH of the
treated waste stream drops below 9. In another embodiment,
the pH level of the treated waste stream is maintained above
4.
0045. In addition to the alkalinity of the wastes from an
electrochemical chlorine dioxide generator, the levels of
chlorite from the anolyte loop wastes can also preferably be
converted or neutralized. This can be done by converting the
chlorite into chloride by reacting the sodium chlorite waste
product with any of a number of compounds. For example,
sodium chlorite can be reacted with ferrous chloride as
demonstrated by the following chemical equation:
In a preferred embodiment, 67.45 grams of chlorite will
react in the above equation with 795.24 grams of ferrous
chloride tetra hydrate.
0046. As another example, sodium chlorite can be
reacted with sodium sulfite as demonstrated by the following
equation:
In a preferred embodiment, 67.45 grams of chlorite will
react in the above equation with 252.08 grams of sodium
sulfite.
0047. In another embodiment, sodium chlorite can be
reacted with sodium metabisulfite as demonstrated by the
following equation:
In a preferred embodiment, 67.45 grams of chlorite will
react in the above equation with 190 grams of sodium
metabisulfite.
0.048 Sodium chlorite can also be reacted with sodium
thiosulfite as demonstrated by the following equation:
In a preferred embodiment, 67.45 grams of chlorite will
react in the above equation with 992.68 grams of sodium
thiosulfate pentahydrate.
0049 Table 1 summarizes preferred chlorite neutralizing
compounds and the concentration of neutralizer compound
that will neutralize 1 ppm of chlorite into chloride.
Oct. 12, 2006
TABLE 1.
Qhemical concentration that will neutralize 1 ppm of chlorite
Neutralizer Concentration
Compound (ppm)
FeCl2.H2O 11.8
Na2SO 3.7
Na2SOs 2.8
Na2(SO).5H2O 14.7
0050. In a preferred embodiment, the chlorite neutraliz
ing compound. Such as those described in Table 1, can be
combined with a dilute acid (for example, a solution of 5
percent acid) for Subsequent neutralizing of the alkaline
anolyte and catholyte waste mixture held in the pH treatment
tank 510. The chlorite neutralizing compound and dilute
acid can be combined in the neutralization solution tank 560.
The amount of neutralizer compound can be calculated
based on the amount of chlorite present in the waste stream.
A typical concentration range of chlorite is 0 to 0.3 moles/
liter (that is, molarity (M)) in an electrochemical chlorine
dioxide generator.
0051 FIG. 5 illustrates the electrochemical chlorine
dioxide generator 100 fluidly connected to the pH treatment
tank 510 by way of connection to the anolyte and catholyte
waste discharges from the electrochemical chlorine dioxide
generator 100. Following the mixing of the catholyte and
anolyte waste streams in the pH treatment tank 510, the pH
of the combined wastes typically ranges from around 12 to
14. A recirculation or mixing process can be performed with
the pH treatment tank 510 using the recirculation and
transfer pump 520. Recirculation is typically performed
when a diverting valve 570 between the recirculation and
transfer pump 520 and the effluent holding tank 550 is
closed. A recirculation process is preferred to help keep the
concentration of the waste products uniform and diluted so
that the wastes in the pH treatment tank 510 do not become
acidic and cause CIO to form.
0052. In a preferred embodiment, residual chlorine diox
ide from the anolyte waste stream reacts with sodium
hydroxide from the catholyte waste stream to form chlorite
and chlorate when the pH in the pH treatment tank 510 is
maintained between approximately 12 and 14. Following the
reaction of the chlorine dioxide waste, the waste product in
the pH treatment tank 510 can be adjusted to have a pH of
less than 10 using a dilute hydrochloric acid (HCl concen
tration less than 30 percent). Adjusting and maintaining a pH
of less than 10 can be accomplished by monitoring the pH
of the waste product in the pH treatment tank 510 using a
probe 545 connected to the pH control system 540 and
automatically adding the neutralizing hydrochloric acid with
the neutralizing feed pump 530 which is also connected to
the pH control system 540. Although the probe can be placed
anywhere in the neutralization system 500 where it can
monitor the pH of the product in pH treatment tank 510, in
a preferred embodiment the pH probe 545 is placed in the
recirculation loop. The recirculation loop includes the recir
culation and transfer pump 520 and the pH treatment tank
510. The waste products in the pH treatment tank 510 are
recirculated in the recirculation loop using the pump 520 to
mix the waste products.
US 2006/0226023 A1
0053. In a further embodiment, chlorite neutralizing
chemicals such as those identified in Table 1 can be mixed
with the dilute hydrochloric acid in the neutralization solu
tion tank 560. Preferably, the chlorite neutralizing chemicals
are in excess of the concentrations identified in Table 1. As
the neutralization feed pump 530 adds neutralization solu
tion to the pH treatment tank 510, the remaining chlorite in
the wastes in the pH treatment tank 510 will be converted
into chloride. In a preferred embodiment, the neutralization
solution tank 560 can have double wall jacketing to provide
leak containment.
0054. In a preferred embodiment, level sensors are used
to control the level of the waste products in the pH treatment
tank 510. A level sensor arrangement can include a level
sensor high (LSH) 580 and a level sensor low (LSL) 585.
LSH 580 can open diverting valve 570 when the level in the
pH treatment tank 510 is high and needs to be lowered by
diverting some of the waste product to the effluent holding
tank 550. When the level in the pH treatment tank decreases
to a level that triggers LSL 585, the diverting valve 550 will
close. Any additional diversion of waste product to the
effluent holding tank 550 occurs by opening the diverting
valve 570. The diverting valve can also be controlled by a
pH sensor 547 that limits waste products of high or low pH
from being discharged into the effluent holding tank 550.
0055. In a preferred embodiment, the neutralization sys
tem 500 and/or electrochemical chlorine dioxide generator
100 can be controlled with a PLC 590. For example, for the
neutralization system 500, the PLC 590 can be used to
control the neutralization feed pump 530, the recirculation
and transfer pump 520, the level sensors 580, 585, the
diverting valve 570, the pH probe 545, pH sensor 547,
and/or the pH control system 540. The PLC 590 can be
further used to control the electrochemical chlorine dioxide
generator 100.
0056 While particular elements, embodiments and appli
cations of the present invention have been shown and
described, it will be understood, of course, that the invention
is not limited thereto since modifications can be made by
those skilled in the art without departing from the scope of
the present disclosure, particularly in light of the foregoing
teachings.
What is claimed is:
1. An electrochemical chlorine dioxide generator com
prising:
(a) an anolyte loop fluidly connected to a neutralization
system; and
(b) a catholyte loop fluidly connected said neutralization
system;
wherein said neutralization system neutralizes waste
products from at least one of said anolyte loop and said
catholyte loop.
2. The electrochemical chlorine dioxide generator of
claim 1, wherein an absorption loop is fluidly connected to
said anolyte loop.
3. The electrochemical chlorine dioxide generator of
claim 1, wherein a stripper column within said anolyte loop
is fluidly connected to said neutralization system.
4. The electrochemical chlorine dioxide generator of
claim 1, further comprising a pH control system to monitor
the pH of said waste products in said neutralization system.
Oct. 12, 2006
5. The electrochemical chlorine dioxide generator of
claim 1, wherein at least one of said electrochemical chlo
rine dioxide generator and neutralization system is con
trolled with a programmable logic controller.
6. The electrochemical chlorine dioxide generator of
claim 1, wherein said neutralization system comprises a pH
treatment tank for receiving waste products, wherein said pH
treatment tank is fluidly connected to at least one of said
anolyte loop and said catholyte loop.
7. The electrochemical chlorine dioxide generator of
claim 6, wherein said neutralization system further com
prises a neutralization Solution tank fluidly connected to said
pH treatment tank.
8. The electrochemical chlorine dioxide generator of
claim 6, further comprising a recirculation pump fluidly
connected to said pH treatment tank, wherein said recircu
lation pump mixes said waste products in said pH treatment
tank.
9. The electrochemical chlorine dioxide generator of
claim 6, further comprising an effluent holding tank fluidly
connected to said pH treatment tank, wherein said effluent
holding tank receives neutralized waste products.
10. The electrochemical chlorine dioxide generator of
claim 9, further comprising a transfer pump for transferring
said neutralized waste products to said effluent holding tank,
wherein a diverting valve controls said fluid connection
between said pH treatment tank and said effluent holding
tank.
11. The electrochemical chlorine dioxide generator of
claim 7, wherein an acidic Solution contained in said neu
tralization Solution tank is used to neutralize said waste
products in said pH treatment tank.
12. The electrochemical chlorine dioxide solution genera
tor of claim 11, wherein said acidic solution comprises
hydrochloric acid.
13. The electrochemical chlorine dioxide generator of
claim 11, wherein said acidic solution further comprises a
chlorite neutralizing compound.
14. The electrochemical chlorine dioxide generator of
claim 13, wherein said chlorite neutralizing compound is
selected from the group of ferrous chloride tetra hydrate,
sodium sulfite, sodium metabisulfite, and sodium thiosulfate
pentahydrate.
15. An electrochemical chlorine dioxide generator with a
neutralization system comprising:
(a) a pH treatment tank for receiving waste products from
said electrochemical generator,
(b) a neutralization solution tank fluidly connected to said
pH treatment tank, wherein a neutralization feed pump
transfers a neutralization solution to said pH treatment
tank;
(c) a recirculation pump fluidly connected to said pH
treatment tank, wherein said recirculation pump mixes
said waste products in said pH treatment tank;
(d) an effluent holding tank fluidly connected to said pH
treatment tank; and
(e) a transfer pump for transferring neutralized waste
products from said pH treatment tank to said effluent
holding tank.
16. The electrochemical chlorine dioxide generator of
claim 15, wherein said neutralization solution is an acidic
Solution.
US 2006/0226023 A1 Oct. 12, 2006

17. The electrochemical chlorine dioxide generator of
claim 18, wherein said acidic solution further comprises a
chlorite neutralizing compound.
18. The electrochemical chlorine dioxide generator of
claim 13, wherein said chlorite neutralizing compound is
selected from the group of ferrous chloride tetra hydrate,
sodium sulfite, sodium metabisulfite, and sodium thiosulfate
pentahydrate.
19. A method for neutralizing waste products from an
electrochemical chlorine dioxide generator comprising:
(a) collecting waste products from said electrochemical
generator in a pH treatment tank;
(b) adding a neutralizing solution to said waste product in
said pH treatment tank;
(c) recirculating said waste products to achieve at least
one of the removal of substantially all chlorite and a pH
between 4 and 10; and
(d) transferring said waste products from said pH treat
ment tank to an effluent holding tank.
20. The method of claim 19, further comprising control
ling said neutralizing of waste products with a program
mable logic controller.
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