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Patent 3088751 Summary

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(12) Patent Application: (11) CA 3088751
(54) English Title: SYSTEM AND METHOD FOR AUTOMATED CONTROL, FEED, DELIVERY VERIFICATION, AND INVENTORY MANAGEMENT OF CORROSION AND SCALE TREATMENT PRODUCTS FOR WATER SYSTEMS
(54) French Title: SYSTEME ET PROCEDE DE COMMANDE, D'ALIMENTATION, DE VERIFICATION DE DISTRIBUTION, ET DE GESTION D'INVENTAIRE DE PRODUITS DE TRAITEMENT CONTRE LA CORROSION ET L'ENTARTRAGE POUR LES SYSTEMES D'EAU
Status: Report sent
Bibliographic Data
(51) International Patent Classification (IPC):
  • C02F 1/00 (2006.01)
  • A01N 37/16 (2006.01)
  • A01N 61/00 (2006.01)
  • A01P 1/00 (2006.01)
  • B08B 9/08 (2006.01)
  • C02F 1/50 (2006.01)
  • C02F 1/68 (2006.01)
  • C02F 5/00 (2006.01)
  • C23F 11/00 (2006.01)
  • B01F 15/02 (2006.01)
(72) Inventors :
  • DREWNIAK, MARTA (United States of America)
  • STEIMEL, LYLE H. (United States of America)
  • LIST, JAMES VICTOR (United States of America)
  • HOLDER, CORY J. (United States of America)
  • BOYETTE, SCOTT M. (United States of America)
(73) Owners :
  • NCH CORPORATION (United States of America)
(71) Applicants :
  • NCH CORPORATION (United States of America)
(74) Agent: MARKS & CLERK
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2019-01-22
(87) Open to Public Inspection: 2019-09-06
Examination requested: 2022-08-16
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2019/014462
(87) International Publication Number: WO2019/168607
(85) National Entry: 2020-07-16

(30) Application Priority Data:
Application No. Country/Territory Date
15/908,163 United States of America 2018-02-28

Abstracts

English Abstract

A system and method of controlling the treatment of water systems comprises multiple feeders for separately feeding treatment products, in the form of concentrated, non-hazardous, liquids with a single active ingredient, to a water system to treat various issues, such as corrosion and biofilms. A sensor verifies delivery of the treatment product to the water system. A controller controls activation of each feeder to control a feed rate according to programmed functions. The controller receives signals from sensors, which can be used as inputs in calculating feed rates or feeder activation times according to the programed functions and can alter treatment product feed rates based on real time data regarding water system chemistry or flow rates. The controller can send and receive data, signals, alerts, alarms or changes in programming to or from remote users, remote computers, or a water system controller.


French Abstract

La présente invention concerne un système et un procédé de régulation du traitement de systèmes d'eau comprenant de multiples dispositifs d'alimentation pour alimenter séparément des produits de traitement, sous la forme de liquides concentrés, non dangereux, avec un ingrédient actif unique, vers un système d'eau pour traiter différents problèmes, tels que la corrosion et les biofilms. Un capteur vérifie la distribution du produit de traitement au système d'eau. Un dispositif de commande commande l'activation de chaque dispositif d'alimentation pour commander un niveau d'alimentation selon des fonctions programmées. Le dispositif de commande reçoit les signaux de capteurs, qui peuvent être utilisés comme entrées dans le calcul de niveaux d'alimentation ou moments d'activation du dispositif d'alimentation selon les fonctions programmées et peut modifier les niveaux d'alimentation en produit de traitement sur la base de données en temps réel concernant les chimies du système d'eau ou les débits d'écoulement. Le dispositif de commande peut envoyer et recevoir des données, des signaux, des alertes, des alarmes ou des changements dans la programmation de ou depuis des utilisateurs distants, des ordinateurs distants, ou un dispositif de commande de système d'eau.

Claims

Note: Claims are shown in the official language in which they were submitted.


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[00108] We claim:
1. A treatment control system for treating water in a water system, the
treatment control system comprising:
a first container containing an initial volume of a first treatment product;
a second container containing an initial volume of a second treatment
product;
optionally one or more of a third through a twelfth container containing an
initial volume of a third through a twelfth treatment product;
a feeder for each container to feed the treatment product in the container to
the water system;
a controller connected to each feeder to activate the feeders according to one

or more programmed functions to control a feed initiation time and feed rate
for each
treatment product through each feeder; and
wherein each treatment product is useful alone or in combination with another
treatment product for treating one or more of corrosion, white rust, scale, or

biological contamination in the water system.
2. The treatment control system according to claim 1 wherein the first
treatment product comprises a single active ingredient, the second treatment
product comprises a single active ingredient different from the first
treatment product
and wherein each feeder comprises (1) a peristaltic metered pump, (2) an
actuator
to actuate a valve for gravity feed, (3) a rotating impeller pump, or (4) a
slide
actuated piston pump.
3. The treatment control system according to claim 2 further
comprising a sensor downstream of at least one of the feeders, wherein the
controller receives a signal from the downstream sensor indicating whether one
of
the treatment products has been fed into the water system.
4. The treatment control system according to claim 3 wherein the
controller is configured to compare the signal received from the downstream
sensor
to pre-programmed data to determine whether the treatment product has been fed
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into the water system according to the programmed function associated with
that
treatment product.
5. The treatment control system according to claim 4 wherein the
controller sends an alert message or activates an alarm when the comparison
indicates the treatment product has not been fed into the water system
according to
the pre-programmed function associated with that treatment product.
6. The treatment control system according to claim 3 wherein the
downstream sensor is a conductivity meter.
7. The treatment control system according to claim 6 wherein the
controller activates each feeder separately so that no treatment product is
fed into
the water system simultaneously with another treatment product.
8. The treatment control system according to claim 1 wherein the
treatment control system optionally comprises one or more sensors upstream of
the
one or more feeders and wherein the controller receives signals from one or
more
sensors in the water system, the one or more optional upstream sensors, or a
combination thereof and utilizes those signals as inputs in the programmed
functions.
9. The treatment control system according to claim 1 wherein at least
one feeder comprises a venturi injector and a valve.
10. The treatment control system according to claim 1 wherein each
feeder has a visual indicator that matches a visual indicator on the treatment
product
container to which the feeder should be connected.
11. The treatment control system according to claim 2 wherein each
feeder is connected to tubing having a visual indicator that is different from
the visual
indicator of the tubing of each other feeder, each tubing configured to
connect in
fluid communication to one container of treatment product comprising a part or
label
that matches the visual indicator of the tubing to which the container should
be
connected.
12. The treatment control system according to claim 11 wherein the
visual indicator is a color.

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13. The treatment control system according to claim 8 wherein the
controller is configured to record data or to send such data to a remote user,
remote
computer, or a water system controller, and wherein the data is one or more of

treatment product feed rates, changes in programmed functions, signals or
measurements based on signals from the water system sensors, or signals or
measurements based on signals from the optional upstream sensors.
14. The treatment control system according to claim 8 wherein a
programmed function is a calculation of feeder activation time for a first
treatment
product based on a desired concentration level for the first treatment product
in the
water system, a measurement of a concentration level for a second treatment
product in the water system based on a signal from a water system sensor or an

optional upstream sensor, and actual feeder activation time for the second
treatment
product to achieve that measured concentration level.
15. The treatment control system according to claim 1.wherein one or
more of the treatments products contain active ingredients for inhibiting
corrosion
and one or more other of the treatment products contain an oxidizing biocide;
and
wherein one of the programmed functions prohibits the one or more corrosion
inhibiting treatment products from being fed into the water system at
substantially
the same time as the one or more oxidizing biocide treatment products.
16. The treatment control system according to claim 1 wherein the first
treatment product comprises AAP as an active ingredient, the second treatment
product comprises a phosphonic acid other than HPA, and the optional third
treatment product comprises HPA to treat corrosion, white rust, scale, or a
combination thereof in the water system; and
wherein one or more of the programmed functions controls the feed rates of
the AAP, phosphonic acid, and optional HPA to provide active concentrations in
the
water system of (1) at least 2 ppm AAP, at least 2 ppm HPA, and at least 1.5
ppm of
the phosphonic acid other than HPA when it is desired to treat scale; or (2)
at least 3
ppm AAP, at least 3 ppm HPA, and at least 2 ppm of the phosphonic acid other
than
HPA when it is desired to treat corrosion; or (3) at least 3 ppm AAP,
optionally at
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least 3 ppm HPA, and at least 2 ppm of the phosphonic acid other than HPA when
it
is desired to treat white rust.
17. The treatment control system according to claim 16 wherein the
one or more programmed functions controls the feed rates of the AAP,
phosphonic
acid, and optional HPA to provide active concentrations in the water system of
(1)
between 2-50 ppm AAP, between 2-50 ppm HPA, and between 1.5-20 ppm of the
phosphonic acid other than HPA when it is desired to treat scale; or (2)
between 3-
50 ppm AAP, between 3-50 ppm HPA, and between 2-20 ppm of the phosphonic
acid other than HPA when it is desired to treat corrosion; or (3) between 2-
50ppm
AAP, optionally between 3-50 ppm HPA, and between 2-20 ppm of the phosphonic
acid other than HPA when it is desired to treat white rust.
18. The treatment control system according to claim 16 wherein the
one or more programmed functions controls the feed rates of the AAP,
phosphonic
acid, and optional HPA to provide active concentrations in the water system of
(1)
between 3-30 ppm AAP, between 2-20 ppm HPA, and between 1.5-10 ppm of the
phosphonic acid other than HPA when it is desired to treat scale; or (2)
between 5-
30 ppm AAP, between 3-20 ppm HPA, and between 2-10 ppm of the phosphonic
acid other than HPA when it is desired to treat corrosion; or (3) between 5-30
ppm
AAP, optionally between 3-20 ppm HPA, and between 2-10 ppm of the phosphonic
acid other than HPA when it is desired to treat white rust.
19. The treatment control system according to claim 16 wherein the
one or more programmed functions also controls the activation time so that the
AAP,
phosphonic acid other than HPA, and optional HPA are fed into the water system

substantially simultaneously or in substantially immediate sequential
succession.
20. The treatment control system according to claim 16 wherein the
fourth treatment product comprises a biocide and wherein another programmed
function controls the activation time for feeding the biocide so that it is
fed
substantially simultaneously or in substantially immediate sequential
succession to
one or more of the AAP, phosphonic acid other than HPA, and optional HPA.
21. The treatment control system according to claim 1 wherein the
controller is configured to calculate a total feed amount for each treatment
product,
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to compare the initial volume of each treatment product in its container to
its
respective total feed amount to determine a remaining volume of treatment
product
in each container, and to send an alert or activate an alarm when the
remaining
volume for any treatment product is below a predetermined threshold.
22. The treatment control system according to claim 21 wherein the
controller is configured to track the number of containers of each treatment
product
used or replaced and to compare an initial inventory amount of containers of
that
treatment product to its respective number of containers used or replaced to
determine a remaining number of containers of that treatment product in
inventory,
and to send an alert or automatically order replacement inventory when the
remaining number of containers for any treatment product is below a
predetermined
threshold.
23. The treatment control system according to claim 8 wherein the one
or more optional upstream sensors comprise an inline fluorimeter, a pH meter,
a
conductivity meter, a flow meter, a flow switch, temperature sensor, an ORP
sensor,
or a sensor to monitor oxidant level.
24. The treatment control system according to claim 6 further
comprising one or more sensors upstream of the one or more feeders,
wherein the one or more upstream sensors comprise an inline fluorimeter, a
pH meter, a conductivity meter, a flow meter, a flow switch, temperature
sensor, an
ORP sensor, or a sensor to monitor oxidant level;
wherein the controller receives a signal from at least one upstream indicating

whether a parameter of the water in the water system and utilizes the signal
from the
upstream sensor as an input in the programmed function for at least one
feeder.
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25. A method of controlling treatment of a water system, the method
comprising the steps of:
providing a first container containing an initial volume of a first treatment
product;
providing a second container containing an initial volume of a second
treatment product;
optionally providing one or more of a third through a twelfth container
containing an initial volume of a third through a twelfth treatment product;
wherein each container has a feeder to feed the treatment product from that
container to the water system;
providing a controller connected to the feeders, the controller having one or
more programmed functions to control a feed initiation time and feed rate for
each
treatment product through its feeder;
activating each feeder according to the programmed function associated with
its treatment product to deliver an amount of each treatment product to the
water
system to achieve a desired initial concentration level for each treatment
product in
the water system;
optionally measuring a parameter of the water downstream of the one or
more feeders using a downstream sensor to verify that at least one treatment
product was delivered to the water system; and
wherein each treatment product is useful alone or in combination with another
treatment product for treating one or more of corrosion, white rust, scale, or

biological contamination in the water system..
26. The method according to claim 25 further comprising sending data
or a signal from the downstream sensor to the controller.
27. The method according to claim 25 wherein the feeders are
activated separately so that no treatment product from one feeder is fed into
the
water system simultaneously with a treatment product from another feeder.
28. The method according to claim 25 wherein the measured
downstream parameter is conductivity.
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29. The method according to claim 26 further comprising comparing the
data or signal received related to the downstream parameter to pre-programmed
data to determine whether the amount of treatment product fed into the water
system is in accordance with the programmed function associated with that
treatment product.
30. The method according to claim 29 further comprising sending an
alert message or activating an alarm when the comparison indicates that
treatment
product has not been fed into the water system according to the programmed
function associated with the treatment product.
31. The method according to claim 25 further comprising sending an
alert message or activating an alarm when the measured downstream parameter
indicates that treatment product has not been fed into the water system.
32. The method according to claim 26 further comprising measuring a
parameter of the water upstream of the one or more feeders using an upstream
sensor, sending data or a signal from the upstream sensor to the controller,
and
utilizing the data or signal from the upstream sensor as an input in at least
one
programmed function, and
wherein the upstream sensor is inline fluorimeter, a pH meter, a conductivity
meter, a flow meter, a flow switch, temperature sensor, an ORP sensor, or a
sensor
to monitor oxidant level.
33. The method according to claim 25 wherein the measured
parameter is a concentration of a first treatment product in the water system
and
wherein at least one of the programmed functions is a calculation of feeder
activation time for a second treatment product based on a desired
concentration
level for the second treatment product in the water system, the measured
concentration level for the first treatment product in the water system, and
actual
feeder activation time for the first treatment product to achieve that
measured
concentration level.
34. The method according to claim 25 further comprising tracking a
total feed amount for each treatment product, comparing the initial volume of
each
treatment product in its container to its respective total feed amount to
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remaining volume for each treatment product, and sending an alert or
activating an
alarm when the remaining volume for any treatment product is below a
predetermined threshold.
35. The method according to claim 34 further comprising tracking the
number of containers of each treatment product used or replaced and comparing
an
initial inventory amount of containers of that treatment product to its
respective
number of containers used or replaced to determine a remaining number of
containers of that treatment product in inventory, and sending an alert or
automatically ordering replacement inventory when the remaining number of
containers for any treatment product is below a predetermined threshold.
36. The method according to claim 25 wherein each treatment product
is for treating a single water system issue and the treatment product is in a
concentrated, non-hazardous liquid form.
37. The method according to claim 25 wherein each treatment product
comprises only one active ingredient for treating water and each treatment
product is
in a concentrated, non-hazardous liquid form.
38. The method according to claim 25 wherein the first treatment
product comprises a single active ingredient in neutralized form and the
second
treatment product comprises a single active ingredient in neutralized form
that is
different from the first treatment product.
39. The method of claim 25 wherein each treatment product comprises
a different active ingredient.
40. The method of claim 25 wherein the first treatment product
comprises AAP, the second treatment product comprises a phosphonic acid other
than HPA, and the optional third treatment product comprises HPA to treat
corrosion, white rust, scale, or a combination thereof in the water system;
and
wherein the one or more programmed functions control the feed rates of the
AAP, phosphonic acid, and optional HPA to provide active initial
concentrations in
the water system of (1) at least 2 ppm AAP, at least 2 ppm HPA, and at least
1.5
ppm of the phosphonic acid other than HPA when it is desired to treat scale;
or (2) at
least 3 ppm AAP, at least 3 ppm HPA, and at least 2 ppm of the phosphonic acid
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other than HPA when it is desired to treat corrosion; or (3) at least 3 ppm
AAP,
optionally at least 3 ppm HPA, and at least 2 ppm of the phosphonic acid other
than
HPA when it is desired to treat white rust.
41. The method of claim 40 wherein the one or more programmed
functions controls the feed rates of the AAP, phosphonic acid, and optional
HPA to
provide active initial concentrations in the water system of (1) between 2-50
ppm
AAP, between 2-50 ppm HPA, and between 1.5-20 ppm of the phosphonic acid
other than HPA when it is desired to treat scale; or (2) between 3-50 ppm AAP,

between 3-50 ppm HPA, and between 2-20 ppm of the phosphonic acid other than
HPA when it is desired to treat corrosion; or (3) between 2-50ppm AAP,
optionally
between 3-50 ppm HPA, and between 2-20 ppm of the phosphonic acid other than
HPA when it is desired to treat white rust.
42. The method of claim 40 wherein the one or more programmed
functions controls the feed rates of the AAP, phosphonic acid, and optional
HPA to
provide active initial concentrations in the water system of (1) between 3-30
ppm
AAP, between 2-20 ppm HPA, and between 1.5-10 ppm of the phosphonic acid
other than HPA when it is desired to treat scale; or (2) between 5-30 ppm AAP,

between 3-20 ppm HPA, and between 2-10 ppm of the phosphonic acid other than
HPA when it is desired to treat corrosion; or (3) between 5-30 ppm AAP,
optionally
between 3-20 ppm HPA, and between 2-10 ppm of the phosphonic acid other than
HPA when it is desired to treat white rust.
43. The method of claim 40 wherein the one or more programmed
functions also controls the activation time so that the AAP, phosphonic acid
other
than HPA, and optional HPA are fed into the water system substantially
simultaneously or in substantially immediate sequential succession.
44. The method claim 40 wherein the fourth treatment product
comprises a biocide and wherein another programmed function controls the
activation time for feeding the biocide so that it is fed substantially
simultaneously or
in substantially immediate sequential succession to one or more of the AAP,
phosphonic acid other than HPA, and optional HPA.
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45. The
method of claim 25 wherein the first treatment product
comprises a single active ingredient and the second treatment product
comprises a
single active ingredient different from the first treatment product.
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Description

Note: Descriptions are shown in the official language in which they were submitted.


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SYSTEM AND METHOD FOR AUTOMATED CONTROL, FEED, DELIVERY
VERIFICATION, AND INVENTORY MANAGEMENT OF CORROSION AND
SCALE TREATMENT PRODUCTS FOR WATER SYSTEMS
Cross-Reference to Related Application
[0001] This application claims the benefit of U.S. Application Serial No.
15/908,163 filed on February 28, 2018.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] This invention relates to a system and method for controlling the
treatment of water in a water system, such as industrial process water,
cooling tower
water, and boilers, with various treatment products, particularly by feeding
individual
or combined, undiluted raw materials treatment products each having one active

ingredient that when combined in the water system are effective at inhibiting
corrosion or white rust on metal components in low LSI (Langelier Saturation
Index)
water systems and for inhibiting scale formation in high LSI water systems and

treating other water system issues, using automated control of feed time and
amount
for each individual treatment component, optional delivery verification, and
optional
treatment product inventory management, to maintain system cycles and water
chemistry in the water system.
2. Description of Related Art
[0003] Industrial and other anthropogenic water systems require some form
of treatment, either chemical or non-chemical, to control the build-up of
scale, biofilm
and other corrosion by-products on components of the water system. For water
systems involving heat exchange, such as cooling towers, effective treatment
to
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remove these contaminants and to prolong the amount of time before the systems

are re-contaminated can save significant amounts of money. An effective and
thorough treatment may save costs for labor and treatment chemicals by
reducing
the frequency of periodic treatments or reducing the amount of chemicals
needed for
routine maintenance and/or periodic treatments. Such a treatment may also save
on
energy costs through the operation of clean heat exchange surfaces.
[0004] To maximize the water usage and minimize waste, many water
systems employ a series of chemical treatments that protect the system against

scaling, biofilm formation, and corrosion. In order to properly maintain the
water
system, it is important to be able to control the amount of treatment products

introduced into the water system and the concentration of those products as
the
water moves through or recirculates through the water system to understand the
rate
of treatment consumption and/or discharge through blowdown. Proper control of
treatment products is particularly important in recirculating water systems
where
scale and biofilm buildup reduce the number of times water may be recirculated

(cycles) before some of the water needs to be bled-off and replaced with make-
up
water or before the conductivity of the water reaches a level that triggers
automatic
blowdown. That blowdown may result in draining treatment products before they
have been consumed or before they have had a chance to circulate long enough
to
be effective, requiring the addition of more treatment product to maintain
desired
concentration levels of treatment products in the water system.
[0005] Many treatment products are fed from diluted multi-component
formulations shipped in large containers or drums, the weight and size of
which
makes freight and delivery more expensive and movement from delivery area to
storage area to the treatment feed location more difficult and potentially
dangerous.
Some water system treatments are sold and shipped in solid form, to be
dissolved at
the treatment site. For
example, U.S. Patent Application Publication No.
2013/0239991 discloses a solid treatment product feeder system where water is
taken from the water system to be treated via a side stream that dilutes the
solid
treatment chemicals and is then reintroduced into the water system with the
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dissolved treatment product. Such a system has the benefit that shipping,
storing,
and moving the treatment product in solid form is easier than large drums of
diluted
liquid treatment. However, control over the amount of treatment introduced
into the
water system is not very precise.
[0006] Some treatment products include a dye or fluorescing agent to allow a
measurement of the concentration of the treatment product in the water system
and
to aid in controlling treatment feed rate, which is effective provided the
sensor is not
fouled. However, a fluorimeter only verifies the presence of the dye or other
fluorescing agents, it cannot differentiate between the various components in
a
multi-component treatment product, which may be required to treat a water
system
with a variety of treatment products or components in order to address
different
issues within the water system, such as scale and biofilm development.
[0007] It is also known to control operations of a water system, including
rates of chemical feed, make-up water, and blow-down, using various control
systems. It is also known to use PLC or computer controlled devices to control
feed
rates of various chemicals or solutions for other purposes. However, it is
believed
that such systems have not been used to control multi-component treatment of
water
systems using automated feed, treatment delivery verification, and optionally
treatment inventory management, to more precisely control the treatment of a
water
system.
[0008] Various water treatment compositions are used to reduce corrosion,
mineral scale, and white rust formation on metal components in contact with an

aqueous solution in water systems such as open recirculating systems, closed
loop
cooling or heating systems, cooling towers and boilers, and help protect the
metal
components of these systems. The metals typically used in these water systems
include ferrous metals, including galvanized steel, aluminum and its alloys,
copper
and its alloys, lead, and solder. Many known corrosion inhibitors contain
regulated
toxic metals, such as zinc, chromate, and molybdate, which are harmful to the
environment and increase the costs. Zinc is typically used as corrosion
inhibitor in
water systems with highly corrosive water (low LSI).
However its usage is
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undesirable due to toxicity issues and its use faces regulations in some
locations.
Tin has also been used as a non-toxic alternative to zinc, but it is more
expensive.
[0009] The performance of many known corrosion and scale inhibitors is also
negatively impacted by the use of biocides, which are frequently used in water

systems to control the growth of microorganisms. The use of polyaspartic acid
and
a single phosphonic acid are disclosed in U.S. Patent No. 5,523,023 as
effective in
inhibiting corrosion and scale, even in the presence of a biocide when the
phosphonic acid is 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC). The
preferred phosphonic acid in the '023 patent is PBTC, but other phosphonic
acids,
including 1-hydroxyethane 1,1-disphosphonic acid and hydroxyphosphonoacetic
acid (HPA) are also mentioned as suitable. The corrosion rate results shown in
the
'023 patent based on the use of polyaspartic acid and PBTC are better than
other
corrosion inhibitors, but there is still a need for even greater corrosion
inhibition,
particularly in the presence of biocides. The scale formation results shown in
the
'023 patent based on the use of polyaspartic acid and PBTC are approximately
the
same as the results obtained by using PBTC alone, indicating no real
improvement
in scale inhibition is obtained with the two-component formula of the '023
patent.
[0010] Currently utilized solutions for white rust prevention include
passivating the metal surfaces with zinc carbonate and control of water
chemistry to
reduce potential for white rust formation. Known treatments include the use of

inorganic phosphates, thiocarbamates, organo-phosphorous compounds and
tannins. For
example, U.S. Patent Nos. 5,407,597 and 6,468,470 disclose
compositions comprising organophosphorus compounds (including PBTC), an alkali

metal salt of molybdenum, titanium, tungsten, or vanadium, and either a
carbamate
compound or a tannin compound. U.S. Patent No. 6,183,649 discloses a white-
rust
treatment composition comprising PBTC, sodium polyacrylate, sodium
tolytriazole,
an alkali metal molybdate, and an alkali metal bromide for treating
circulating water
systems. The '649 patent also discloses the addition of a 1.5% aqueous
solution of
decyl thioethyletheramine (DTEA) at a rate of 251b/1,000 gallons of water/week
to
the circulating water system prior to adding the white rust treatment
composition at a
rate of 600 ppm per cycle for ten cycles of recirculation after addition of
the DTEA.
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[0011] Previously known water treatments involve pre-mixed compositions
including multiple ingredients that are pre-mixed into a single composition.
Most
water systems require treatment with several different pre-mixed compositions
to
address different problems associated with the water system. These different
pre-
mixed compositions may include some of the same ingredients, which may be
wasteful when two or more pre-mixed compositions with the overlapping
ingredients
are used in the same water system. Additionally, some pre-mixed treatment
compositions have ingredients that negatively impact ingredients in other pre-
mixed
compositions, such as the biocide/corrosion inhibitor issue discussed above.
Pre-
mixed liquid treatment compositions are frequently used, which involve large
volumes of liquids, typically including water. This makes shipping and storage
of the
treatment costly and difficult. When
a pre-mixed composition needs to be
replenished, a worker typically has to carry the pre-mixed composition, which
may
be in a multi-gallon container of significant weight, over distances and/or up
one or
more flights of stairs to reach a treatment destination.
[0012] There is a need for treatment products and a treatment method that
can be used to inhibit corrosion, white rust, and scale, along with other
issues, such
as biological contamination, in a water system using a few ingredients that
may be
separately added, rather than in a pre-mixed composition. There is also a need
for
an effective system and method to allow delivery of individual ingredients or
small
groupings of ingredients that can be fed separately into a water system to
control the
amount of ingredients fed, the timing of addition for each ingredient to
combine
synergistic ingredients and aid in avoiding negative interactions, to allow
treatment
for multiple types of water system issues, and to optionally control inventory

management for the treatment ingredients.

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SUMMARY OF THE INVENTION
[0013] This invention provides a treatment control system and method for
treating water in a water system, such as industrial process water, cooling
tower
water, boilers, closed loops, pasteurizers, and retorts, with various
treatment
products using automated control of treatment feed, monitoring treatment use,
treatment delivery verification, and optional treatment product inventory
management, to maintain system cycles and water chemistry in the water system.

This invention also provides treatment product to treat a water system to
inhibit
corrosion, white rust, and scale using ingredients that may be separately
added and
controlled with preferred embodiments of the treatment control system and
method
of the invention. According to one preferred embodiment of the invention, an
improved corrosion inhibitor, white rust inhibitor, and scale inhibitor
products
comprise an amino-acid based polymer (AAP), hydroxyphosphonoacetic acid (H PA)

or its water soluble salt, and another phosphonic acid or its water soluble
salt, which
may be stored separately and added to the water system as separate
ingredients.
[0014] According to one preferred embodiment, a treatment control system
comprises an injection manifold for injecting treatment products into a slip
stream or
side stream drawn from the water system being treated, one or more containers
of
treatment product, one or more feeders, such as pumps, to feed treatment
product
from the containers to the injection manifold or otherwise into the water
system, and
a controller for activating the feeders to deliver an amount of treatment
product
needed for the particular water system according to programmed time intervals
(programmed timing functions) or programmed calculation or data comparison
functions. As used herein, a "treatment product" refers to a single ingredient
(or a
solution having a single active ingredient) or a pre-mixed composition of two
or more
active ingredients useful in treating one or more issues associated with water

systems, such as biological contamination, corrosion, white rust, or scale. A
variety
of functions may be pre-programmed into a preferred treatment control system
and
those programs may be modified by a user as needed to better suit the actual
water
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system operating parameters and actual treatment issues for the water system
in
which the treatment control system is being used.
[0015] According to another preferred embodiment, the treatment system
controller comprises processing and telemetry capabilities that allow it to
send and
receive signals, make calculations, display data, store data and/or save data
to a
removable memory card or other connected device, and activate/deactivate feed
mechanisms for each container of treatment product. A preferred treatment
system
controller is also capable of automatically sending signals to alter the feed
rate of
treatment products and accepting manual input of programming changes or manual

changes in treatment feed rates. A preferred treatment system controller is
also
capable of receiving signals from other sensors within the water system, such
as pH
meter ,a flow meter, or an opto-electrochemical sensor, which may be used in
calculating treatment product feed rates. The data and information collected
and
calculated by the treatment system controller may be displayed on an optional
screen on the housing for the controller or it may be communicated to a
separate or
remote control system (such as the water system controller), directly (through
a
plug-in connection) or by wireless communication, to remote users (such as
supervisors or remote operators), to achieve automated control over the water
system. Similarly, a computer can talk remotely to the system and prescribe a
feed
program based on laboratory testing of system samples.
[0016] The treatment product chemicals fed into the water system through
the treatment control system would provide the needs for scale, corrosion,
white
rust, and biological inhibition. Prior art treatments are typically fed from
diluted multi-
component pre-mixed formulations (e.g. one pre-mixed composition that contains

chemicals to treat more than one water system issue, such as treating scale
and
biofilm, or that contains several active ingredients to treat a single
product, such as
scale) out of large drum containers, such that the precision of the pump
becomes
less important. However the weight and size of the container complicates
shipping,
storage, and the movement of the product from storage to the feed location.
The
treatment products according to one preferred embodiment of the invention are
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provided as individual, separate components or undiluted mixtures of raw
materials
(rather than multi-component formulations) in flexible packages in a non-
hazardous
form. These treatment containers reduce freight, provide easier movement of
the
product containers to the point of feed, and minimize injuries from carrying
and
possible chemical contact. Disposal of the containers is simplified because
the
packaging will be collapsible and preferably more biodegradable. The chemical
feed
pumps are designed to maintain prime, and the device will monitor pump times
to
notify personnel when the container will need replacement with a full
container.
[0017] According to another preferred embodiment, a treatment control
system also comprises a sensor, such as a conductivity meter, for verifying
delivery
of a treatment product into the water system. The sensor is placed downstream
of
the treatment product feed point, such as downstream of the injection
manifold, to
measure a parameter of the water to verify treatment product delivery of each
component to the system. Each treatment product is fed into the manifold (or
otherwise fed into the water system) separately, so that the sensor can make a

measurement for each product being added. The controller receives a signal
from
the sensor regarding the measured parameter, which indicates whether treatment

product was injected when it was supposed to be or whether sufficient (or too
much)
product was injected according to the pre-programmed functions. If the product
was
not injected or an incorrect amount of product was injected, the controller
will alert a
user that there is a malfunction or that a container of treatment product is
empty and
needs replacing.
[0018] According to another preferred embodiment, the treatment system
controller tracks the amount of treatment product injected compared to the
initial
volume of product in the container and provides an alert when the remaining
volume
in the container is below a predetermined threshold, such as 10% or 5% volume
remaining to indicate the container is near empty (or actually empty, if
desired) so
that it may be replaced. According to yet another preferred embodiment, the
controller also tracks inventory of each type of treatment product used and
can
provide an alert or automatically send a replacement order to replenish
inventory
when the supply of any particular treatment product at the treatment location
is low.
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[0019] A preferred treatment control system and method according to the
invention allows treatment feed rates of individual treatment products or
components
to be adjusted based on programmed functions. Those functions may be based on
time, measurements from water system sensors, measurements from system water
meters, or a combination thereof. This allows the treatment for a water system
to be
automatically adjusted in real time based on actual water chemistry and/or
actual
water system operating parameters, such as blowdown rate. The functions may
also be manually changed on-site or via a remote connection to a preferred
treatment control system to accommodate changes in treatment protocols or
regulations or changes in desired concentrations of any particular treatment
product.
Preferably, a treatment control system has alarming functionality to indicate
a
problem with treatment delivery verification, low inventory, system
malfunction, or
other issues to provide a visual or audible alarm or to send a message to a
remote
user. A preferred treatment control system also records data regarding
treatment
feeds, calculations related to treatment feeds and programmed functions,
programmed desired residual concentrations of treatment chemicals, and sensor
readings or measurements and/or can send such data to a remote computer,
terminal, or user. This data aids in demonstrating compliance with treatment
protocols and regulations.
[0020] According to one preferred embodiment of the invention, an improved
corrosion inhibitor, white rust inhibitor, and scale inhibitor treatment
products
comprise an amino-acid based polymer (AAP), hydroxyphosphonoacetic acid (H PA)

or its water soluble salt, and another phosphonic acid or its water soluble
salt, which
may be added as separate treatment products using the delivery and control
systems and methods of the invention. Hydroxyphosphonoacetic acid has the
following general structure:
OH
HO __ P CH COOH
[0021] 0 OH
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[0022] Most preferably, the amino-acid based polymer is polyaspartic acid or
its water soluble salt, but other compounds such as polyglycine acid,
polyglutamic
acid and their salts may also be used. Most preferably, the amino acid based
polymer has the following formula:
0
Rffi CH C N H
x n 2
[0023]
[0024] where R1 = H, R2=0H, and R3=COOH and x=1 for polyaspartic acid.
Most preferably, the other phosphonic acid is a phosphonocarboxylic acid or
any
organic phosphonate may also be used. Most preferably, the phosphonocarboxylic

acid is 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or 2-phosphonobutene-
1,2,4-tricarboxylic acid (PBTC) or phosphonosuccinic acid. Preferably the
weight
ratio of AAP to HPA in the inhibitor treatment products is 90:10 to 10:90 and
the ratio
of combined AAP and HPA (which may be combined together, pre-mixed into a
single container, but are more preferably maintained as separate ingredients)
to
other phosphonic acid is in the range of 90:10 to 60:40. More preferably, the
weight
ratio range of AAP to HPA in the inhibitor treatment products is 80:20 to
80:20 and
the ratio of combined AAP and HPA to other phosphonic acid is 80:20 to 70:30.
[0025] Most preferably, all treatment products used in connection with the
AAP/HPA/phosphonic acid treatment products according to a preferred embodiment

of the invention are all organic and do not contain regulated metals such as
zinc,
chromate, and molybdate and their combined performance is not affected by
addition of biocides. Most preferably, all treatment products used in
connection with
the AAP/HPA/phosphonic acid treatment products according to a preferred
embodiment of the invention do not contain tin.
[0026] It was previously known to use both HPA and AAP, such as
polyaspartic acid, separately as corrosion inhibitors. It was also disclosed
in the
'023 patent that AAP could be used together with phosphonocarboxylic acid to
inhibit
corrosion and scale, but it was not previously known to use AAP and HPA
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along with another phosphonic acid, preferably a phosphonocarboxylic acid, or
an
organic phosphonate to inhibit corrosion or scale.
[0027] When added to the water in the water system being treated, preferred
AAP/HPA/phosphonic acid treatment products according to the invention for
inhibiting corrosion yield at least 3 ppm active AAP, at least 3 ppm active
HPA, and
at least 2 ppm of the other phosphonic acid. More preferably, when added to
the
water in the water system being treated, preferred AAP/HPA/phosphonic acid
treatment products yield 3 ppm-50 ppm AAP, 3 ppm-50 ppm HPA, and 2 ppm-20
ppm of the other phosphonic acid and most preferably between 5ppm-30ppm AAP,
3ppm-20ppm HPA, and 2 ppm-10 ppm of the other phosphonic acid. Additionally,
the combined total of the three components of preferred AAP/HPA/phosphonic
acid
treatment products yield at least 8 ppm active corrosion inhibitors when added
to the
water being treated. These ingredients have the unexpected synergistic effect
of
improved corrosion inhibition in low LSI water systems (LSI <-0.5) without
requiring
the use of toxic metals and without being adversely impacted by biocides.
[0028] In addition to unexpected and synergistic effect of the
AAP/HPA/phosphonic acid inhibitor treatment products on ferrous metal
corrosion
inhibition in low LSI water, the same AAP/HPA/phosphonic acid treatment
products
also have a positive effect on preventing formation of white rust on
galvanized steel.
Galvanized steel consists of a thin coating of zinc fused to a steel
substrate. White
rust is a rapid, localized corrosion attack on zinc that usually appears as a
voluminous white deposit. This rapid corrosion can completely remove zinc in a

localized area with the resultant reduction in equipment life. White rust
formation
tends to increase with increased alkalinity levels in the water.
Neither
hydroxyphosphonoacetic acid nor amino-acid based polymers, such as
polyaspartic
acid, alone or in combination, has been previously utilized in commercial
products
for white rust prevention. Without being bound by theory, it is believed that
the
AAP/HPA/phosphonic acid treatment products according to the invention may be
forming a protective layer on the surface of galvanized steel and reduce white
rust
formation. For treating white rust according to the invention, it is preferred
to use
hydroxyphosphonoacetic acid, an amino-acid based polymer, and another
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phosphonic acid in the amounts indicated above for inhibiting corrosion (both
weight
ratios and concentrations when added to the water in the water system being
treated), but it has also been found that the use of an amino-acid based
polymer
without hydroxyphosphonoacetic or the other phosphonic acid is beneficial at
inhibiting white rust.
According to another preferred embodiment, treatment
products for treating white rust comprise an amino-acid based polymer used
together with hydroxyphosphonoacetic acid, and without another phosphonic
acid.
According to yet another preferred embodiment, treatment products for treating

white rust comprise an amino-acid based polymer, without any
hydroxyphosphonoacetic acid. The preferred concentrations and ranges for these

treatment product components when added to the water being treated for white
rust
are the same as for inhibiting corrosion.
[0029] In addition to unexpected and synergistic effect of the inhibitor
treatment products on white rust and on ferrous metal corrosion inhibition in
low LSI
water, the same AAP/HPA/phosphonic acid treatment products also have a
positive
effect on preventing formation of mineral scale in high LSI water (LSI >1).
Mineral
scale includes calcium and magnesium carbonate, calcium phosphate, calcium
sulfate, and silica. Solubility of calcium carbonate and phosphate decreases
when
temperature increases, making calcium carbonate and calcium phosphate more of
an issue in water systems with higher temperatures, such as cooling towers.
LSI is
determined by the following formula:
[0030] LSI = pH - pHs, where pHs is pH at CaCO3 saturation point.
[0031] An LSI > 0 indicates scaling, as scale can form and CaCO3
precipitation may occur. An LSI 0 indicates nonscaling, as there is no
potential to
scale and the water will dissolve CaCO3. As will be understood by those of
ordinary
skill in the art, LSI is an indication of driving force and not strict
quantitative
indication of scale formation, which will depend on the water characteristics,

temperature, and water systems operations. However, without a scale inhibitor,

scale will typically precipitate out of water when the LSI is greater than
0.2. Using
treatment products according to preferred embodiments of the invention, no
scale
will form (calcium carbonate will not precipitate out of the water) at LSI
values of 1-3.
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[0032] When added to the water in the water system being treated,
preferred AAP/HPA/phosphonic acid treatment products according to the
invention
for inhibiting scale yield at least 2 ppm active AAP, at least 2 ppm active
HPA, and at
least 1.5 ppm of the other phosphonic acid. More preferably, when added to the

water in the water system being treated, preferred AAP/HPA/phosphonic acid
treatment products yield 2 ppm-50 ppm AAP, 2 ppm-50 ppm HPA, and 1.5 ppm-20
ppm of the other phosphonic acid and most preferably between 3 ppm-30ppm AAP,
2 ppm-20 ppm HPA, and 1.5 ppm-10 ppm of the other phosphonic acid.
Additionally, the combined total of the three components of preferred
AAP/HPA/phosphonic acid treatment products yield at least 6.5 ppm active scale

inhibitors when added to the water being treated. These ingredients have the
unexpected synergistic effect of improved corrosion inhibition in high LSI
water
systems (LSI >1) without requiring the use of toxic metals and without being
adversely impacted by biocides.
[0033] Treatment products according to preferred embodiments of the
invention work together to inhibit corrosion of metals such as ferrous metals,

aluminum and its alloys, copper and its alloys, zinc and its alloys,
galvanized steel
(including white rust), lead, or solder, and to prevent mineral scale
formation. The
treatment products are particularly useful in water systems such as open
recirculating systems, closed loop cooling or heating systems, and boilers
that may
experience corrosion, white rust, and scale formation during different times
of the
year or under different operating conditions, including use in both low LSI
(high
corrosively water) and high LSI (high scale tendency) waters.
[0034] According to other preferred embodiments, additional treatment
products may be used with preferred AAP/HPA/phosphonic acid treatment products

for inhibiting corrosion or white rust or scale. These additional treatment
products
include one or more of the following ingredients: a neutralizing amine,
chlorine
stabilizer, such as monoethanol amine (MEA); a secondary scale inhibitor
(since the
treatment products themselves also work as a scale inhibitor) and dispersion
agent,
such as
polycarboxylate polymer and/or carboxylate/sulfonate functional
copolymers (typical examples: polyacryclic acid (PAA), polymethacrylic acid
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(PMAA), polymaleic acid (PMA), and copolymers of acrylic acid and 2-acylamido
¨
methylpropane sulfonic acid (AA/AMPS); other scale and corrosion inhibitors,
chelant agents; azole corrosion inhibitors, such as benzotriazole,
alkylbenzotriazole
(tolyltriazole); and/or a fluorescent dye tracer, such as 1,3,6,8-
Pyrenetetrasulfonic
acid tetrasodium salt (PTSA). Although it is preferred to use the
AAP/HPA/phosphonic acid treatment products as separate ingredients with the
delivery and control system of the invention, these products may also be pre-
mixed,
optionally with one or more of the additional treatment products noted above,
into a
single pre-mixed composition. The overall pre-mixed composition preferably
comprises around 2%-15% (by weight) of an amino-acid based polymer (such as
polyaspartic acid), around 2% to 10% (by weight) of hydroxyphosphonoacetic
acid,
and around 2% to 10% (by weight) of another phosphonic acid.
[0035] According to one preferred method of preventing corrosion of metal
components, white rust on galvanized steel components, and/or scale in a water

system, AAP/HPA/phosphonic acid treatment products according to the preferred
embodiments of invention as described above are added to the water system as
separate ingredients using a delivery and control system according to a
preferred
embodiment of the invention. Depending on the type of issue being treated, one
or
more of the AAP/HPA/phosphonic acid treatment products are added to the water
system (with combinations of two or more ingredients added at substantially
the
same time) to provide the above noted preferred concentration ranges. For
preventing corrosion and white rust inhibition, a preferred delivery and
control
system operates to feed one or more of the AAP, HPA, and another phosphonic
acid
as described above, into the water at an effective feed rate of 20ppm - 600
ppm, or
more preferably 100 ¨ 300ppm, of treatment products, depending on the treated
water chemistry and the amount of optional treatment products used in
connection
with the AAP/HPA/phosphonic acid treatment products. Preferably, a sufficient
amount of treatment products are added to the water system to provide
effective
active amounts of one or more of the three treatment components (depending on
whether white rust is being treated or both corrosion and white rust) of at
least 3
ppm AAP, at least 3 ppm HPA, and at least 2 ppm of another phosphonic acid,
each
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as initial concentrations when added to the volume of water in the water
system
being treated. More preferably, the treatment products are added in a
sufficient
amount to provide effective active amounts one or more of the components of
between 3 ppm ¨ 50 ppm AAP, between 3pm ¨ 50 ppm HPA, and between 2 ppm -
20 ppm of another phosphonic acid when added to the water in the water system.

Most preferably, these effective active amounts are 5ppm ¨ 30 ppm AAP, 3 ppm ¨

20 ppm HPA, and 2 ppm - 10 ppm other phosphonic acid when added to the water
in the water system.
[0036] For scale inhibition, a preferred delivery and control system feeds one

or more of the AAP, HPA, and another phosphonic acid as described above into
the
water at an effective feed rate of 20ppm - 600 ppm, or more preferably 50
¨300ppm, of treatment products, depending on the treated water chemistry and
the
amount of optional treatment products used in connection with the
AAP/HPA/phosphonic acid treatment products. Preferably, a sufficient amount of

treatment products are added to the water system to provide effective active
amounts of one or more of the three treatment components of at least 2 ppm
AAP,
at least 2 ppm HPA, and at least 1.5 ppm of another phosphonic acid, each as
initial
concentrations when added to the volume of water in the water system being
treated. More preferably, the treatment products are added in a sufficient
amount to
provide effective active amounts of the three treatment components of 2 ppm -
50
ppm AAP, 2 ppm - 50 ppm HPA, and 1.5 ppm -20 ppm of another phosphonic acid,
each as initial concentrations when added to the volume of water in the water
system being treated. Most preferably, the treatment products are added in a
sufficient amount to provide effective active amounts of the three components
of
between 3 ppm ¨ 30 ppm AAP, between 2pm ¨ 20 ppm HPA, and between 1.5 ppm
- 10 ppm of another phosphonic acid when added to the water in the water
system.

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BRIEF DESCRIPTION OF THE DRAWINGS
[0037] The system and method of the invention are further described and
explained in relation to the following drawings wherein:
FIG. 1 is a front elevation view of one preferred embodiment of treatment
control system according to the invention;
FIG. 2 is a front elevation view of one preferred embodiment of the internal
components of a portion of the treatment control system according to FIG. 1;
FIG. 3 is a front elevation view of an alternate preferred embodiment of the
internal components of FIG. 2;
FIG. 4 is a front elevation view of one preferred embodiment of the internal
components of another portion of the treatment control system according to
FIG. 1;
FIG. 5 is a perspective view of a preferred treatment storage and feed
container for use with a treatment control system according to the invention;
FIG. 6 is a front elevation view of another preferred embodiment of treatment
control system according to the invention;
FIG. 7 is a chart showing conductivity readings for various treatment
components fed at different flow rates;
FIG. 8 contains photographs showing corrosion levels on steel coupons after
spinner tests at flow rates of 3ft/sec and 5ft/sec;
FIG. 9 contains photographs showing corrosion levels on steel coupons after
spinner tests run in presence of biocide at flow rates of 3ft/sec and 5
ft/sec;
FIG. 10 contains photographs showing corrosion levels on steel coupons after
spinner tests at a flow rate of 3ft/sec; and
FIG. 11 contains photographs showing white rust levels on galvanized
coupons after spinner tests.
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DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0038] Referring to FIG. 1, one preferred embodiment of a treatment delivery
and control system 10 is shown. System 10 preferably comprises control housing
12 and treatment housing 40. Each housing 12 and 40 preferably has a box like
body 13, 41 and a closable or removable door or cover 15, 43 that protects the

interior components in the housing but also allows access for service and for
replacement of treatment product containers 42. Most preferably, each housing
12
and 40 is a NEMA 4 equivalent box.
[0039] Referring to FIGS. 1-4, system 10 also preferably comprises a
controller 14 that controls a feeder 32 for each container 42 of treatment
product, to
initiate feed of each treatment product into the water system at a
preprogrammed
time or in response to one or more measurements of the water, to feed an
amount of
treatment product over a period of time or at periodic intervals in accordance
with
programmed feed rate functions based on desired concentrations of treatment
products, sensor readings or measurements, and/or preset feeder activation
times.
Feed rates for each treatment product may be calculated by controller 14 based
on
duration of time a valve is opened, duration of time a feeder pump is on,
calculated
flow rates based on pump capacity or tubing size, measured based on readings
from
a flow meter, or any other combination of parameters and measurements for the
various components of system 10 as will be understood by those of ordinary
skill in
the art. Preferably controller 14 is a programmable logic controller ("PLC")
or
industrial computer 14. Treatment system 10 also preferably comprises one or
more
feeders 32 (preferably pumps), a manifold 20, and a conductivity meter 22 (or
other
sensor) downstream of the manifold, one or more sensors 21 upstream of the
manifold, all inside housing 12. System 10 also preferably comprises one or
more
treatment containers 42 inside housing 40. Disposed through a wall of housing
body
13 are connection ports 16 and 26, which allows system 10 to be connected to a

side or slip stream drawn off of the water system and to return that water
with
injected treatment products back into the water system using tubing or piping,
as will
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be understood by those of ordinary skill in the art. Also disposed through
housing
body 13 and body 41 are connection ports 28 and 48, connected together by
tubing
46, to allow treatment products to flow from containers 42 within housing 40
to the
injection manifold 20 via pump 32. Connection ports 16, 26, 28, and 48 are
preferably quick connecting type ports. Preferably, there is one connection
port 28,
48 for each container 42 (e.g. 28a, 28b, etc.). Alternatively, housing body 41
may
have an aperture(s) to allow tubing 44 connected to a treatment container 42
to pass
through to connection port 28, without using a separate connection port 48 or
separate tubing 46.
[0040] A feeder is used to feed treatment product into the water system.
Preferably there is one feeder for each container of treatment product. A
preferred
feeder for system 10 is a pump 32, preferably a metering peristaltic pump, but
other
types of pumps may also be used. Peristaltic pumps are preferred because they
provide consistent metered feed with no loss of prime, which has been a
problem
with prior art treatment feeds and a major cause of prior art treatment
failures. A
pump 32 is preferably provided for each treatment container 42 to pump the
treatment from the container 42 to a port 34 on manifold 20. For example, pump

32a pumps treatment product from container 42a through tubing 44a, through
port
48a and tubing 46a (if port 48a is used), through port 28a, and through tubing
30a to
port 34a on manifold 20. Ports 28 for containers 42b and 42d are not shown in
FIG.
2 because they are located rearwardly of ports 28a and 28c. A slip stream or
side
stream from the water system passes through port 16, through tubing 18 into
manifold 20, where one or more treatment products from containers 42 are
injected
through ports 34. Treatment control system 10 may be plumbed to an existing
water
system pressurized line to feed a slip stream or side stream to system 10
through
port 16, or a submersible pump may be placed in a sump to pump water from the
water system to system 10 through port 16. The treated water exits manifold 20
and
passes through a sensor 22, preferably a conductivity meter, then through
tubing 24
and out through exit port 26. Tubing or piping connected to port 26 then
reintroduces the treated water back into the water system. One or more sensors
21
(such as 21a, 21b, etc.) may also be placed upstream of manifold 20 to detect
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properties of the water prior to injection of the treatment product (although
the water
passing through sensor 21 may have one or more treatment products in it from
previous injections of treatment product). Sensor(s) 21 may include an inline
fluorimeter, a pH meter, another conductivity meter (other than conductivity
meter
22), a flow meter, a flow switch, temperature sensor, and/or an ORP sensor or
similar sensor to monitor oxidant level.
[0041] Although pumps 32 are preferred feeders for treatment product into
the water system, other feeders or feed systems may also be used with
treatment
control system 10. For example, containers 42 may be located to feed into
water
system via gravity feed, such as feeding directly to the water system sump, or
a
venturi injector with PLC 14 controlling valves to block or allow treatment
flow in
order to control the feed rate of the treatment products.
[0042] Referring to FIGS. 4 and 5, each treatment container 42 preferably
comprises a flexible pouch with integrated tubing 44, similar to an IV bag,
having an
end fitting to allow connection to port 48 or port 28. Container 42 is
preferably hung
inside housing 40 via hooks or clips attached to an interior wall of housing
40.
Optionally, a flexible pouch container 42 may be placed within another
container,
such as a box 50 or a "Cubitainer," to provide further protection for
container 42 and
support for container 42 within housing 40. As an alternative, housing 40 may
be
omitted from system 10 and containers 42 may be hung or set in a location
adjacent
housing 12, particularly if a protective and supportive box 50 is used. Other
types of
containers 42, such as a cylindrical vessel, may also be used. For any stiff
sided
container, the container may rest on a bottom wall of housing body 41, rather
than
being hung, and connection port 48 (or aperture) may be disposed through a
bottom
wall of housing 40. Other configurations may also be used.
[0043] Referring to FIG. 6, another preferred embodiment of a treatment
delivery and control system 110 is shown. System 110 preferably comprises a
housing 112, which preferably has a box like body and a closable or removable
door
or cover that protects the interior components in the housing but also allows
access
for service and for replacement of treatment product containers 142 and feeder

mechanism or pump mechanism 132. Most preferably, housing 12 is a NEMA 4
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equivalent box. System 110 preferably comprises a plurality of containers 142,
each
comprising a cap 145 having a one-way valve and an exit tube, connectable in
fluid
communication with tubing 144 to dispense fluid from container 142 to manifold
120
and into the water system being treated. Each container 142 and cap 145 is
preferably made of inexpensive plastic, that is easily replaceable when a
container is
empty or when the valve mechanism in cap 145 needs to be replaced. Containers
142 may come in different sizes depending on the size of the water system
being
treated and/or the treatment product contained in a particular container. A
feeder or
pump mechanism 132 is preferably provided for each container 142. Pump
mechanism 132 may comprise a simple actuator to open and close a one-way valve

in cap 145 to allow fluid to pass via gravity feed from container 142 through
tubing
144. Alternatively pump mechanism 132 may comprise a motor configured to
rotate
an impeller to pump or move fluid from container 142 through tubing 144 and
port
134 to deliver a treatment product to the water system without relying on
gravity
feed. As another alternative, pump mechanism 132 may comprise a motor
configured to rotate a wheel with a crank pin that engages with a slide plate
to
actuate a piston in cap 145 to pump fluid from container 142. Other pumping
mechanisms may also be used, as will be understood by those of ordinary skill
in the
art. Each pump mechanism 132 may be battery powered or powered through
controller 114. Pump mechanism 132 is preferably inexpensive and easily
replaced
when needed. Although container 142 may be a flexible pouch, like preferred
containers 42, more preferably they are stiff-sided or rigid plastic
containers capable
of standing on any stable, flat surface. Each pump mechanism is preferably
attached to a rear wall of housing 112 or may sit on a bottom side of housing
112
and each preferably has a flange on which container 142 or a portion of cap
145
may be supported in an inverted position (cap 145 facing down).
Other
configurations may also be used.
[0044] Treatment system 110 also preferably comprises a manifold 120 and
a plurality of ports 134, each connected to a tubing 144. A slipstream from
the water
system being treated is diverted to system 110, passes through manifold 120
where
treatment product(s) are added according to programmed functions, and the

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slipstream with the added treatment product(s) is returned to the water
system.
Although two separate housings may be used (as with system 10), preferably
only a
single housing 112 is used with system 110. Ports (not shown) may be included
through walls of the housing 112 to allow connection of the slipstream to
manifold
120, as previously described with system 10. System 110 may also include one
or
more sensors, such as a conductivity meter, upstream or downstream of the
manifold (similar to sensors 21, 22 in system 10). Preferably, such sensors
are
contained inside housing 112.
[0045] System 110 also preferably comprises a controller 114 that controls a
feeder mechanism or pump mechanism 132 for each container 142 of treatment
product, to initiate feed of each treatment product into the water system at a

preprogrammed time or in response to one or more measurements of the water, to

feed an amount of treatment product over a period of time or at periodic
intervals in
accordance with programmed feed rate functions based on desired concentrations

of treatment products, sensor readings or measurements, and/or preset feeder
activation times. Feed rates for each treatment product may be calculated by
controller 114 based on duration of time a valve in cap 145 is opened/duration
of
time a feeder pump 132 is onto actuate the valve in cap 145, calculated flow
rates
based on pump capacity or tubing size, measured based on readings from a flow
meter, or any other combination of parameters and measurements for the various

components of system 110 as will be understood by those of ordinary skill in
the art.
Preferably controller 114 is a small single board computer with wireless and
blue
tooth capabilities, HDMI or other data connection ports, and optionally one or
more
DC drive units to power pump mechanisms 132.
Controller 114 may be
preprogrammed with a variety of programs to operate pump mechanisms 132 to
dispense various amounts of each treatment product at specified time
intervals. An
optional, but preferable, display screen 152 may be used for communication of
data
and manual data entry, as needed.
[0046] Most preferably, each treatment container 42a, 42b, 42c, 42d, 142a,
142b, 142c, etc. contains a different treatment product in concentrated form,
such as
the AAP in container 42a or 142a, the HPA in container 42b or 142b, and the
other
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phosphonic acid in container 42c or 142c. Other optional ingredients may be in

different containers 42 or 142. Additionally, other treatment products, such
as other
scale inhibitors, corrosion inhibitors, biocides (preferably one oxidizing and
one non-
oxidizing), etc. may be contained in other containers 42 or 142. Most
preferably,
each container 42 contains an individual treatment chemical or ingredient
(each with
a single active ingredient, although combinations or two or more active
ingredients
may also be used), which allows the use of 8-12 common chemical components for

treatment of a typical water system instead of 50-100 formulated, pre-mixed
treatment compositions to achieve the same results. This allows the use of
twelve
or fewer containers 42, 142 for treatment system 10, 110 to cover most typical
water
system treatment issues. Most commercial formulated multi-component treatments

can be reduced to around 4 core components, allowing the use of only four
containers 42, 142 with treatment system 10, 110 for most water systems.
Although
any particular treatment container 42, 142 may contain a pre-mixed treatment
composition having multiple chemicals or active components (such as a
corrosion
inhibitor and a biocide) to treat one or more water system issues, it is
preferred that
each container 42, 142 have only one or two active components or ingredient to

target a single water system issue, either alone or in combination with
another
component or ingredient in another container. The treatments in the various
containers 42a, 42b, 142a, 142b, etc. may be compatible for use together or
may be
incompatible, since system 10, 110 is capable of controlling when each
treatment is
dosed to the water system, as discussed below, the timing may be controlled to

avoid any adverse interactions between treatment products. Most preferably,
the
treatment products are concentrated liquid products, so that each container
42, 142
is small, lightweight, and easy to ship, store, and change out. Although other
sizes
may be used, each container 42, 142 preferably holds around 5L of treatment
product. The use of four containers 42a-42d (or 142a-142d) each containing a
core
treatment chemical (such as AAP, HPA, other phosphonic acid, and a biocide),
at 5L
each will treat a 100 ton cooling system for an average of 3 months. Larger
sized
containers, up to 25L pouches or even larger drums, may also be used to treat
larger sized water systems. More than four containers 42, 142 may also be
used,
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depending on the number of treatment products that are needed to treat the
issue of
a given water system.
[0047] Systems 10, 110 also allows for easy change-out of the treatment
products being used by simply disconnecting the tubing for one treatment
container,
removing the treatment container and replacing it with another having the same
or a
different product. This allows flexibility in systems 10, 110 to accommodate
larger
scale changes in the treatment requirements of the water system, which require

different treatment products. The use of preferred flexible pouches for
containers
42, or bottles 142, facilitate inventory control and ease of handling and
reduce waste
of the larger bucket or drum previously used with diluted treatment products;
however, larger container sizes may be used for larger systems, including
drums if
necessary, to meet demands of the water system being treated. Each pouch-type
container 42 preferably has a fitment designed to simplify connection to the
pump
feeder through ports 28 and minimize user contact with the treatment products.

Similarly, each container 142 allows for easy connection of tubing 144 to an
outlet
fitting on cap 145 and placement within pump mechanism 132 to minimize or even

eliminate user contact with the treatment products. Since feed rate of each
treatment product is based on feeder or pump 32, 132 activation time, most
preferably each container 42, 142 has coloration or a label that coordinates
with
coloration or a label on a component to which the container is to be
connected, such
as tubing 44a, 44b, 144a, 144b, pump tubing 30a, 30b, etc., tubing 46a, 46b,
etc. (if
used), port 34a, 34b, 134a, 134b, etc. to ensure that treatment products in
containers 42a, 42b, 142a, 142b, etc. are aligned with the proper pump 32a,
32b,
etc. or port or tubing so that each treatment product has the proper feed rate

according to the pre-programmed functions. Preferably, the color or label used
with
each set of components (e.g. pump tubing 30a) is different from each other set
of
components (e.g. pump tubing 30b, 30c). Other visual indicators, such as
patterns,
shapes, numbers, or writing, may also be used on these components or any
combination thereof to aid in aligning a pump or other feeder with the
container and
manifold port to which it should be connected.
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[0048] Most preferably, treatment products as one or two treatment
components or ingredients (single or mixtures of active ingredients with no
dilution)
would be packaged in neutralized form, to allow for transport of non-hazardous

materials and safer handling. Because the components are individually
packaged,
dilution with water and high pHs would not be required to maintain solution
solubility,
as may be required with pre-mixed compositions. The reduction in water,
caustic,
and other binder also reduces shipping weight by 50% or more, significantly
reducing shipping costs. This is particularly useful with certain types of
treatment
products. For example, polymers and phosphonates are stable at neutral pH's
(2.5
to 11) in high concentrations (35 to 60 % solids). Triazoles can be sourced in
glycol
solutions at 25 to 50 % solutions (propylene glycol, for example, is non-
hazardous
and safe for use in food plants). Phosphonates and triazoles are easily tested
in the
system to determine the level of treatment within the water system. Polymer
might
be mixed with tracers such as pyrene tetrasulfonic acid (PTSA) for on-line
testing
using a fluorimeter. All other components might be fed in ratio to the polymer
(as an
example) to achieve the desired treatment residuals. Components, such as
sulfites
are typical fed to boiler systems to maintain a prescribed residual based on
system
needs. Neutralization to a DOT non-hazardous weight might increase the weight
slightly. But most current formulas have enough sodium hydroxide added to
raise
the pH levels to over 12. Since triazole is added separately, the extreme pH
will not
be required to keep solutions homogeneous. The triazole may be sourced as a
propylene glycol solution. Additionally, a more effective triazole may be used
which
isn't as easily formulated with other components (such as butyl benzyl
triazole, or
chlorotriazole solutions). Although minimal dilution of the treatment products
is
preferred, they may be diluted with water or another suitable diluent if
desired.
[0049] Most commercially available formulated, pre-mixed water treatment
compositions are diluted to contain approximately 70% water, typically
requiring
shipment in large drum containers. By shipping individual components in
containers
42 in concentrated form, shipping weights are reduced to 25 to 50 % as shown
below:
[0050] Example 1: Cooling Water Treatment 1 (Chem-Aqua 31155)
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Package size: 47.9 pounds; 5-gallons
Contains: Triazole, 2 polymers, phosphonate, and a tracer.
Individual component weights: 14.2 pounds (29.6% of formula weight).
[0051] Example 2: Cooling Water Treatment 2 (Chem-Aqua 8500 MPT)
Package size: 50.4 #, 5-gallons
Contains: Triazole, polymer, phosphonate, Zinc as Zinc Sulfate, and a tracer
Individual component weights: 14.6 pounds (29% of formula weight).
[0052] PLC 14 or controller 114 is connected to each pump 32, 132 and
preferably to an optional conductivity meter (or other sensor) 22, and to
optional
sensor(s) 21. PLC 14 or controller 114 is also preferably connected to a
separate
control system for the water system, which is typically pre-existing and is
used to
control valves and other components of the water system, such as activating
blowdown or altering make-up water addition. This allows interaction between
the
treatment control system 10, 110 and the water system controller, to further
enhance
the overall control of the water system. PLC 14 or controller 114 may
optionally be
connected to other water system sensors (already existing in the water system
and
not sensors 21, 22 of system 10, 110) and such a connection is preferred if
system
10, 110 does not include that particular type of sensor as a sensor 21
upstream of
manifold 20, 120. Water system sensors may include inline fluorimeter, a pH
meter,
another conductivity meter (other than conductivity meter 22), water system
flow
meters (such as a bleed-off flow meter or a make-up water flow meter), and/or
an
ORP sensor or similar sensor to monitor oxidant level, to receive signals from
these
sensors or meters to indicate when certain treatment action should be taken
according to pre-programmed functions. For example, corrosion or scaling
sensors
may be used to adjust levels of chemical residuals to reduce corrosion or
scale
incidents. Alternatively, the water system controller may be (and likely
already is)
connected to those other sensors and meters and signals or measurements from
those sensors may be sent to PLC 14 or controller 114 from the water system
controller. PLC 14 or controller 114 also preferably has other telemetry
capability (if
not provided through connection to the water system controller), to send
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remote users via text, email, or to a remote computer monitoring station, to
allow a
user to review current treatment system status, and verify treatment levels
and
chemical inventory remotely. It also preferably allows a remote user to make
changes to the treatment program, alter calculation functions, modify various
calculation inputs, such as desired residual concentration levels for
individual
treatment products, and change timer durations to alter pumping time to meet
changing requirements of water chemistry, system needs, or the needs of the
customer account. PLC 14 or controller 114 may also be connected to an
optional
visible or audible alarm to alert users of an issue with treatment system 10,
110.
PLC 14 or controller 114 is also preferably capable of recording treatment
system
data, such as pumping time, conductivity readings, pH readings, etc., and/or
sending
such data to a remote computer or the water system controller for recording.
This
helps to demonstrate compliance with treatment protocols or regulations
established
by trade organizations (such as Association of Water Technologies, or Cooling
Tower Institute) and state or federal agencies for proper corrosion, scale,
and
microbial control (including legionella protocols).
[0053] PLC 14 or controller 114 activates each pump 32a, 32b, 32c, 32d, etc.
or pump mechanism 132a, 132b, 132c, 132d, etc. when it is time to inject the
treatment product corresponding to that pump and maintains the pump in an
active
state until a sufficient amount of that treatment product has been injected
into the
water system based on pre-programmed functions and/or pre-programmed feed
rates, which will vary based on pumping rate and water system needs.
Activation of
one or more pumps 32, 132 may be based on (1) a pre-programmed timer function
(to start and shut off each pump at predetermined time intervals to achieve
the
desired injection rate of treatment product); (2) a measurement from one or
more
water system sensors or sensors 21 (for example, if a pH measurement or
fluorimeter measurement is above or below a predetermined threshold or outside
of
a predetermined range of values, then the feed rate of one or more treatment
products (e.g. from container 42a or 142a) may be increased or decreased
according to pre-programmed calculation or comparison functions); (3) make-up
water feed rate; (4) bleed-off or blow-down rate; or (5) any combination
thereof.
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Preferably, there is a combination of pump rate/activation triggers used in
system
10. For example, a pump 32a or 132a may be activated or deactivated for a pre-
set
period of time based on a fluorimeter reading indicating a decrease in
treatment
level concentrations, a water meter reading indicating displacement of treated
water
with untreated or fresh water such that additional treatment needs to be added
to the
water system, or calculated system bleed rates.
[0054] Most preferably, pumps 32, 132 are controlled by a combination timer
functions, water system sensor measurements, measurements from sensor(s) 21,
and/or water meter measurements or a combination of measurements from multiple

water system sensors/flow meters and/or sensor(s) 21. For example, a pump
32a/132a may be set to pump treatment product from container 42a/142a on a
timed
basis, by activating the pump for one minute every hour. Pump 32a/132a may
also
be activated by PLC 14/controller 114 if a fluorimeter 21a (or a fluorimeter
in the
water system) sends a signal indicating a fluorimetric measurement is below a
pre-
determined threshold value or outside of a predetermined range of values, in
which
case pump 32a/132a is activated again. Calculated time intervals for
subsequent
pumps (32 b¨d/132b-c) may be based on the actual feed time of a first
treatment
component needed to achieve a desired concentration level in the water system
for
that component based on the fluorimeter reading and calculating ratio-based
feed
times for other components based on the desired concentrations of those
components according to pre-programmed functions (see the example calculation
below). The programming of PLC 14 or controller 114 may also preferably be
modified remotely, to adjust various inputs such as high or low threshold
values or
ranges or desired concentration levels in feed rate functions, adjust time
intervals,
and/or adjust calculated deviation and time values.
[0055] System 10, 110 allows the ratio of treatment components to be easily
adjusted, by activating and deactivating pumps 32a-32d or altering pump rate,
if the
treatment requirements of the water system change, such as if the makeup water

chemistry changes. PLC 14 or controller 114 preferably is capable of
calculating
treatment product feed rates for one treatment product based on a water system

sensor or sensor 21 reading for another treatment product component (a primary
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chemical). For example, a primary chemical could be controlled by fluorimetric
or
other means and the feed amounts for other treatment chemicals can be based
off
of that fluorimetric reading using ratios to calculate feed rates based on
desired
residual concentrations in the water system for each treatment chemical. A
variety
of functions (calculation formulas, desired concentration levels, and sensor
reading
or measurement parameters) for various water system scenarios/issues may be
pre-
programmed into PLC 14 or controller 114 to determine and implement real time
treatment product feeds needed to achieve desired treatment levels. The
following
are example calculations that may be used as part of the programmed functions
for
PLC 14/controller 114 to control pumps 32a-32d/132a-132c based on a timed
function, a sensor measurement function, or a flow meter function to achieve
the
desired concentration of a particular treatment product within the water
system.
[0056] Timed feed assumes a constant depletion of chemical and feeds at
pre-set time intervals to maintain chemical level. Timed feed is the least
accurate
control system, particularly since water system demands frequently change
which
increases or decreases the rate of treatment chemical consumption/depletion,
but is
still useful in controlling treatment product feed. For a 100 ton cooling
system, at
85% efficiency, there are 1836-gallons of bleed per day. To maintain chemical
feed
of a 100-ppm dose treatment, 1.53 lbs/day of treatment must be added to the
water
system. To maintain 2.9-ppm of a polymer fed from a 50% solution would require

0.056 lbs/day (or 31.24-ml/day) fed incrementally throughout the day. To
achieve
this feed rate using a 1.3 ml/minute pump rate, would require pump 32a be on
(activated) for 1.0012 minutes/hour (the "on-time"). For simplicity,
calculation of the
other times for various components of a multi-component treatment (such as
Chem-
Aqua 31155) would be based on the on-time for this chemical, ratioed to the
desired
component concentration and the components concentration. For component
concentrations of Chem-Aqua 31155, this would require an accumulated run time
of
5.31 minutes per hour assuming the components are fed sequentially.
[0057] As described earlier, the feed program could be determined using a
shipped, laboratory tested set of one or more water samples, and the results
from
these tests could be used to prescribe a feed program that would be
communicated
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either through standard communication and input into the controller or through
direct
modification using remote communication.
[0058] Water meter based feed monitors either the volume of the water
entering or leaving the system and feeds to treat the water volume bled or
displaced
(VB). If the meter is a on the makeup water (Vmw) line, the feed is based on
the
volume divided by the number of cycles (VB = Vmw/(Cycles)). If the meter is on
the
bleed line then feed is based on the meter reading. This type of control
assumes no
water leaves or enters by other routes; but it does (by cooling tower drift
and system
leaks) so feed rates are adjusted as the product level slips. Then chemical
feed
would be initiated after a number of water meter pulses. If a water meter on a

makeup water line pulsed every 10-gallons and for a system maintained at 4
cycles,
and the pump timers are set for every 10 pulses representing 100-gallons of
makeup
water, the 25-gallons of water was bled (100/4). Chemical feed would be timed
to
add treatment for 100 gallons (378 liters) of makeup. For a 50% polymer
solution
(Specific gravity @ 1.25) fed to maintain 2.9-ppm active, using a 1.3-
ml/minutes
pump 32 (as an example), 378-Lx2.9-mg/L/1.25g/m1/1000-mg/g/1.3m1/min/4cyc1e5
results in an on-time of 0.169-min (10.13 seconds). For
simplicity the other
component could be ratioed off the primary chemical. Or each component run
time
could be calculated for run times based on the set number of water meter
pulses. If
the water meter is on the bleed line, then for calculated cycles = 1. Assuming
that
the other components are ratioed off the primary component, the component
level in
the system can be traced. If this component is 10 % low, then the time
fed/feed
sequence can be increased 10%. Alternately if one of the other components is
low
and the primary component is adequate, the proportion of time it runs can be
adjusted.
These functions are pre-programmed into PLC 14 to allow it to
automatically calculate and initiate treatment feeds based on meter readings.
[0059] For fluorimeter based feed, a primary component could be fed until
the fluorimeter reading indicates the primary component has reached its target

concentration. The time required to meet the desired level is noted and used
to
calculate the feed times for other treatment components, such as a triazole,
based
on a ratio calculation. For example, if the primary component (polymer) was
fed 0.20
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minutes to reach the desired fluorimeter level equivalent of a 2.9-ppm polymer

residual concentration in the water system, then the feed time to achieve a
residual
concentration of a triazole of 4 ppm using a 40% active liquid triazole
product with a
specific gravity of -1.2 is calculated as follows:
[0060] 4-ppm TT x 50% Polymer x 1.25 Sp. G polymer = 1.80
40% TT Sol 2.9 ppm Polymer 1.20 Sp. G Triazole
[0061] Triazole feed time = 0.2[polymer feed time] X 1.80 = 0.36 minutes.
[0062] Based on this example, if the primary component fed for 0.2 minutes,
the Triazole component would feed 0.36 minutes. Other treatment components
could be calculated the same way and these functions programed into PLC 14 or
controller 114 to allow treatment feed times to be automatically calculated
and
initiated. The process is periodically repeated at pre-determined time
intervals or at
pre-determined triggers (such as a reading of another sensor 21 or a water
system
sensor or meter) to recalculate the feed time for the primary component and
adjust
the feed times for the other components.
[0063] PLC 14 or controller 114 preferably controls each pump 32, 132 so
that treatment product components from each container 42, 142 are fed
separately
(not simultaneously) or sequentially, which allows for treatment delivery
verification
using a sensor 22, preferably a conductivity meter. PLC 14 is configured to
receive
a signal from conductivity meter 22 indicating the conductivity level of the
water
passing through the meter. When a treatment product is injected through
manifold
20, the conductivity reading will change, which will indicate that the
treatment
product was injected. If the conductivity reading does not indicate that a
treatment
product has been injected when it was supposed to be, or that the proper
amount of
treatment product has been injected, PLC 14 may send an alert to a user
through
text, email, an alarm, or through a message sent to the water system
controller or a
remote computer monitoring station that treatment system 10 needs service to
correct a malfunction (such as a malfunctioning pump) or that a treatment
container
42 may be empty and need replacing. This functionality may also be
incorporated
into system 110 and controller 114. FIG. 7 shows a chart of conductivity
readings
from conductivity meter 22 of equivalent dilutions of treatment components fed
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ml/minute in 3 gpm and 6 gpm slip streams through manifold 20, showing that a
conductivity meter is effective at indicating whether treatment has been
injected and
whether the proper amount of treatment has been injected in accordance with
pre-
determined feed rate functions. This may be particularly beneficial in
allowing
treatment system users to be alerted to a potential problem and to take
remedial
action before the lack of treatment (or lack of sufficient treatment) actually
impacts
with water system.
[0064] Separate, sequential feeding of each treatment product also helps
avoid any inadvertent or undesired chemical interactions or incompatibilities
between different treatment components. Separate feeding of individual
treatment
chemicals also provides greater flexibility in adjusting the water system
treatment as
needed based on changes in water chemistry, local regulations, or
recommendations from consultants or engineers. As used herein, sequential
feeding refers to feeding one treatment product by itself and then feeding
another
treatment product by itself, etc. so that the products are not simultaneously
fed. The
sequential feeding of the second product may be immediately after the
conclusion of
feeding the first product (a continuous sequential feeding) or there may be a
time
lapse between concluding the feeding of one product and initiating the feeding
of
another product.
[0065] Most preferably, PLC 14 or controller 114 also has treatment product
inventory management capability. For example, a certain number of each
container
42a, 42b, 42c, 142a, 142b, etc. containing the desired treatment products may
be
ordered for a particular water system. The initial amount in each container
42, 142
(e.g. 5L) and, optionally, the number of containers for each treatment product

contained in the supply shipment may be programmed into PLC 14 or controller
114
(or the water system controller). Product inventory may be managed by PLC 14
or
controller 114 tracking the amount of treatment product injected from each
container
42a, 42b, 142a, 142b, etc., calculating when each treatment container 42, 142
will
be emptied based on current usage level and initial amount in the container,
and
sending a message to a remote user or the water system controller when the
available level of treatment product reaches a predetermined low-level
threshold, so
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that the container may be replaced or more closely monitored for replacement
when
emptied (or substantially emptied). PLC 14/controller 142 may also track the
number of replacement containers 42, 142 being used as compared with the
number
received in the last shipment of treatment product to provide a message or
alert that
available inventory of any given treatment product is below a predetermined
low
threshold, so that the supply may be re-ordered to ensure there will be
sufficient
replacement containers 42, 142 available when needed. A
small batch of
replacement containers 42, 142 for each treatment product may then be ordered
as
needed.
[0066] Alternatively, PLC 14 or controller 114 may automatically send a
replacement order to a predesignated supplier (or the replacement order may be

sent by the water system controller) for any depleted or near depleted
treatment
product, with or without alerting a remote user that inventory is low. By
using
smaller sized containers 42, 142, preferably with non-hazardous forms of
treatment
products, shipping costs will be reduced both by weight of the product and by
allowing use of non-hazardous shippers. In order to treat a 100 to 500 ton
cooling
system, for example, a case of 4 containers 42, 142 of 5L each would weigh
less
than 75 pounds (likely around 56 pounds), so the shipping costs would be
modest.
Larger systems might require a larger package size, as will be understood by
those
of ordinary skill in the art. Although it is preferred to not use large drum
(e.g. 55
gallon) size containers 42, 142 for ease of shipping, storage, and on-site
handling,
such larger containers may also be used with system 10, 110 by connecting the
container 42 to ports 28 on housing 12 or a similar port on housing 112.
[0067] Although one sensor 22 and four pumps 32, four manifold ports 34,
four containers 42, four sensors 21, and four connection ports 28 are shown
and
described with the preferred embodiments of treatment control system 10, other

numbers of these pieces of equipment may also be used. Similarly, although 3
containers 142, 3 pump mechanisms, and 4 manifold ports are shown and
described
with preferred embodiments of system 110, other numbers of pieces of equipment

may also be used. Most preferably, there is one pump, one manifold port, and
one
connection port for each container and there is one container for each
treatment
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product (individually or each multi-component treatment product) to be used
for a
particular water system. Most preferably, downstream sensor 22 is in close
proximity to the downstream side of the treatment product feeders (or manifold
20)
and upstream sensor(s) 21 is in close proximity to the upstream side of the
treatment product feeders (or manifold 20), to facilitate ease of connection
to PLC 14
and to provide protection for the sensors inside housing 12. However,
treatment
control system 10 may utilize pre-existing sensors in the water system for the

properties measured by sensors 21 and 22. System 110 may also be connected to
pre-existing sensors in the water system and utilize data from those sensors.
Any
component, feature, method, or functionality described with respect to system
10 or
110 may also be used with the other system, as will be understood by those of
ordinary skill in the art.
[0068] With respect to the AAP/HPA/other phosphonic acid treatment
products for corrosion, white rust, and scale treatment according to preferred

embodiment of the invention, several lab tests were run to test the
effectiveness of
these treatment products. The effectiveness of the AAP/HPA/other phosphonic
acid
treatment products according to the invention were evaluated using spinner
tests to
simulate flowing water over metal components in a water system. Each spinner
test
set-up comprises a stainless steel container of water with four metal coupons
(mild
steel coupons (C1010) and copper coupons (CDA 11) were used) suspended in the
water in each container from holders hanging from a rotating shaft. The shaft
rotates the coupons in the water in the stainless steel container at 147
rotations/min,
representing a flow rate of 3-5 ft/s, depending on coupon distance from center
of the
rotating shaft. The
initial volume of water used in each spinner test was
characteristic of corrosive, low hardness water typically found in water
systems. The
water used had the characteristics shown in Table 1 below.
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[0069] Table 1. Low hardness, corrosive water used in Spinner test
experiments
Characteristic Value Unit
pH 8 to 8.5
Conductivity 220 cP
Ca Hardness 30 ppm, (as CaCO3)
Mg Hardness 10 ppm, (as CaCO3)
Chlorides, Total 25 ppm Cl
M Alkalinity 30 ppm, (as CaCO3)
Sulfate, Total 28 ppm, as SO4
[0070] During each spinner test the water is aerated and maintained at
constant temperature of 120F and constant volume (any evaporation is
compensated with automatic addition of deionized water when water level drops
below sensor level). Standard test duration is 48 hours.
[0071] Using the spinner test set-up, AAP/HPA/other phosphonic acid
treatment products according to preferred embodiments of the invention
(Example
Nos. 1-3 including AAP, HPA, and another phosphonic acid - HEDP) without any
added zinc or tin (as shown in Table 2) were compared to treatments using only
zinc
(Comp. Ex. 4), only tin (Comp. Ex. 5), only AAP (Comp. Ex. 6), only HPA (Comp.
Ex.
7), HPA combined with tin (Comp. Ex. 8), and AAP combined with tin (Comp. Ex.
9)
(all as shown in Table 3) as the primary inhibitor(s). The ppm concentrations
of the
various treatments are concentrations when added to the volume of water in the

spinner test container. The treatments with zinc or tin were for comparison to
those
without. Zinc is typically used as corrosion inhibitor in water systems with
highly
corrosive water (low LSI). However its usage is undesirable due to toxicity
issues
and its use face regulations in some locations. Tin has been promoted and
patented
as a non-toxic alternative to zinc, but it is more expensive. In addition to
the primary
corrosion inhibitor components listed in Tables 2 and 3, all of the tests were
carried
out in the presence 4 ppm active AA/AMPS copolymer and 4 ppm active TTA.
These ingredients were added to the water in each spinner test set-up to
provide
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those concentration levels. In Examples 1 and 2, the AAP and HPA were
separately
added to the spinner test water and the other components (HDPE, AA/AMPS, TTA,
caustic) were pre-mixed before adding to the spinner test water. In Example 3,
all
ingredients were pre-mixed as a composition before adding to the spinner test
water.
In each of Comparative Examples 4-9, the inhibitor was added to the water in
the
spinner test separately from any other ingredients, but HEDP was premixed with

AA/AMPS, TTA, and caustic before adding to the water. The corrosion and
pitting
level for mild steel coupons after spinner tests in presence of different
inhibitors are
presented in Figure 8.
[0072] Table 2. Corrosion inhibitor treatment products according to the
invention
Inhibitor Unit Example 1 Example 2 Example 3
AAP (amino acid based ppm 7.5 5.2 5.2
polymer ¨ such as a active*
commercially available
water solution containing
about 40% of salt)
HPA ppm 2.5 5.0 5.0
(hydroxyphosphonoacetic active
acid)
HEDP ppm 3 3 3
active
MEA ppm 0.25 1.0
Zn (zinc) ppm N/A N/A N/A
active
Sn (tin) ppm N/A N/a N/A
active

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*ppm active refers to the amount of active raw material, in contrast to ppm
which
refers to the weight of raw material in mg/L. For example, HPA is commercially

available as a 50% water solution, so adding 10 ppm raw material will provide
5
ppm active HPA.
[0073] Table 3. Corrosion inhibitor treatment products ¨ Comparative
Examples
Inhibitor Unit Comp. Comp. Comp. Comp Comp. Comp.
Ex 4 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9
AAP ppm active 15 7.5
HPA ppm active 5 5
HEDP ppm active 3 3 3 3 3 3
M EA ppm
Zn ppm active 1
Sn ppm active 1 1 0.5
[0074] Spinner tests were run with each treatment at a flow rate equivalent to

around 3ft/second and at a flow rate equivalent to around 5ft/second. A
control test,
without any treatment was also carried out for comparison.
FIG. 8 shows
photographs of a representative mild steel coupon after each spinner test with
the
control and with Example Treatment Products Nos. 1-9. The amount of corrosion
and pitting on the coupons is shown in the photographs. As can be seen, the
control
coupons show extensive corrosion (dark areas on photographs). The coupons used

with treatment products according to preferred embodiments of the invention
(Ex.
Nos. 2-3) show little, if any, corrosion or pitting (very few dark areas on
photographs). The
coupons used with Ex. No. 1, which contains all three
components according to a preferred embodiment of the invention for corrosion
inhibition, but only contains 2.5 ppm HPA (less than the more preferred amount
of at
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least 3 ppm), shows improved results over the control and the comparative
examples (Comp. Nos. 4-9), but shows slightly more corrosion than Ex. Nos. 2-
3,
where 5 ppm of HPA was used. The coupons used with the comparative treatments
(Comp. Nos. 4-9) are significantly better than the control, but do show
evidence of
corrosion and pitting that is greater than with Ex. Nos. 1-3. Based on the
results, it
appears that the combination of AAP, HPA, and another phosphonic acid (in
these
examples, HEDP) interact synergistically to provide improved corrosion
control,
without requiring the use of zinc, tin or other regulated metals.
[0075] Some prior art water treatment corrosion inhibition treatments do not
provide effective protection when oxidizing biocides are used in the same
system to
prevent biological growth. The most widely used oxidizing biocides are
chlorine and
stabilized bromine. Additional spinner corrosion tests were carried out using
Example compositions Nos. 2 and 3 compared to comparative Example treatments
Nos. 4 (zinc only) and 7 (HPA only) in the presence of a stabilized bromine
biocide
composition (commercially available as Chem-Aqua 42171). Example treatments 4
and 7 were selected because they showed the best results in the spinner tests
of the
comparative examples. Both Comp. Ex. Nos. 4 and 7 perform fairly well in low
LSI
water, but as discussed below, significantly worse when biocide is added.
Also,
Comp. Ex. No. 4 is based on zinc, which is undesirable to use due to toxicity
concerns. As with the prior tests, these tests were carried out in presence 4
ppm
active AA/AMPS copolymer and 4 ppm active TTA. A slug dose of 40ppm of biocide

was added at the beginning of each spinner test (after the corrosion
inhibition
treatment products were added and the test started) to yield about 1ppm FHR
(free
halogen residue).
[0076] FIG. 9 shows photographs of a representative mild steel coupon after
each spinner test with the Example Treatment Products in the presence of
biocide.
As can be seen, the coupons used with treatment products according to
preferred
embodiments of the invention (Ex. Nos. 2-3) show little, if any, corrosion or
pitting,
indicating that the functionality of preferred products according to the
invention is not
negatively affected by a biocide. The coupons used with the comparative
treatment
products (Comp. Ex. Nos. 4 and 7) show substantially more corrosion than with
Ex.
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Nos. 2-3. It is noted that Comp. No. 7 was the use of HPA and HEDP, without
any
AAP, which showed good results without biocide, but significantly more
corrosion
occurred when a biocide was added. The comparative treatments having AAP and
HEDP, without any HPA, (Comp. Ex. No. 6) did so poorly without biocide (Fig.
8)
that it was not tested with biocide because the results would be expected to
be even
worse than in FIG. 8. Based on the results, it appears that the combination of
AAP,
HPA, and another phosphonic acid together interact synergistically to provide
improved corrosion control even in the presence of a biocide and show improved

results over the use of HPA alone.
[0077] Corrosion rates for the mild steel coupons were also measured and
calculated from weight loss of the coupons. The results of both the spinner
tests
without added biocide and with added biocide are summarized in Table 4.
Information on corrosion mode, particularly the presence of pitting (which is
important in many applications and some corrosion inhibitors, including HPA
used
alone, are known to be poor protectors against pitting), is also included in
Table 4.
Most preferably, corrosion inhibitor treatment products according to the
embodiments of the invention achieve corrosion rates of 3 MPY or less for
corrosion,
even in the presence of a biocide.
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[0078] Table 4. Corrosion Rates form spinner test experiments
Mild Steel Coupon Corrosion Rate, MPY [mil/yr]
Low Hardness Water +
Low Hardness Water
Biocide
Corrosion
Test 3ft/sec 5ft/sec 3ft/sec 5ft/sec Pitting
Pitting Scale
Control 370 243 N/A
Example 1 2.7 2.5 None
Example 2 2.9 2.4 None 2.2 2.0 None
Example 3 2.5 2.5 None 2.7 2.4 None
Sever
Comp. Ex 4 2.7 2.7 Limited 8.0 11
pitting
Comp. Ex 5 4.0 4.6 Pitting
Severe
Comp. Ex 6 13.6 8.2
pitting
Severe
Comp. Ex 7 2.6 3.2 Limited 6.4 5.7
pitting
Comp. Ex 8 3.9 5.2 Pitting
Comp. Ex 9 3.8 3.2 Sever pitting
Pitting scale description:
None = no pitting observed
Limited = few (1-5) pitts per coupon, usually very shallow
Pitting = significant number of pits on coupons (5-50)
Sever pitting = a large number of pits (> 50), usually dipper and larger
[0079] The AAP/HPA/other phosphonic acid treatment products according to
preferred embodiments of the invention contain organic phosphate from the HPA
and from the other phosphonic acid used in these examples (HEDP). In the
presence of a biocide, the organic phosphate is often reverted to
orthophosphate,
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which is not as good in preventing corrosion or scale and also may cause
issues
with forming calcium phosphate scale. When the combination of AAP,HPA, and
HEDP (or another phosphonic acid) is used as a corrosion inhibitor according
to a
preferred embodiment of the invention, virtually no reversion of organic
phosphate
to orthophosphate was detected. Samples from treatment product Example Nos. 2
and 3 and comparative Example No. 7 were tested for the presence of
orthophosphates upon mixing of the treatment products and again after 48
hours.
The results are listed below in Table 5. Example Nos. 2 and 3, which use AAP,
HPA, and HEDP (and contain AA/AMPS and TTA as noted above), showed very
little orthophosphate increase over the 48 hour period, but comparative
Example
No. 7 which contains HPA and HEDP (and contains AA/AMPS and TTA as noted
above), but no AAP, showed a substantial increase.
[0080] Table 5. Orthophosphate levels in low hardness test water in
presence of biocide during the spinner corrosion test
Orthophosphate (ppm PO4)
Test Initial 48hr (End of Test)
Example 2 0.4 0.5
Example 3 0.2 0.4
Comp. Ex -7 0.3 1.6
[0081] According to another preferred embodiment, water treatment products
as listed in Table 6 (which is the same as Ex. 2 tested above) are effective
at
inhibiting corrosion and scale in a water system over a broad range of LSI
values (-
2.5 to >3) and in the presence of a biocide. The percentages listed are
percentages
for use with a pre-mixed composition, rather than individual treatment
products
separately added to a water system, but preferred amounts and ratios for
separate
addition of each ingredient may be easily determined based on these amounts.

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[0082] Table 6.
Active %* in
Component Wt % Pre-
mixed
Composition
Sodium polyaspartate (AAP) 13.0 5.2%
as AAP
Hydroxy phosphonoacetic Acid (HPA) 10.0 5.0%
as HPA
1-Hydroxyethylidene 1,1-
diphosphonic acid (HEDP) 1.2-
3.0% as
5.25-6.4
or PO4
2-phosphonobutane-1,2,4,tricarboxylic acid (PBTC)
Monoethanolamine (MEA) (optional) 1.0 0.99%
Copolymer of acrylic acid and sulfonated monomer 3.9% as
8.78
(AA/AMPS)
AA/AMPS
Tolyltriazole (TTA) 9.40 4.0%
as TTA
1,3,6,8-Pyrenetetrasulfonic acid tetrasodium salt
1.00 1%
as PTSA
(PTSA)
15.00-
NaOH or KOH N/A
16.25
35.17-
Deionized water N/A
36.57
*Active % refers to active weight percent. Wt% is raw material weight percent.
Most
of the raw materials are aqueous solutions and contain only a certain amount
of
solids that is the actual chemical component. The amount of active (Active %)
is
calculated based on raw material weight percent and the amount of the chemical
in
the solution per the information provided by the supplier. For
example, a
commercially available source of AAP may be a 40% solution of AAP in water, so
if
13% of that product is used, the active amount of AAP equals: 0.13*0.401 00% =

5.2% of AAP (active) in the formula
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[0083] NaOH and/or KOH is preferably also added to the pre-mixed
composition according to an embodiment of the invention. These ingredients are

typically added to water treatment formulations in order to neutralize acid
and to
bring the pH of the final pre-mixed composition to the desired level. Most of
the pre-
mixed compositions will have pH > 8, some will have pH > 12. In pre-mixed
compositions where TTA is used (as with a preferred embodiment of a
composition
according to the invention) it is desirable to have higher pH (> 11) for the
composition in order to ensure solubility of TTA, which has very poor
solubility at
lower pH. Additionally, any individual treatment product may be neutralized,
such as
through the addition of NaOH or KOH in a container 42, 142 of the treatment
product, to make the treatment product non-hazardous for shipping and storage
purposes.
[0084] Additional spinner tests in low LSI water were carried out in order to
test the effectiveness of various concentrations of treatment products for
inhibiting
corrosion according to preferred embodiments of the invention. The same
spinner
test parameters and low LSI water (Table 1) described above were used for
these
tests. The concentrations of the ingredients when added to the spinner test
water
and the results of these tests are shown below in Table 7. Figure 10 shows
photographs of the test coupons (tested at a flow rate of 3 ft/sec) for each
treatment
after the test was completed.
[0085] Table 7 ¨ Additional Spinner Test Treatments & Results
Comp. Comp. Comp. Comp.
Inhibitor Unit Ex. 11 Ex. 12 Ex. 14 Ex. 16
Ex. 10 Ex. 13 Ex. 15 Ex. 17
PPm
AAP 2.6 5.2 7.8 5.0 10 10 5.0 5.0
active
PPm
HPA 2.5 5.0 7.5 2.5 5 2.5 5.0 5.0
active
AAP:HPA
51:49 51:49 51:49 67:33 67:33 80:20 51:49 51:49
Ratio
HEDP PPm 1.6 3.26 4.7 3.26 3.26 3.26
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Comp. Comp. Comp. Comp.
Inhibitor Unit Ex. 11 Ex. 12 Ex. 14 Ex. 16
Ex. 10 Ex. 13 Ex. 15 Ex. 17
active (1.5 (3 ppm (4.4 (3 ppm (3 ppm (3 ppm
ppm PO4) ppm P0.4) P0.4) PO4)
PO4) P0.4)
2.6
ppm (0.95
PBTC
active ppm
P0.4)
MEA ppm 0.5 1 0.5
TTA ppm TTA 4 4 4 4 4 4 4 4
AA/AMPS ppm
4 4 4 4 4 4 4 4
Copolymer active
Corrosion Results from Spinner Test (low LSI water), mild steel (C1010)
coupons at
3ft/sec flow rate
Corrosion MPY
5.2 2.3 1.5 3.1 2.2 3.5 2.1 3.3
Rate* (mil/yr)
Pitting Pitting none none none none none none None
* Average for 2
coupons from the same spinner test pot at 3 ft/sec
[0086] Comparative Examples 10, 13, and 15 use AAP, HPA, and HEDP but
in amounts less than the preferred concentrations. These examples show
increased
corrosion (and Comp. Ex. 10 showed moderate pitting) at low levels of the
inhibitors.
Example Nos. 11-12, 14, and 16 according to preferred embodiments of the
invention show good performance (low corrosion rate and no pitting) for
different
optional components and varying concentrations and ratios of AAP to HPA. The
examples also show that the change from HEDP to PBTC (Ex. 16) and reduction of

secondary chelates does not affect the corrosion inhibition performance of
treatment
products according to preferred embodiments of the invention. Example No. 17
used AAP and HPA, without a second phosphonic acid, similar to the composition

described in the '023 patent. It shows improved results in controlling
corrosion in
low LSI water, but the results are not as good as in the examples according to

preferred embodiments of the invention.
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[0087] Additional spinner tests were conducted to compare treatments using
AAP and PBTC as disclosed in the '023 patent with AAP/HPA/phosphonic acid
treatment products according to preferred embodiments of the invention. The
test
set-up was the same as described above using low LSI water, mild steel (C1010)

coupons, and a flow rate of 3 ft/sec. The results are shown in Table 8 below.
[0088] Table 8 ¨ Comparing Treatments Using One Phosphonic Acid to
Treatments Using Two Phosphonic Acids
Comp. Comp.
Example 12
Example 18 Example 19
Inhibitor Unit Example 20 Example 21 (same
as in
80:20 40:60
Table 7)
PBTC/AAP PBTC/AAP
PPm
PBTC 16 8 4.8 8
active
PPm
HEDP 4.7
active
PPm
AAP 4 12 7.8 4 7.8
active
PPm
HPA 7.5 8 7.5
active
PPm
TTA 4 4 4 4 4
TTA
AA/AMPS ppm
4 4 4 4 4
Copolymer active
Corrosion MPY
3.1 3.1 1.9 1.7 1.5
Rate* (mil/yr)
Pitting none none none none None
*Average for 2 coupons from the same pot at 3 ft/sec
[0089] As can be seen, the examples according to preferred embodiments of
the invention (Example Nos. 20, 21, and 12) with AAP, HPA, and a second
phosphonic acid (HEDP or PBTC) show much beter corrosion inhibition results
than
the comparatve examples using only AAP and PBTC (without any HPA). It is also
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noted that Comp. Ex. Nos. 18-19 resulted in corrosion rates greater than 3 MPY

even when using 20 ppm total inhibitor (AAP and PBTC), which is higher than
the
corrosion rate achievable with preferred treatment products according to the
invention using substantially less total inhibitor, such as Example No. 11,
which had
a corrosion rate of 2.3 MPY using only 13.5 ppm total inhibitors (AAP, HPA,
HEDP),
and Example No. 16, which had a corrosion rate of 2.1 MPY using only 12.6 ppm
total inhibitors (AAP, HPA, PBTC). Additionally, the corrosion rates of Comp.
Ex.
Nos. 18-19 are comparable to those in Comp. Ex. Nos. 13 and 15, which use AAP,

HPA, and a second phosphonic acid, but the total amount of inhibitor needed to

achieve the results in Comp. Ex. Nos. 18-19 (20 ppm total) is much higher than
that
needed in Nos. 13 and 15 (10.76 and 15.76 ppm total, respectively). The
results of
these experiments show that the addition of a second phosphonic acid, in
combination with AAP and HPA, provides an unexpected synergistic effect that
improves corrosion inhibition even when less total inhibitor is used and even
in the
presence of a biocide.
[0090] Those of ordinary skill in the art will understand that other sutiable
or
equivalent chemical compounds and other treatment compounds, including other
corrosion inhibitors, may be substituted for any of the above ingredients or
added to
any of the above ingredients within the scope of this invention.
AAP/HPA/phosphonic acid treatment products according to the embodiments of the

invention are effective in inhibiting corrosion on metal components in water
systems
over a broad range of LSI values, including LSI <0, and without requiring the
use of
regulated toxic metals. The AAP/HPA/phosphonic acid treatment products are
also
effective at higher pH values (7-9) typically found in water systems, such as
cooling
towers and boilers, whereas some prior art inhibitors are ineffective or their

effectiveness is reduced at such pH levels (for example, a polyaspartic
acid/stannous salt treatment is effective only at pH 5-7). The
use of
AAP/HPA/phosphonic acid treatment products according to the invention also
prevent reversion of organic phosphate to orthophosphate to maintain
effectiveness
in the presence of a biocide.

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[0091] Other experiments using an electrochemical method were conducted
to test AAP/HPA/phosphonic acid treatment products according to the invention
for
white rust prevention. The results in Table 9 below show synergistic effect of

combining HPA and AAP (without another phosphonic acid) in reducing white rust

formation as compared to use of each individual component (HPA alone and AAP
alone). The cyclic voltammetry test was conducted in 0.1M sodium carbonate
solution using zinc electrode. The measure of oxidation is the area under the
oxidation curve peak observed; the lower the area the less oxidation occurs,
meaning lower corrosion rate. The results are the averages of 6-10 experiments
with
standard deviation.
[0092] Table 9
Inhibitor Concentration Measure of Oxidation
[ppm active] [Coulombs*10-3]
AAP 50 1.2 0.2
HPA 50 1.0 0.1
AAP/HPA (1:1 ratio) 25: 25 0.8 0.1
[0093] Additional spinner corrosion tests were carried out in stainless steel
containers in high alkalinity water known to form white rust on galvanized
surfaces to
test the effectiveness of treatment products according to preferred
embodiments of
the invention for the prevention of white rust formation. The water chemistry,

characteristic of high alkalinity synthetic water, in these tests is detailed
in Table 10
below. Four Hot Dip Galvanized steel coupons (HDG G70) with dimensions
1.0x4.0x0.02in were installed in each container on the holders hanging from a
rotating shaft that rotates at 147 rotations/min that represents flow rate of
3-5 ft/s,
depending on coupon distance from center of the rotating shaft. During the
tests the
water was aerated and maintained at constant temperature of 120F and constant
volume (any evaporation was compensated with automatic addition of DI water
when the water level dropped below a sensor level). Standard test duration was
48
hours. The active ingredients used in two comparative examples and three
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examples of preferred treatment products according to the invention, along
with
corrosion rates, are listed in Table 11.
[0094] Table 10 - High alkalinity/no hardness water used in Spinner test
experiments for white rust prevention
Characteristic Value Unit
pH 8.7-8.9
Conductivity 2300 cP
Ca Hardness 0 ppm, (as CaCO3)
Mg Hardness 0 ppm, (as CaCO3)
Chlorides, Total 250 ppm Cl
M Alkalinity 200 ppm, (as CaCO3)
Sulfate, Total 500 ppm, as SO4
[0095] Table 11 - Active Ingredients and Galvanized Coupon Corrosion Rate
Inhibitor Unit Comp. Ex. Comp. Ex. 24 Ex. 25 Ex. 26
22 - No Ex. 23
Inhibitor
AAP ppm 15 7.5 15
active
HPA ppm 7.5 7.5 2.5
active
HEDP ppm 3.26 3.26 3.26 3.26
active (3 ppm (3 ppm (3 ppm (3 ppm
PO4) p04) p04) p04)
TTA ppm TTA 4 4 4 4
AA/AMPS ppm 4 4 4 4
Copolym active
er
Corrosion Results- Galvanized Coupons (HDG G70)
Corrosion MPY
53.7 24.3 9.9 14.0 10.7
Rate* (mil/yr)
47

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*Average for 4 coupons from the same pot (two at 3 ft/sec and two at 5 ft/sec
flow rate)
[0096] In order to calculate the corrosion rate using the weight loss method,
the galvanized coupons from these tests were cleaned according to standard
procedure by immersing coupons in concentrated ammonium acetate and rinsing.
FIG. 11 shows photographs of the galvanized coupons after the spinner tests
with
the treatment products described in Table 12, both before and after cleaning.
The
white deposit visible on the coupons before cleaning is white rust. The damage
of
the galvanized layer due to corrosion, shown as dark spots, is visible on the
coupons
after cleaning. The blank (Comp. Ex. 22 ¨ No Treatment) coupon was completely
covered in white deposit and after cleaning most of the galvanized layer was
removed with visible mild steel corrosion. The coupon treated with HPA and
HEDP
without an amino-acid based polymer (Comp. Ex. 23) showed substantial white
rust
formation, but was still a great improvement over the control (Comp. Ex. 22).
Significantly better results were obtained with treatment products in Examples
24-26.
The best results were achieved with Ex. 24 using AAP, HPA at greater than 3
ppm,
and a second phosphonic acid (HEDP). Although the use of HPA is important in
inhibiting mild steel corrosion, its use is optional for white rust treatment.
As can be
seen from Example 26, the results of using AAP and HEDP without HPA were
almost as good as the three combined. Accordingly, a preferred pre-mixed
composition for treating white rust according to the invention comprises 2-15%

amino-acid based polymer, 0-10% HPA, and 0-10% of a second phosphonic acid.
Preferably, the amount of active amino-acid based polymer in a treatment
product
according to the invention is at least 3ppm, more preferably 3 ppm ¨ 50 ppm,
and
most preferably 5 ppm ¨ 30 ppm, all as initial concentrations when added to
the
volume of water in the water system being treated. More preferably, the AAP is

used in conjunction with HPA in an amount of at least 3 ppm, more preferably
from 3
ppm - 50 ppm, and most preferably from about 3 ppm - 20 ppm and/or another
phosphonic acid in an amount of at least 2 ppm more preferably from 2 ppm- 20
ppm, and most preferably from about 2 ppm - 10 ppm.
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[0097] For treating white rust according to the invention, it is preferred to
use
both hydroxyphosphonoacetic acid and an amino-acid based polymer, and more
preferably in conjunction with a second phosphonic acid, in the weight range
amounts indicated above, but it has also been found that the use of an amino-
acid
based polymer or hydroxyphosphonoacetic without the other is beneficial at
inhibiting white rust.
[0098] A pilot cooling tower scale test using AAP/HPA/phosphonic acid
treatment products according to a preferred embodiment of the invention was
also
conducted to test the ability to inhibit scale formation in high LSI water
(LSI >1). The
objective of the cooling tower scale test was to determine the number of
cycles at
which the tower can operate without scaling and the LSI limit of treatment in
typical
water with scaling characteristics as it cycles up. The cooling tower pilot
test used 4
heat transfer surface rods and a DATS (Deposit Accumulation Testing System)
operating at 800 Watts. The number of cycles of concentration (COC) is
calculated
as the ratio of concentration of any ions in the cooling tower water to the
concentration of the same ion in makeup (starting) water. Conductivity ratio
can also
be used to calculate COC. It is desirable to operate at as high COC as
possible to
reduce water usage. Typically, the COC in a cooling tower is maintained at a
certain
level by measuring water conductivity, bleeding the system when conductivity
increases over a set limit and adding more makeup water. The initial volume of

water used in the cooling tower pilot test was characteristic of high LSI
water having
100 ppm alkalinity as CaCO3 and 100 ppm calcium hardness as CaCO3 typically
found in cooling tower water systems. The water used had the characteristics
shown in Table 12 below.
49

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[0099] Table 12. High LSI water used in Pilot Cooling Tower Scale Test
Characteristic Value Unit
pH 8
Conductivity 450-520 IAS
Ca Hardness 100 ppm, (as CaCO3)
Mg Hardness 30 ppm, (as CaCO3)
Chlorides, Total 71 ppm Cl
Total Alkalinity 100 ppm, (as CaCO3)
Total Hardness 130 ppm, (as CaCO3)
Sulfate, Total 30 ppm, as SO4
LSI at 60 C 1.1
[00100] Scale is indicated when the HTR (Heat Transfer Resistance)
suddenly increases above stable level and exceed 12x10-6 Cm2/W and/or heater
%
clean drops below 97% (as determined from the Heater Transfer coefficient
fouled
(UF) and clean (UC) values, where UF = 1/HTR Scaled+ UC and % Cleanliness =
UF/UC x 100). The LSI limit (the LSI measurement at which scale will form) can

also be determined by monitoring changes in water chemistry, water turbidity
and
visually by observing scale formation. A pre-mixed AAP/HPA/phosphonic acid
composition according to Table 6 at a concentration of 100 ppm (when added to
the
water in the pilot cooling tower system) was found to increase the operational
limit of
cooling tower to 6 COC and LSI of 3.2 based on HTR and water chemistry data.
The pilot cooling tower was operated for 7 days before scale began forming.
The
test was started with high scaling water, LSI around 1, and was cycled up to 6
COC,
which increased LSI to 3.2 before scale began to form.
[00101] For comparison, a typical prior art scale treatment, such as Chem-
Aqua 31155 (which contains PBTC, sodium tolytriazole, sodium polyacrylate,
polymaleic acid (sodium salt) and sodium hydroxide), at the same 100 ppm
concentration allows to operate cooling tower only 3 COC that is at LSI limit
of only
2.6. Even at double the treatment concentration (200 ppm) of Chem-Aqua 31155,

CA 03088751 2020-07-16
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the COC in cooling tower can only be increased to 3.4, with LSI limit of 2.85,
which
is well under the COC increase and LSI limit achieved using a preferred
embodiment
of the treatment products of the invention. In another experiment using the
same
treatment products used in the previous pilot cooling tower scale test at 50
ppm
(when added to the water in the pilot cooling tower system), the system
reached 4.3
COC and LSI of 2.84 before scale began to form. These results further indicate
that
this three component formula is far better at scale prevention that prior art
formulas
containing PBTC, even when the prior art formulas are used at 2 to 4 times the

concentration. With AAP/HPA/phosphonic acid treatment products according to
the
invention, water in the water system (such as a cooling tower) may be
cycled/recirculated more times before scale formation begins compared to prior
art
treatments. This provides substantial savings on water, since there will be
less
blow-down and less make-up water added to the water system.
[00102] According to one preferred method of preventing corrosion of metal
components and/or white rust on galvanized steel components and/or mineral
scale
formation in a water system, AAP/HPA/phosphonic acid treatment products
according to the invention as described above are contained in containers 42a,
42b,
42c (with any other optional or other treatment products in additional
containers 42)
of delivery and control system 10. System 10 adds each of these treatment
products to the water system at an effective feed rate.
[00103] For corrosion and white rust inhibition, one or more of the AAP,
HPA, and another phosphonic acid as described above are fed into the water
simultaneously or substantially simultaneously at an effective total feed rate
of
20ppm - 600 ppm, or more preferably 100 ¨ 300ppm, depending on the treated
water chemistry and the amount of optional components also added. Preferably,
a
sufficient amount of is the AAP/HPA/phosphonic acid treatment products are
added
by system 10 to the water system to provide effective active amounts of one or
more
of the three treatment components (depending on whether white rust is being
treated
or both corrosion and white rust) of at least 3 ppm AAP, at least 3 ppm HPA,
and at
least 2 ppm of another phosphonic acid, each as initial concentrations when
added
to the volume of water in the water system being treated. More preferably, the
51

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AAP/HPA/phosphonic acid treatment products are added by system 10 in
sufficient
amounts to provide effective active amounts one or more of the components of
between 3 ppm ¨ 50 ppm AAP, between 3pm ¨ 50 ppm HPA, and between 2 ppm -
20 ppm of another phosphonic acid when added to the water in the water system.

Most preferably, these effective active amounts are 5ppm ¨ 30 ppm AAP, 3 ppm ¨

20 ppm HPA, and 2 ppm - 10 ppm other phosphonic acid when added to the water
in the water system. For treating white rust, the use of HPA is optional, so
system
may not include a container 42 of HPA or may include a container 42 of HPA but

be programmed to not add it to the water system each time AAP is added, only
added AAP in amounts sufficient to provide the above concentration ranges of
AAP
in the water of the water system being treated.
[00104] For scale inhibition, one or more of the AAP, HPA, and another
phosphonic acid as described above are fed into the water by system 10
simultaneously or substantially simultaneously at an effective total feed rate
of
20ppm - 600 ppm, or more preferably 50 ¨ 300ppm, depending on the treated
water
chemistry and the amount of optional components that may be added along with
the
AAP/HPA/other phosphonic acid treatment products. Preferably, a sufficient
amount
of AAP/HPA/phosphonic acid treatment products are added to the water system to

provide effective active amounts of one or more of the three treatment
components
of at least 2 ppm AAP, at least 2 ppm HPA, and at least 1.5 ppm of another
phosphonic acid, each as initial concentrations when added to the volume of
water
in the water system being treated. More preferably, the treatment products are

added in a sufficient amount to provide effective active amounts of the three
treatment components of 2 ppm - 50 ppm AAP, 2 ppm - 50 ppm HPA, and 1.5 ppm -
ppm of another phosphonic acid, each as initial concentrations when added to
the volume of water in the water system being treated. Most preferably, the
treatment products are added by system 10 in a sufficient amount to provide
effective active amounts of the three components of between 3 ppm ¨ 30 ppm
AAP,
between 2pm ¨20 ppm HPA, and between 1.5 ppm - 10 ppm of another phosphonic
acid when added to the water in the water system
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[00105] According to another preferred embodiment, (for treating corrosion,
white rust, and/or scale) a fluorescent tracer is included with one of the
AAP/HPA/phosphonic acid treatment products so that the level of that treatment

product in the water system can be measured and monitored. A fluorescent
tracer
may also be a separate treatment product in its own container 42 added
simultaneously with one or more of the AAP/HPA/phosphonic acid treatment
products. Additional amounts of the AAP/HPA/phosphonic acid treatment products

are added to the water system as needed, based on the tracer measurements, to
maintain an effective amount of treatment within the water system.
[00106] All ppm concentrations of the various treatments in the example
tests described herein are concentrations when added to the water in the
spinner
test, to correlate to the concentrations when added to the water in the water
system
being treated. Unless specifically excluded, all references to acids herein
and in the
claims include water soluble salts of the acid, as will be understood by those
of
ordinary skill in the art.
[00107] References herein to calculating or measuring a value, parameter,
or property and the like are intended to include any form of direct
measurement,
converting data or a signal, making a calculation based on one or more data
points
or signals, or otherwise comparing, interpreting, correlating, or manipulating
one or
more data points or signals. Those of ordinary skill in the art will also
appreciate
upon reading this specification and the description of preferred embodiments
herein
that modifications and alterations to the device may be made within the scope
of the
invention and it is intended that the scope of the invention disclosed herein
be
limited only by the broadest interpretation of the appended claims to which
the
inventors are legally entitled.
53

Representative Drawing
A single figure which represents the drawing illustrating the invention.
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Administrative Status

Title Date
Forecasted Issue Date Unavailable
(86) PCT Filing Date 2019-01-22
(87) PCT Publication Date 2019-09-06
(85) National Entry 2020-07-16
Examination Requested 2022-08-16

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None
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