U.S. patent number RE28,553 [Application Number 05/491,384] was granted by the patent office on 1975-09-16 for method for inhibiting corrosion and mineral deposits in water systems.
This patent grant is currently assigned to Henkel & Cie GmbH. Invention is credited to Helmut von Freyhold.
United States Patent |
RE28,553 |
von Freyhold |
September 16, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Method for inhibiting corrosion and mineral deposits in water
systems
Abstract
Addition to a water system a composition comprising a compound
having the following formula ##EQU1## wherein X is OH or NH.sub.2,
and R is alkyl radical of 1 to 5 carbon atoms; And a water soluble,
complex-forming compound which contains at least one .[.phosphonate
or.]. N-dimethylenephosphonic acid .Iadd.or -phosphonate
.Iaddend.group. Water-soluble salts of the first-mentioned compound
can also be used. Relative amounts of the compounds in the
composition varies from a molar ratio of from 1:3 to 3:1,
respectively. Amount of the composition to be used in water may
vary from 1 mg/liter and up to 150% of the quantity of composition
necessary for substantially completely converting into complexes
the substances imparting hardness to the water.
Inventors: |
von Freyhold; Helmut
(Dusseldorf, Oberkassel, DT) |
Assignee: |
Henkel & Cie GmbH
(Dusseldorf-Holthausen, DT)
|
Family
ID: |
27430705 |
Appl.
No.: |
05/491,384 |
Filed: |
July 24, 1974 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
821487 |
May 2, 1969 |
|
|
|
Reissue of: |
821487 |
May 2, 1969 |
03723333 |
Mar 27, 1973 |
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Current U.S.
Class: |
252/175; 210/700;
422/15; 510/469; 252/180; 510/531 |
Current CPC
Class: |
C23F
11/1676 (20130101); C23F 11/08 (20130101); C02F
5/145 (20130101) |
Current International
Class: |
C23F
11/167 (20060101); C23F 11/08 (20060101); C02F
5/14 (20060101); C23F 11/10 (20060101); C02F
5/10 (20060101); C23F 011/18 () |
Field of
Search: |
;252/175,180,82,87,181,387,389,390 ;21/2.7 ;210/50,59 ;260/502.4
P./ ;260/502.5 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Kyle; Deborah L.
Attorney, Agent or Firm: Hammond & Littell
Parent Case Text
PRIOR APPLICATION
This application is a streamlined continuation of copending,
commonly assigned application Ser. No. 821,487 field May 2, 1969,
now abandoned.
PRIOR ART
Readily or sparingly soluble polymeric phosphates, such as
tetrasodium pyrophosphate, pentasodium tripolyphosphate or
hexametaphosphate, are generally pentasodium tripolyphosphate
preventing corrosion and mineral depositions. The polymeric
phosphates are usually added in less than the stoichiometric
amounts. Stoichiometric amounts may, of course, be used in order to
completely bind, in the form of complexes, the substances, such as
the alkaline earth ions which impart hardness to water. The
polymeric phosphates may also be used in order to solubilize
precipitated complexes.
One disadvantage of these polymeric phosphates is their low
resistance to hydrolysis, i.e., the conversion to orthophosphates,
which takes place relatively quickly at elevated temperatures. For
instance, in the temperature region above 60.degree.C., where the
danger of mineral deposition is particularly great, the activity of
the otherwise very suitable polymeric phosphates is, at least
temporarily, almost completely inhibited.
It is also known that certain phosphonic acids, such as for
example, hydroxyethane-1, 1-diphosphonic acid or
amino-tri-(methylenephosphonic acid), are good complex-forming
compounds. Such compounds do not hydrolyze at the temperature in
question and may also be used as complex-forming compounds in less
than the stoichiometric amounts. Since these compounds have no
corrosion-inhibiting effect, however, they hinder any formation of
a protective layer, which again can give rise to corrosion by
carbon dioxide or oxygen. If other inhibitors having
corrosion-inhibiting effects are added, such as potassium, sodium
or ammonium orthophosphates, and/or water-soluble zinc salts,
satisfactory results are not obtained, since these additives easily
precipitate under the operating conditions.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a method for
treating water in order to inhibit corrosion and mineral
deposition.
Another object of the invention is the treatment of water systems
for inhibiting formation of broiler scale.
A further object of this invention is the treatment of a water
system to inhibit corrosion and mineral deposition with a
composition comprising a compound of the following formula:
##EQU2## and a water soluble, complex-forming compound which
contains at least one .[.phosphonate or.]. N-dimethylenephosphonic
acid .Iadd.or -phosphonate .Iaddend.group. X in above formula is OH
or NH.sub.2 and R is an alkyl radical of from 1 to 5 carbon atoms.
Amount of the compounds in said composition varies from a mole
ratio of 1:3 to 3:1.
A still further object of this invention is the treatment of a
water system to inhibit corrosion and mineral deposition with a
composition which does not form precipitates under operating
conditions.
DESCRIPTION OF THE INVENTION
The present invention relates to the treatment of hot water systems
for prevention of corrosion and mineral depositions, especially for
prevention of deposition of boiler scale.
The herein method described for the prevention of corrosion and
mineral deposition in a water system comprises adding to the water
used in the system a compound of the formula I ##EQU3## in which X
is OH or NH.sub.2 and R is an alkyl radical with 1 to 5 carbon
atoms; and a water-soluble, complex-forming compound which contains
at least one N-dimethylenephosphonic acid or -phosphonate group.
The compound of formula I and the water-soluble, complex-forming
compound are used in the molar ratio of 1:3 to 3:1, and in an
amount of from 1 mg per liter of water up to 11/2 times the
quantity which is necessary for substantially completely converting
into complexes the substances imparting hardness to the water
system. Water-soluble salts of the compound of formula I are also
suitable as substitutes thereof.
Examples of compounds of formula (I) are hydroxyalkane-1,
1-diphosphonic acids such as hydroxyethane-, hydroxypropane-,
hydroxybutane-, hydroxypentane- and hydroxyhexane-1,1-diphosphonic
acids; or aminoethane-, aminopropane-, aminobutane-, aminopentane-
and amino-hexane-1,1-diphonsphonic acids. Instead of the acids, the
water-soluble salts, preferably the alkali metal salts, may also be
used. The sodium and potassium salts, which can be easily prepared,
are especially suitable.
Water-soluble complex-forming compounds, which contain at least one
N-dimethylenephosphonic acid group, are compounds of formula II
##EQU4## in which, n represents an integer of from 1 to 6, and
preferably from 4 to 6. Of this group,
hexamethylenediaminotetraphosphonic acid is particularly suitable.
Instead of the phosphonic acids, the water-soluble salts, such as
the sodium and potassium salts may also be used. In particular,
however, preferred water-soluble, complex-forming compounds are
those which correspond to formula III ##EQU5## in which, R.sub.1
and R.sub.2 which may be same or different, represents a
(--PO.sub.3 H.sub.2) group, or the formula ##EQU6##
Examples of above-mentioned compounds are
aminotri(methylenephosphonic acid),
ethylenediaminotetra(methylenephosphonic acid), and
diethylenetriaminopenta(methylenephosphonic acid). Instead of the
acids, the corresponding water-soluble salts, such as sodium and
potassium salts, may also be used. Furthermore, mixtures of the
various compounds mentioned above may also be used, if desired.
A preferred embodiment of the process employs mixtures of
hydroxyethane-1,1,diphosphonic acid and
aminotri(methylenephosphonic acid), or their water-soluble salts,
as complex-forming compounds, the said components being present in
the molar ratio of 1:3 to 3:1. The addition to water is effected in
the previously stated amounts of from 1 mg per liter to 11/2 times
the amount which is necessary for the complete formation of the
complexes of the hardness-imparting substances present in the
system. In practice, quantities of 2 to 20 mg per liter are
generally used.
Other conventional inhibitors which can be added to hot water
systems are water-soluble orthophosphates, of the type previously
mentioned, such as mono-, di- or trialkali metal phosphates. In
many cases, it is advantageous to use sodium dihydrogen phosphate
(NaH.sub.2 PO.sub.4). Furthermore, water-soluble zinc salts, such
as zinc sulphate or zinc nitrate may be added instead of the
orthophosphates, however, preferably together with the alkali
orthophosphates. Further inhibitors, which may also be used if
desired, are alkali metal nitrites, such as potassium or,
especially sodium nitrite. An addition of alkali metal silicates,
such as potassium or sodium silicate, may also be made. The
inhibitors are added in amounts from 0.5 to 500 mg, and preferably
from 1 to 100 mg per liter. These inhibitors may be added in the
solid or solution form. There is no difficulty in adding these
products while simultaneously regulating pH of the water which is
being treated in case this is desired or necessary, either by
further addition of alkali or by a choice of a suitable mono-, di-
or tri-alkali metal phosphate.
The advantages of the method reside in that no hydrolysis of the
complex-forming compounds occurs and therefore, the agents are
active for a very long duration. Furthermore the combination with
the other components and the complex-forming compounds enables the
desired formation of a protective layer to take place. The
premature precipitation of the inhibitors, such as phosphates and
zinc salts, in the pH range from 7 to 10, does not take place.
Claims
I claim:
1. A method for inhibiting corrosion and mineral deposition in a
water system comprising the steps of adding to said water system
from 1 mg./liter of said water up to 11/2 times the quantity which
is necessary for substantially completely converting into complexes
the substances imparting hardness to said water, of a composition
comprising a first compound selected from the group consisting of a
diphosphonic compound of the formula ##EQU7## wherein X is OH or
NH.sub.2, and R is an alkyl of 1 to 5 carbon atoms, water soluble
salts of said diphosphonic compound, and a mixture of said
diphosphonic compound and said water-soluble salts thereof; and a
second compound selected from the group consisting of
water-soluble, complex forming compounds containing at least one
radical selected from the group consisting of .[.phosphonates
and.]. N-dimethylenephosphonic acid radicals, water soluble salts
thereof and mixtures of said compounds and their water soluble
salts; said first and second compounds are present in said
composition in molar ratio of from 1:3 to 3:1 and from 0.5 to 500
mg./liter of water of an inhibitor selected from the group
consisting of (A) water-soluble orthophosphates, water soluble zinc
salts and mixtures thereof and (B) alkali metal silicates, alkali
metal nitrites, and mixture thereof.
2. Method of claim 1 wherein said second compound is selected from
the group consisting of compounds having the following formulas:
##EQU8## wherein n represents an integer from 1 to 6; and R.sub.1
and R.sub.2, which can be the same or different, represent a
radical selected from the group consisting of (--PO.sub.3 H.sub.2)
and ##EQU9##
3. Method of claim 2 wherein n is an integer from 4 to 6.
4. Method of claim 2 wherein amount of said composition added to
said water is from 2 to 20 mg./liter. .[.5. Method of claim 2
wherein said composition is added to said water in the amount of 2
to 20 mg./liter..].
. Method of claim 2 wherein said composition also includes 1 to 100
mg./liter of water of an inhibitor selected from the group
consisting of disodium hydrogen phosphate, zinc sulfate, zinc
nitrate, potassium
nitrite, sodium nitrite, and mixtures thereof. 7. The method of
claim 1 wherein the first compound is selected from the group
consisting of 1-hydroxyethyane-1,1-diphosphonic acid, water-soluble
salts thereof and mixtures of said acid and its water-soluble salts
and the second compound is selected from the group consisting of
amino tri(methylene phosphonic acid), water soluble salts thereof
and mixtures of said acid and its water
soluble salts. 8. Method of claim 1 wherein said inhibitor is
present in
an amount of 1 to 100 mg./liter of water. 9. A composition for
inhibiting corrosion and mineral deposition in water systems
comprising a first compound selected from the group consisting of a
diphosphonic acid of formula ##EQU10## wherein X is selected from
the group consisting of OH and NH.sub.2 and R is an alkyl of 1 to 5
carbon atoms, water soluble salts thereof and mixtures of said acid
and its water soluble salts and a second compound selected from the
group consisting of water-soluble, complex forming compounds
containing at least one member selected from the group consisting
of .[.phosphonates and.]. N-dimethylenephosphonic acid radicals,
water soluble salts thereof and mixtures of said compounds and
their water-soluble salts; said first and second compounds are
present in said composition in molar ratio of from 1:3 to 3:1; and
an inhibitor selected from the group consisting of (A)
water-soluble orthophosphates, water-soluble zinc salts, and
mixtures thereof and (B) alkali metal
silicates, alkali metal nitrites, and mixtures thereof. 10. A
composition for inhibiting corrosion and mineral deposition in
water systems comprising a first compound selected from the group
consisting of 1-hydroxyethane-1,1-diphosphonic acid, water-soluble
salts thereof and mixtures of said acid and its water-soluble
salts; a second compound selected from the group consisting of
amino tri(methylene phosphonic acid), water-soluble salts thereof
and mixtures of said acid and its water-soluble salts, said first
and second compounds being present in said composition in molar
ratio of 1:3 to 3:1; and an inhibitor selected from the group
consisting of (A) water-soluble orthophosphates, water-soluble zinc
salts and mixtures thereof and (B) alkali metal silicates,
alkali
metal nitrites and mixtures thereof. 11. A composition for
inhibiting corrosion and mineral deposition in water systems
comprising a first compound selected from the group consisting of
1-hydroxyethane-1,1-diphosphonic acid, water soluble salts thereof
and mixtures of said acid and its water-soluble salts, a second
compound selected from the group consisting of amino
tri(methylenephosphonic acid), water-soluble salts thereof and
mixtures of said acid and its water-soluble salts and as a third
compound disodium hydrogen phosphate, said first and second
compounds being present in said composition in molar
ratio of from 1:3 to 3:1. 12. A composition of claim 11 which
includes an inhibitor selected from the group consisting of
water-soluble
orthophosphates, water-soluble zinc salts and mixtures thereof. 13.
A method for inhibiting corrosion and mineral deposition in a water
system comprising the steps of adding to the water system from 1
mg./liter of said water up to 11/2 times the quantity which is
necessary for substantially completely converting into complexes
the substances imparting hardness to water, of a composition
comprising a first compound selected from the group consisting of
1-hydroxyethane-1,1-diphosphonic acid, water-soluble salts thereof
and mixtures of said acid and its water-soluble salts; a second
compound selected from the group consisting of amino tri(methylene
phosphonic acid), water soluble salts thereof and mixtures of said
acid and its water soluble salts, said first and second compounds
being present in said composition in molar ratio of 1:3 to 3:1; and
from 0.5 to 500 mg./liter of water of an inhibitor selected from
the group consisting of (A) water-soluble orthophosphates,
water-soluble zinc salts and mixtures thereof and (B) alkali metal
silicates, alkali metal
nitrites, and mixtures thereof. 14. The method of claim 13 wherein
the
amount of said composition added to said water is 2 to 20
mg./liter. 15. The method of claim 14 wherein the composition
includes 1 to 100 mg. of disodium hydrogen phosphate.
Description
In the following Examples, the percentages are on weight basis, in
absence of other designation.
EXAMPLE I
Iron sheets of dimensions 100 .times. 50 .times. 0.5 mm were
suspended in 1 liter of water containing the particular additive,
amount of which is indicated in the table below. The water had a
total hardness of 14.3.degree. (German hardness), pH of 6.9,
carbonate hardness of 8.7.degree. (German hardness), oxygen at 5.33
mg per liter, corrosive carbonic acid at 8.44 mg per liter, and
chloride ions at about 190 mg per liter. The temperature was
maintained at 80.degree. C. The solution which was renewed every 6
hours, was moderately agitated by stirring. After 24 hours, the
sheets were examined and their deposit of rust and change in weight
were compared. The results are tabulated below: The abbreviations
used are ATMP (for aminotri-(methylenephosphonic acid), and HEDP
for hydroxyethane-1,1-diphosphonic acid in the form of its disodium
salt. The experiments were repeated several times.
__________________________________________________________________________
No of Amount Additive Result expt. mg/liter
__________________________________________________________________________
1 500 Na.sub.2 HPO.sub.4 with decreasing phosphate concentration
during the experiment, there was increasing corrosion, pitting
considerable erosion. Loss in wt., 80 to 160 mg/100 cm.sup.2. 2 6
ATMP Erosion of the metal without rust deposition. Loss in wt., 20
to 60 mg/100 cm.sup.2. 3 60 ATMP Considerable erosion without rust
deposition. Loss in wt., >100 mg/100 cm.sup.2. 4 10 HEDP Erosion
of the metal without rust deposition. Loss in wt., 20 to 60 mg/100
cm.sup.2. 5 100 HEDP Considerable erosion without rust deposition.
Loss in wt., >100 mg/100 cm2. 6 50 ATMP Considerable erosion
without 50 HEDP rust deposition. Loss in wt., about 100 mg/100
cm.sup.2. 7 40 Na.sub.2 HPO.sub.4 No surface corrosion. Change in
weight of the sheets, 4 ATMP <0.5 mg/100 cm.sup.2. Turbid
solution. 8 40 Na.sub.2 HPO.sub.4 No surface corrosion. Change in
weight of the sheets, 6 HEDP <0.5 mg/100 cm.sup.2. Turbid
solution. 9 40 Na.sub.2 HPO.sub.4 No surface corrosion. Change in
weight of the sheets, 2 HEDP <0.5 mg/100 cm.sup.2. No turbidity
2 ATMP of the solution even with renewed solution which had
carbonate hardness of 10.degree. and pH of 9. No separation of
scale on the sheet 10 40 Na.sub.2 HPO.sub.4 No corrosion. Change in
weight of the sheets, 2 HEDP <0.5 mg/100 cm.sup.2. No 2 ATMP
turbidity in the solution. 1 zinc nitrate
__________________________________________________________________________
EXAMPLE 2
To each cubic meter of water present in a hot water system
maintained at temperature 80.degree.C and having a total hardness
of 30.degree. (German hardness), 1 kg of a solution was added of
the following composition.
______________________________________ Na.sub.2 HPO.sub.4.2H.sub.2
O 44 % HEDP (free acid) 3.6% ATMP 3.5% Zinc nitrate 2% Water 46.9%
______________________________________
During this treatment, the pH value of the water was adjusted to
9.5. No corrosion occured in neither the galvanized pipe system,
the heating unit, nor in the non-ferrous metal valves. Furthermore,
no turbidity of the water was observed during a period of 6
weeks.
EXAMPLE 3
To each cubic meter of water of Example 2 was added 1.2 kg of a
solution of the following composition:
______________________________________ NaH.sub.2 PO.sub.4.2H.sub.2
O 25% HEDP (free acid) 9% ATMP 9% Zinc nitrate 2% Water 55%
______________________________________
Prior to the treatment, the hot water system was strongly scaled,
so that reduction of the heating efficiency and boiling noises in
the boiler occurred. After a treatment time of 2 weeks, the boiling
noises were eliminated and full heating efficiency was restored.
Inspection of the pipe system showed that it was completely free
from scale. Formation of a sludge was not observed, and there was
just a little corrosion in the entire system, including the
valve.
EXAMPLE 4
120 g of the solution described in Example 2 was added per cubic
meter of the water in a cooling circuit exposed to evaporation
losses. This water had a total hardness of 20.3.degree. (German
hardness), carbonate hardness of 14.degree. (German hardness),
corrosive carbonic acid at 4.5 mg per liter oxygen at 2.0 mg per
liter, and chloride ions at 260 mg per liter. During the 6-week
test period, no new encrustations were formed. After each 14 days,
a small amount of sludge had to be removed from the system (caused
by evaporation losses of water).
Various modifications of the herein described method for inhibiting
corrosion and mineral deposition in a water system may be made
without departing from the spirit and the scope thereof, and it is
to be understood that the invention is to be limited only as
defined by the appended claims.
* * * * *