U.S. patent number 3,639,263 [Application Number 04/748,916] was granted by the patent office on 1972-02-01 for corrosion inhibition with a tannin, cyanohydrinated lignosulfonate, and an inorganic metal salt composition.
This patent grant is currently assigned to Nalco Chemical Company. Invention is credited to Reed S. Robertson, Edwin S. Troscinski.
United States Patent |
3,639,263 |
Troscinski , et al. |
February 1, 1972 |
CORROSION INHIBITION WITH A TANNIN, CYANOHYDRINATED LIGNOSULFONATE,
AND AN INORGANIC METAL SALT COMPOSITION
Abstract
A corrosion-inhibiting composition and process consisting of (a)
a water-dispersible tannin, (b) a cyanohydrinated lignosulfonate or
naphthalene sulfonate, and (c) a polyvalent metal ion masking agent
for the chelating system, e.g., zinc nitrate.
Inventors: |
Troscinski; Edwin S. (Oak Lawn,
IL), Robertson; Reed S. (Glen Ellyn, IL) |
Assignee: |
Nalco Chemical Company
(Chicago, IL)
|
Family
ID: |
25011452 |
Appl.
No.: |
04/748,916 |
Filed: |
July 31, 1968 |
Current U.S.
Class: |
252/389.52;
252/387; 422/19; 252/181; 422/14 |
Current CPC
Class: |
C23F
11/08 (20130101); C02F 5/105 (20130101); C02F
2303/08 (20130101) |
Current International
Class: |
C23F
11/08 (20060101); C02F 5/10 (20060101); C23f
011/14 () |
Field of
Search: |
;252/389,387,8.55E,181,178,85 ;21/2.7 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lovering; Richard D.
Assistant Examiner: Gluck; Irwin
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. A corrosion-inhibiting composition useful in preventing
corrosion of iron surfaces in contact with cooling water consisting
essentially of a chelating system to complex water-dispersible iron
species existing in said cooling water which chelating system
comprises 10-70 parts by weight of a water-dispersible tannin and
5-50 parts by weight of a substance selected from cyanohydrinated
lignosulfonates and cyanohydrinated naphthalene sulfonates; and
10-60 parts by weight of a masking agent to retard said complexing
action of said chelating system, which comprises a water-soluble
inorganic metal salt containing a multivalent metal ion selected
from the group consisting of zinc, aluminum, cadmium, cobalt,
nickel and manganese.
2. The composition of claim 1 wherein said water-dispersible tannin
is a natural tannin having been modified by reaction with a
material selected from the group consisting of an alkali metal
sulfite, an alkali metal bisulfite, ammonium sulfite, ammonium
bisulfite, an alkali metal haloacetate, an alkali metal
halopropionate, an alkali metal halobutyrate, ammonium cyanide, an
alkali metal cyanide, ammonium thiocyanate, alkali metal
thiocyanate, nitric acid, and sulfuric acid.
3. The composition of claim 2 wherein said inorganic salt is zinc
sulfate and said cyanohydrinated compound is cyanohydrinated
lignosulfonate.
4. The composition of claim 1 which additionally contains about
2.35 to about 7.8 percent by weight of a compound selected from the
group consisting of 2-mercaptobenzothiazole and its alkali metal
salts.
5. A process for inhibiting corrosion of a ferrous metal surface in
contact with a corrosive cooling water medium which comprises
maintaining contact of said surface with said water which
additionally contains a corrosion-inhibiting composition consisting
essentially of a chelating system to complex water-dispersible iron
species existing in said cooling water which chelating system
consists essentially of 10-70 parts by weight of a
water-dispersible tannin, and 5-50 parts by weight of a compound
selected from the group consisting of cyanohydrinated
lignosulfonates and cyanohydrinated naphthalene sulfonates, and
10-60 parts by weight of a masking agent to retard said complexing
action of said chelating system which consists essentially of a
water-soluble inorganic metal salt containing a multivalent metal
ion selected from the group consisting of zinc, cobalt, aluminum,
cadmium, manganese and nickel.
6. The process of claim 5 wherein said water-dispersible tannin is
a natural tannin having been modified by reaction with a material
selected from the group consisting of an alkali metal sulfite, an
alkali metal bisulfite, ammonium sulfite, ammonium bisulfite,
alkali metal haloacetate, an alkali metal halopropionate, an alkali
metal halobutyrate, ammonium cyanide, an alkali metal cyanide,
ammonium thiocyanate, an alkali metal thiocyanate, nitric acid and
sulfuric acid.
7. The process of claim 6 wherein said water-soluble salt is zinc
sulfate and said sulfonate compound is cyanohydrinated
lignosulfonate.
8. The process of claim 5 wherein said composition additionally
contains about 2.35 to about 7.8 percent by weight of a compound
selected from the group consisting of 2-mercaptobenzothiazole and
its alkali metal salts.
9. The process of claim 5 wherein said cooling water has a pH
ranging from about 6.0 to 8.0 and said inhibitor composition is
present in said cooling water in the amount of 10-500 parts per
million.
Description
The instant invention is directed to a process of inhibiting
corrosion of iron surfaces in contact with cooling waters. More
specifically, the subject invention relates to compositions which
inhibit corrosion of iron in presence of cooling waters by aiding
in formation of a protective iron oxide film over the iron
substrate.
One of the best known ways to inhibit corrosion of iron surfaces,
such as carbon steel, which are in contact with corrosive cooling
waters is to somehow increase the tendency of the iron surface to
form a protective iron oxide film. However, in the usual situation
corrosion or rusting occurs because either the type or form of the
oxide produced is nonprotective or because the film-forming
reaction is too slow. Thus, soluble iron species are allowed to
migrate too far from the surface to be of any appreciable value in
forming a surface barrier to ionic and/or molecular corrodants or
corrosion products. Dissolved oxygen in the aqueous environment in
contact with the iron equipment or container then diffuses to the
free metal surface more rapidly and high-corrosion rates ensue.
If this diffusion could somehow be slowed down and controlled,
corrosive attack would cease or be greatly reduced. Specifically,
if, by some means formation of a thin, tightly bonded, uniform film
of the proper type of iron oxide over the iron surface could be
promoted, the iron system under attack from cooling water media
would be less prone to corrode, or in many cases would be
substantially noncorrosive.
In order to somehow aid formation of a protective iron oxide film,
a chemical composition must not form strong complexes or chelates
with soluble iron species which would increase the demand for iron
in the cooling water and thereby increase corrosion rates. Yet,
such a composition must be able to react with or absorb on iron or
the iron oxides at the iron surface to control the crystallinelike
growth and habit of the oxides. Also, a chemical treating agent
when added to the cooling water system as a corrosion inhibiting
substance must be able to reach the metal surface under attack or
at least make a very close approach to the surface, certainly
within the ionic double layer, while still in active form. In
brief, a useful chemical anticorrosive material should be able to
help produce an ideal oxide film in a quick and efficient manner by
a facile, close approach to an iron surface to which it can attach
itself or be in close proximity. The additive would then be able to
absorb or react with iron species just formed through the
additive's active sites, thereby enhancing filming on the iron or
steel surface to be protected.
The above problem is a particularly arduous one with which prior
art materials have not been dependably able to cope. In some
instances, the additive reagents while tying up in some manner the
iron which has escaped from the surface of the corroding metal and
through the ionic double layer, are thereby rendered almost
immediately ineffective. In other words, such prior art material
becomes quickly exhausted after some type of reaction or absorption
with the iron ions, and is no longer effective in combating
corrosion by promotion of protective iron oxide film. On the other
hand in some cases, substances added to cooling waters to inhibit
corrosion of iron substances in contact with these liquids, are so
aggressive in their reaction with iron ions by some types of
complexing or chelation, that the concentration of iron ions in
solution is rapidly depleted. This then has the adverse effect of
shifting the equilibrium reaction at the metal surface and actually
increasing the release of iron ions to the water. Metal attack is
thereby increased. If, therefore, a corrosion inhibiting
composition could be devised to somehow enhance formation of a
protective iron oxide film on surfaces of corrodible iron metals,
and obviate the just discussed problems, a substantial advance in
the art would be made.
It, therefore, becomes an object of the invention to provide
cooling water compositions and method for their use.
Another object is to provide cooling water compositions which will
promote formation of a protective iron oxide film upon the surfaces
of corrodible iron metals and thereby control the diffusion of
oxygen to the free iron metal surface which is susceptible to its
corrosive effects.
A special object of the invention is to provide a combination of
compounds in a single composition which will protect corrodible
iron surfaces in the presence of cooling water over long periods of
time even at relatively low dosages, which compositions are not
quickly depleted of activity by rapid reaction of their active
sites with water dispersible iron species.
In accordance with the invention, a method of inhibiting corrosion
of iron metal surfaces such as heat exchange surfaces in contact
with cooling waters, has been discovered. Generally, corrosion as
well as fouling of the iron metal surfaces can be controlled
through the use of a corrosion-inhibiting composition comprising a
chelating system which includes both a water-dispersible tannin and
an HCN modified lignosulfonate or naphthalene sulfonate and a
masking agent for the chelating system which comprises a
multivalent metal ion.
The above three constituents of the corrosion-inhibiting
compositions are all essential to efficient control of corrosion.
Omission of any one of the three ingredients, as will be seen more
clearly later, does not give the proper corrosion protection when
compared to a cooling water treatment involving all three
components.
The specific compounds making up the sum total corrosion-inhibiting
composition may be added to a cooling water separately, or they may
be combined into a single product in either liquid or granular
form, or in the form of a shaped article of manufacture, e.g., a
water-treating ball. The subject composition may be readily formed
into compact balls which may then be conveniently added to the
cooling water.
The chelating system which is added to the cooling water in order
to complex or tie up water-dispersible iron species existing in the
cooling water includes a water-dispersible tannin and an HCN
modified lignosulfonate or naphthalene sulfonate.
A. Water-Dispersible Tannin Substituents
Greatly preferred water-dispersible tannins are those which have
been modified by a variety of synthetic method by reaction of
natural tannins with various chemical reagents. Mixtures of these
modified tannins may also be used in preparing the subject
compositions.
The tannins have been divided into two principal groups--the
catechol tannins and the pyrogallol tannins. After dry distillation
the catechol tannins yield catechol as a principal product of
decomposition, and the pyrogallol tannins after dry distillation
yield pyrogallol. Solutions containing catechol give a
greenish-black precipitate with ferric salts, whereas solutions
containing pyrogallol tannins give a bluish-black precipitate with
ferric salts. In general, only pyrocatechol derivatives are found
in catechol tannins, whereas gallic acid is always present in
pyrogallol tannins. The preferred tannins for use in the subject
process are the catechol tannins although pyrogallol tannins can
also be used in the process.
Natural tannins can be obtained from a number of materials. One of
the principal sources is the quebracho trees, the wood of which
contains about 20 to 23 percent easily extractable tannin of the
catechol type. Other sources include chestnut wood, redwood bark,
divi-divi pods, mangrove bark cutch (one of the preferred sources
along with quebracho trees), wattle bark, gallnuts, hemlock bark,
sumac, and oak bark.
A discussion of tannins and tannin chemistry is set forth in the
Encyclopedia of Chemical Technology, Vol. 13, pages 578-599, which
article is by reference included as part of this disclosure.
In the modification step the tannins are bisulfited by reaction
with sulfite, bisulfite or formaldehyde and bisulfite, or are
modified by reaction with sodium or ammonium cyanides, with sodium
chloroacetate, with sulfuric acid (either sulfonation or
oxidation), with nitric acid (which would involve either oxidation
or nitration), etc., to produce functional group changes in the
natural tannin. Thereby its performance is markedly improved as an
aid to its action in the subject treatment.
A preferred group of modified tannins which can be used in the
subject invention is described in U.S. Pat. No. 2,831,022. In the
process disclosed in this patent, water solutions of sulfurous acid
salts of alkali metals or ammonia are caused to react with the
insoluble portion of Western hemlock bark at increased temperatures
and in the presence of an excess of sulfurous acid. The
water-soluble alkali sulfonic acid salts which are produced are
separated as water solutions from the reaction mixture. The water
solutions can include aqueous sodium sulfite and aqueous sodium
bisulfite. The produced compounds are sulfonic acid derivatives or
sodium sulfonate derivatives of the tannins occuring in the bark.
Such compounds have a high content of phenolic hydroxyl and are
relatively nonmethoxylated. The disclosure of U.S. Pat. No.
2,831,022 is included in this specification by reference. In the
instant process tannins from sources other than hemlock bark which
are modified as described in U.S. Pat. No. 2,831,022 also can be
used with great success.
The following examples will serve to illustrate synthetic modes of
preparation of modified tannins which are usefully employed in the
invention.
EXAMPLE I
This example shows one method which can be used to modify tannins.
In the method, 100 grams of mangrove tannin was dissolved in 150
ml. of distilled water. A second solution was formed by dissolving
16.6 grams of sodium chloroacetate in 50 ml. of distilled water.
The second solution was added slowly to the first solution as the
tannin was being heated. The mixture of the two solutions was
agitated for 1 hour at a temperature slightly below boiling. During
the mixing 10 ml. of a sodium hydroxide solution was added to
maintain the pH of the mixture above 8. The final solution could be
used as one of the component inhibitors of the invention or further
processed to active solid form.
EXAMPLE II
This example illustrates a second method which can be used to
produce the modified tannins of the subject invention. In this
method, 50 grams of chestnut tannin was mixed with 0.1 gram of
V.sub.2 O.sub.5, 0.5 ml. of ethyl silicate "40" and 1 ml. of
distilled water. The chestnut tannin had previously been passed
through an ion exchange resin to remove cations.
Twenty-five ml. of concentrated sulfuric acid was added to the
above mixture and the mixture was allow to react in its own heat
for 20 minutes. After 20 minutes, 275 ml. of distilled water was
introduced into the reaction mixture. Initially a thick paste was
formed which thinned as more water was added. Twenty-five ml. of
isopropanol was added to precipitate the reaction product. The
precipitate on filtration gave a black-brown cake. The cake was
solubilized in water by raising its pH to above 11 with caustic.
Again, the solution as diluted could be directly employed or active
solid material extracted out.
The tannins can be reacted with nitric acid in a manner similar to
sulfuric acid. In both cases the reaction is a nitration or
sulfonation and/or oxidation reaction. Likewise, the modification
can be carried out through the use of sodium, potassium or ammonium
cyanide or sodium, potassium or ammonium thiocyanate in which case
the modification procedure would be carried out in a manner similar
to those shown above in example I in connection with sodium
chloroacetate. As a substitute for sodium chloroacetate one can use
any sodium or potassium haloacetate, halopropionate or
halobutyrate. The preferred halogens are chlorine, bromine and
iodine. As has been indicated previously, the tannins can also be
modified by the method shown in U.S. Pat. No. 2,831,022. The
sulfite or bisulfite modifications shown in the patent are
preferred for preparation of tannins for use in connection with
this invention. In the bisulfite treatment, the reaction is carried
out initially at a moderate pH (5-7) whereby the bisulfite addition
takes place with the oxy ring structure being split to form
additional --OH groups. The solubilizing of the product with
caustic preferably is then carried out under sufficiently mild
condition (pH of 8-9) so as not to cause the product to hydrolyze
or to revert to its original condition. Potassium or ammonium
sulfite or bisulfite can be substituted for sodium sulfite or
bisulfite in the process. As was indicated above, any natural
tannin may be substituted for the hemlock tannin of U.S. Pat. No.
2,831,022. The preferred tannins, however, are the mangrove and/or
quebracho tannins.
B. The HCN Modified Lignosulfonate Substituent
Lignin, a waste product in the processing of wood during the
manufacture of paper and other cellulosic products is converted
into lignosulfonate in the so-called sulfite process designed to
remove lignin as water-soluble derivatives. Modern chemical
theorists believe that the reaction goes due to the replacement of
phenolic hydroxyl groups by bisulfite as described, for example, in
Organic Chemistry, Cram and Hammond, 2nd Edition, 1964, page 697.
Since the basic substance, lignin, is a wood fraction which is a
noncarbohydrate polymer, the soluble product obtained by digestion
with alkali bisulfite known as lignosulfonate is a mixture of
polymers containing various groups. In the present invention there
is utilized a further modification of the solubilized lignin which
comprises reacting HCN with the lignosulfonate to produce an HCN
modified lignosulfonate. The term "HCN modified lignosulfonate" is
defined as a modification by use of HCN or its alkali metal or
ammonium salt of a lignosulfonate and its normally contained wood
sugars. It is presently theorized that either in the soluble lignin
mixture there are sufficient carbonyl groups for nucleophilic
attack by HCN in a type of cyanohydrin reaction or a portion of the
phenolic hydroxyl groups are attached. See, for example, Organic
Chemistry, 3rd Edition, 1956, Fieser & Fieser, pages 203-204.
These cyanide modified lignosulfonates may be prepared by
conventional chemical techniques and optionally in catalyzed
environment. The HCN modified constituent is also presently in
commercial supply under the following MARATHON (American Can
Company) marks and trade designations, Chelig 32, Marathon B-10-7,
Marathon B-22-15 and Marathon B-40-5. Marathon B-10-7 is identified
as about 25 percent cyanohydrinated.
Similar to the cyanohydrin products with aldehydes and reactive
ketones, the HCN modified lignosulfonate products are extremely
stable and practically irreversible, having an extremely negligible
HCN release factor.
In the substitution of the HCN modification of the present
invention for the sugar complex substituent described in the
Robertson patent, it may additionally be necessary to add, in
certain cases, a minor but effective amount of an antifoam. A
preferred antifoam is described in British application No.
22,771/47, Aug. 15, 1947, and comprises an intimate mixture of an
inorganic aerogel and a methyl siloxane polymer having perceptible
rubbery characteristics and containing an average of from 1.75 to
two carbon atoms per atom of silicon. Such a composition is
commercially available under the name Dow-Corning Antifoam A, and
is effective in an amount less than about 0.1 percent by weight,
ordinarily at about 0.03 percent.
Additionally, it may be necessary in selected cases in the
utilization of the new substituent vice previous formulations to
incorporate a nonelectrolyte freezing point depressant, for
example, isopropanol, ethylene glycol, glycerol and the like. At
least about 0.3 oz. of the depressant composition, having reference
only to the ingredients comprising the invention, is incorporated
in each gallon of liquid. The composition is ordinarily added in an
amount of about 0.3-3 oz. per gallon, or about 0.225-2.25 percent
by weight of the liquid based on a liquid specific gravity of 1.
Preferably, at least 0.75 oz. per gallon is added, and at least 1.0
oz. per gallon is further preferred for optimum metal
protection.
Alternative to the water-dispersible lignosulfonate precursors
there may be utilized additionally water-soluble naphthalene
sulfonates which contain one or more sulfonated naphthalene nuclei,
for example, polymethylene-bis-naphthalene sulfonate in its sodium
or potassium salt form, alkyl naphthalene sulfonates or the sodium
or potassium salts thereof in which the alkyl group contains about
one -12 carbons as described in U.S. Pat. No. 3,173,864, Freedman
(Nalco). The HCN modified naphthalene sulfonates may be used in the
same manner and proportions as the lignosulfonates when treated
with HCN, NaCN, KCN or NH.sub.4 CN.
In conventional lignosulfonates there are contained wood sugars
which when present provide the major increase in functionality by
conversion of the sugars to sugar acids as for example by oxidation
of the terminal carbon of the aldose to glycaric acid.
In treating copper containing surfaces, preferable starting
materials for HCN modification are lignosulfonates wherein the
usual appreciable quantities of reducing sugars have been
previously removed or reduced as by oxidation. This is especially
true in utilizing the compositions of the present invention in
treating admiralty metal surfaces where such sugars induce pitting
but does not appear critical where the cooling water system
surfaces are ferrous or carbon steel.
C. Polyvalent Metal Ion Masking Agent.
The third component comprising the compositions of the invention is
what is termed as a "masking agent." This is a material which when
added with the above-described chelating system, associates with
the chelating or complexing agents. This reaction or absorption
upon the active sites of the chelating agents tends to retard the
complexing or chelating reaction of these chemicals with soluble
iron species. This allows the "masked" organics to pass through the
ionic double layer in a relatively undisturbed state. At the metal
surface the organics are then "demasked" by release of the metal
cation, allowing more effective reaction or adsorption at the
surface than otherwise obtainable. As mentioned above, rapid
depletion of iron concentration near the surfaces of the walls of
the corrodible metal causes either a more severe case of corrosion
than would be the situation in absence of additives, or, at the
very least, the additives are quickly rendered ineffective by their
active sites being blocked by reacting with or adsorbing soluble
iron species. The masking agents then, in effect, help to slow down
the reaction of the chelating agents with iron to the proper rate
whereby both chelating agents remain in an active state long enough
for effective reaction at the surface. The masking agents must
themselves be capable of being displaced or exchanged by iron at
the metal surface as the masked complexing agents approach the
surface.
It has been discovered that excellent masking agents which help to
retard the complexing action of the chelating agents with soluble
iron bodies are polyvalent metal ions. These ions are preferably
selected from among zinc, nickel, cadmium, manganese, aluminum and
cobalt. These metal ions, as mentioned above, react with the
organic active sites whereby the entire corrosion inhibiting
composition is allowed to make a close approach to the surface
before being inactivated by iron species. Preferred sources of the
above ions are water-soluble salts of these metals such as halides,
acetates, nitrates, and sulfates. Most preferred are the zinc and
cobalt salts in any water-soluble form.
The portion of the three constituents making up the corrosion
compositions of the invention may be varied over a wide range
according to the type of water under treatment and the type of iron
metal being protected. Preferred though are corrosion compositions
which contain 10-70 parts by weight of water-dispersible tannin,
5-50 parts by weight of HCN modified lignosulfonate and 10-60 parts
by weight of inorganic water-soluble metal salt. The most preferred
compositions comprise 20-60 parts by weight of tannin, 20-50 parts
by weight of HCN modified lignosulfonate and 20-60 parts by weight
of inorganic salt. Actual plant procedure from experience gained
since the filing date of Robertson U.S. Pat. No. 3,256,203 has
shown that where solid or balled compositions are utilized,
preferably about one-third additional HCN modified lignosulfonate
is used as compared with the liquid formulations.
The compounds disclosed here are useful in protecting any type of
corrodible iron such as mild or carbon steel and alloys of
iron.
Again, use amounts of the corrosion-inhibiting composition may be
varied according to the severity of the corrosion problem.
Generally, from about 10 parts of composition per million parts of
cooling water to about 500 p.p.m. should be employed. More
preferably 25-300 p.p.m. are used, with the most preferred use
range being from about 30 to about 100 p.p.m. One specific type of
useful application involves a short term high-level initial
treatment followed by continual low-level treatment. For example, a
cooling water may be treated with about 300 p.p.m. of the
composition of the invention for several days followed by a 30-75
p.p.m. level treatment. The pH of the water itself is preferably
adjusted prior to treatment. For optimum results the pH should
range from about 6.0 to about 8.0.
It has also been discovered that the corrosion compositions of the
invention are useful not only in inhibiting corrosion but have a
pronounced tendency to retard deposition of suspended matter upon
the corrodible iron surface. Turbid waters are often used as the
cooling source and generally contain suspended clay and other forms
of suspended silt, calcium and iron salts, microbiological growths,
alumina floc, corrosion products themselves, and other suspended
solids. These contaminants are present in the natural water or are
subsequently introduced by standing in presence of air or through
water pretreatment processes. The compositions of the invention
help to keep these solids from building up voluminous flocculant
deposits upon the surfaces of the iron heat exchange tubes or other
surfaces susceptible to such deposition. These deposits can
severely reduce heat transfer coefficients in the feedwater flow to
heat exchangers, unless controlled. Deposition may be prevented to
a substantial degree by addition of the compositions of the
invention to cooling water, preferably in the above-stated use
ranges.
Other materials may also be added to the cooling water along with
the masked chelating system in order to increase the performance of
that composition under special circumstances. For example, where
nickel or copper alloys as well as iron come in contact with the
cooling water, sulfhydryl-containing compounds may be employed.
These may be classified broadly as nitrogen-containing heterocyclic
compounds, characterized by a ring nitrogen bonded to a ring
carbon. To the ring carbon is attached a nonring sulfhydryl group.
Compounds of this type are 2-mercaptothiazole,
2-mercaptobenzimidazole, 2-mercaptobenzoxazole,
2mercaptobenzothiazole and alkali metal salts of the foregoing.
Preferably the mercaptobenzothiazole is utilized in the amount
ranging from about 2.35 to about 7.8 percent by weight.
Although the direct thrust of the present invention is directed to
nonphosphate, nonchromate corrosion inhibitors, of course, if
commercially needed, the present corrosion inhibitors may be
combined with other well-known inhibitors such as the sodium salt
of a copolymer of ethylene and maleic anhydride, phosphates and
chromates. For example, both ortho and polyphosphates may be used,
as well as hexavalent chromium such as sodium chromate and sodium
dichromate.
COMPARATIVE EXAMPLE I
Liquid Formulation According to
Example III of U.S. Pat. No. 3,256,203 Robertson
Ingredient %
__________________________________________________________________________
ZnO 5.60 H.sub.2 SO.sub.4 7.25 ClCH.sub.2 CO.sub.2 H 1.85 Sucrose
6.24 Rayflo C 16.95 50% NaOH 1.36 Soft H.sub.2 O 60.76
__________________________________________________________________________
A Liquid Formulation According to
the Present Invention
Ingredient %
__________________________________________________________________________
ZnSO.sub.4 H.sub.2 O 12.35 Rayflo C 16.95 Marathon B-10-7 8.47 Soft
H.sub.2 O 62.23
__________________________________________________________________________
(Rayflo C is a bisulfited tannin produced by the method disclosed
in U.S. Pat. No. 2,831,022.) (Marathon B-10-7 is an HCN modified
lignosulfonate produced by American Can Co.)
COMPARATIVE EXAMPLE II COMPARISON OF DRY FORMULATIONS PREPARED
ACCORDING TO TEACHINGS OF U.S. PAT. NO. 3,256,203 ROBERTSON ('203)
TO SOLID COMPOUNDS PREPARED ACCORDING TO TEACHINGS OF THE PRESENT
INVENTION (HCN)
Ingredient '203 HCN '203 HCN
__________________________________________________________________________
Rayflo C 41.4 43.6 39.00 42.50 Sucrose 14.9 14.90 40% C1CH.sub.2
CO.sub.2 Na 13.7 13.70 Marathon B-10-7 21.8 21.30 ZnSO.sub.4 .sup..
H.sub.2 O 30.0 31.6 30.05 30.80 MBT 2.07 2.13 BZT 0.28 0.25 Soft
Water 3.0 3.02
__________________________________________________________________________
Total 100.0 100.0 100.00 100.00
__________________________________________________________________________
It was found that a superiority margin exists for the new products
as versus the liquid and dry formulations prepared according to
Robertson U.S. Pat. No. 3,256,203 especially in the areas of
storage stability in the liquid version of comparative example
I.
Additionally, as to the dry formulations of comparative example II,
extensive testing showed that the Marathon-based formulas of the
present invention were superior to the formulations of Robertson
U.S. Pat. No. 3,256,203 in the areas of plant balling operations,
corrosion inhibition and deposit control performance. The deposit
control laboratory results were especially rewarding, being
uniformly in the desired area of 2.0 MPY (mils per year) in the
standard deposit coupon test utilized. This value was substantially
lower than the Robertson U.S. Pat. No. 3,256,203 results which at
times appeared erratic in shifting pH media.
* * * * *