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Jan. 22, 1963 G. S.

GARDNER 3,074,825
METHOD OF REMOWING COPPER-CONTAINING TRON OXIDE
INCRUSTATIONS FROM FERRIFEROUS SURFACES
Filed April 3, 1962 2 Sheets-Sheet l

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MNMLM AMOUNT MTU REQUIRED
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TEMPERATURE
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NVENTOR
METHYOL THOUREA CONCENTRATION-MOLS/TER 5.4 lion)
st vigov AT TORNEYS
Jan. 22, 1963 G, S, GARDNER 3,074,825
METHOD OF REMOViNG COPPER-CONTAINING IRON OXIDE
INCRUSTATIONS FROM FERRIFEROUS SURFACES
Filed April 3, 1962 2. Sheets-Sheet 2

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MNIMUM AMOUNT OMTU REGUIRED


TO PREVENT CU PLATING
CONDITIONS
TEMPERATURE 6of
MMERSON 2ORS
3. ACD 5% by wt.
coRROSION NHBTOR O.1% by wit.

O.O5 O.O6
NVENOR
DIMETHYLOL THIOUREA conCENTRATION-MOLS/ITERlegist
--
2, ATToRNEYs
United States Patent Office 3,074,825
Patented Jan. 22, 1963
2
tain agents which in no way interfere with the action
3,074,825 of any corrosion inhibitors which may have been em
METHOD OF REMOVING COPPER-CONTAINING ployed and which agents under certain circumstances
RON OXDE INCRUSTATIONS FROM FERRF may, in themselves, actually provide an excellent measure
EROUS SURFACES 5 of corrosion inhibition.
George S. Gardner, Elkins Park, Pa., assignor, by mesne Other objects and advantages of this invention will
assignments, to Chemical Cleaning, Inc., a corporation become apparent in considering the following disclosure
of Louisiana
Filed Apr. 3, 1962, Ser. No. 184,736 and the accompanying drawings wherein
8 Claims. (Cl. 134-41) FIGURE 1 is a semi-logarithmic graph illustrating the
0 use of monomethylol thiourea in the acids employed in
This invention relates to the art of removing copper the removal of copper-containing incrustations; and
containing iron oxide incrustations from ferriferous metal FIGURE 2 is a semi-logarithmic graph illustrating the
surfaces and is particularly useful in connection with use of dimethylol thiourea under conditions similar to
the removal of such incrustations from the internal Sur those illustrated in FIGURE 1. -
faces of industrial heating equipment such, for example, Under the conditions of both FIGURES 1 and 2 the
as boilers, radiators, condensers and generators. In this quantities of thiourea involved are those which are re
art, as is well known, it is common practice to employ quired for essentially complete removal of the copper
aqueous solutions of hydrochloric or other acids which content under the conditions of the tests.
are capable of dissolving the incrustations, which in The present invention is based upon the discovery that
crustations include iron oxide and certain salts coming 20 a methylol thiourea having the formula:
from impurities in the water plus a small but troublesome E.
content of copper picked up from various sources familiar
to those skilled in this art.
The removal of such copper-containing iron oxide in S PC
crustations, especially from industrial equipment of the N-OHO
type referred to, involves certain difficulties. For in
stance, use of hydrochloric or other acid solutions per Se
is not always fully effective because, although the iron wherein X is selected from the group consisting of hydro
oxide or other contaminants are readily dissolved by the 30 gen and CHOH, when added to the acid solution em
acid solution, the copper component of the incrustations ployed makes it possible to effect complete removal of
is sometimes merely redeposited as a plating on the fer copper-containing iron oxide incrustations from metal
riferous metal surfaces. This problem is referred to in surfaces without redeposition of the copper ion and with
U.S. Patent 2,567,835 which relates to a method for out interfering with the action of any organic nitrogen
removing copper-containing boiler incrustations without base corrosion inhibitor which also may have been em
redeposition of the copper. However, the technique de ployed.
scribed in this patent involves a number of disadvantages Acids which are known to be suitable for use in dis
in that it requires a multiplicity of steps which are not solving copper-containing iron oxide incrustations include
only laborious but also excessively time-consuming. mineral acids such as hydrochloric, phosphoric and sul
For instance, according to the disclosure in the patent furic, also sulfamic acid, as well as organic acids such
referred to, copper-containing incrustations are removed as acetic, oxalic, citric and gycolic. These acid solu
by subjecting them first to the action of a hydrochloric tions, containing a methylol thiourea either with or with
acid solution containing a corrosion inhibitor followed out a suitable corrosion inhibitor, may be brought into
by a water rinse. Secondly, the surfaces are subjected contact with the iron oxide incrustations in any con
to the action of an ammoniacal solution containing a venient manner. For example, when treating the inside
strong oxidizing agent followed again by a water rinse. of a boiler the latter may simply be filled with the solu
As a third step, they are subjected to the action of a tion of the present invention so as to contact the area
dilute hydrochloric acid solution and finally, as a fourth of incrustation. Where very large vessels are to be
step, to the action of a hot dilute aqueous alkaline solu treated it is generally more economical to direct a stream
tion. While this technique ultimately accomplishes the of the acid treating solution against the incrustation in
desired objective, namely the removal of the incrusta stead of filling the vessels.
tion including its copper component yet, as noted above, While my process may be at least partially useful at
it is complex, laborious, time-consuming and expensive. lesser or greater temperatures, I have found that the
More recently, it has been discovered that such copper desired copper and iron oxide removal action, without
containing iron oxide incrustations can be removed redeposition or plating of copper, is obtained to an opti
through use of an aqueous acid solution containing cer mum extent at temperatures between about 75° F. and
tain urea derivatives, for example, thiourea, 1,3-dimeth 200 F. Because of this temperature requirement, it
ylthiourea, ethylene thiourea, 1,3-diethylthiourea, and may be necessary in some cases to supply heat to the
1,3-diisopropylthiourea. Although this process is capable solution or to the equipment being cleaned, or to both
of removing the iron oxide deposits without redeposition 60 the solution and the equipment in order to insure having
of the copper component, such thioureas are not capable the incrustations and the solution in contact with each
of functioning per se as corrosion inhibitors, and they other at a temperature at which the incrustations will be
interfere with the inhibiting action of other corrosion acted upon by the solution and thereby removed.
inhibitors which may have been added to the acid solu So far as concerns the amount of methylol thiourea
tions, thereby allowing undesirable acid attack on the compound to be employed in the process of this inven
basis metal under the incrustation. tion, it has been found that this will depend upon sev
With the foregoing in mind, the principal object of eral factors. For example, where the monomethylol
the present invention is the provision of a process for thiourea compound is employed, generally smaller
removing copper-containing iron oxide incrustations from amounts thereof are required on a molar basis, per mol
ferriferous surfaces and more especially from the inte 70 of copper ion sought to be removed, than would be
rior surfaces of industrial heating equipment, which required when using the dimethylol thiourea compound.
process involves the use of acid solutions containing cer Variations in the acid systems utilized, the acid con
3,074,825
3 4.
centrations, the temperature, as well as the organic cor invention introduce no apparent deleterious effect upon
rosion inhibitor employed, if any, all tend to influence the corrosion inhibitors employed in the acid solutions,
the amount of methylol thiourea compound to be used. but actually in themselves impart an excellent degree of
Varying amounts of copper ion in the solution also re corrosion inhibition with respect to the metal and even
quire different concentrations of methylol thiourea com provide some synergistic effect with other corrosion in
pounds, praticularly where complete copper removal is hibitors which may be used so that the use of corrosion
desired. Nevertheless, generally speaking, there is a semi inhibitors per se may be desirable depending upon the
logarithmic relationship which has been found to exist be particular acid employed. Where such additional in
tween the minimum amount of the methylol thiourea com hibitors are used it is, of course, essential that they be
pound which should be employed and the aomunt of cop O soluble in the acidic solutions.
per to be removed by the solution provided, of course, Well known types of organic nitrogen-base corrosion
that other variables remain substantially constant. The inhibitors which may be incorporated in the solutions of
accompanying graphs show the relationship between the this invention include the aromatic and heterocyclic coal
thiourea compound employed and the copper to be re tar bases produced from the distillation of coal tar. Typi
moved, the graph of FIGURE 1 showing this relationship 5 cal examples of these are pyridine, alpha picoline, beta
for methylol thiourea, and the graph of FIGURE 2 for picoline, gamma picoline, 2-n-amylpyridine, 4-n-amyl
dimethylol thiourea. The other factors, namely the tem pyridine, 2-hexyl-pyridine, various substituted lutidines,
perature, the period of treatment (immersion), the type collidines, quinolines, lipidines, and quinaldines. The well
of acid and its concentration and the content of inhibitor known rosin amine based inhibitors are also suitable for
employed, are all constant as shown by the graphs. use in this respect and, of course, there are many others
In developing both graphs the inhibitor employed was familiar to those skilled in the art. The concentration or
prepared in accordance with Example I of U.S. Patent amount of the corrosion inhibitor depends upon its effec
2,758,970. tiveness in the particular acid solution employed and at
At this point I wish to explain what I mean by "copper the temperature at which it is used. Generally, the amount
removal.' The copper, of course, forms a part of the effective to inhibit or reduce the corrosive effect of the
incrustation which must be removed from the surface acid is in the range of 0.1 to 1% based on the weight
of the work being treated and this must be done without of the acid in the treating solution.
redeposition of the copper as a plating on the surface. In order to illustrate the excellent copper removing
However, as an actual matter of fact, it is my belief or chelating properties of the mono and dimethylol thio
that the action is more one of a chelating procedure, i.e., 30 urea compounds of the present invention there is present
the dissolved copper ion is in some way held or retained ed below, in Table I, a series of test results wherein hot
in the solution in a relationship which prevents its rede rolled steel (SAE 1010) test strips were subjected to the
position on the surface. In presenting this theory of action of 5% by weight hydrochloric acid solutions, some
the action involved, it should be understood that I am of which had dissolved therein 0.001 mol/liter of cop
not fully aware of just what takes place except that the 35 per ion, 0.01 mol/liter of a methylol thiourea compound
copper ion is not redepositioned upon the surface when as indicated by the designation "MTU or “DMTU” for
the teachings of this invention are employed. However, the mono or dimethylol thioureas, respectively, and/or
this theory is substantiated by the results of the tests which 0.1% inhibitor identified in the table by letters in ac
I have conducted, as shown in the tables hereinafter cordance with the following identification:
introduced. In making the tests it was, of course, impos 40
A=Inhibitor prepared in acocrdance with Example I of
sible to obtain pieces of ferrous metal carrying incrusta U.S. Patent 2,758,970.
tions of the kind with which the invention is intended
to deal. For this reason the acid solutions employed in B=Inhibitor prepared in accordance with Formula 2 of
the tests were prepared to include certain copper concen U.S. Patent 2,807,585.
trations as set forth and the concentrations utilized are 45 C=Inhibitor prepared in accordance with U.S. Patent
strictly representative of copper concentrations which 2,510,063 and containing 15 mols of ethylene oxide.
are generally encountered in the removal of copper-con All of these tests were conducted at 115° F. for a six
taining iron oxide incrustations of the kind referred hour period.
to. The minimum amount of methylol thiourea com Table I
pound required in the solution to prevent copper from 50
depositing upon ferrous metal pieces is plotted in the Methylol Moll. Corrosion Weight,
graphs. thiourea Culion inhibitor loss, lbs.f Cu deposition
It will be observed for both graphs that, under the compound ft.2124 hrs.
conditions employed, the amounts of methylol thiourea
compounds required per unit of copper ion present are 55 None------------ 0.001 None-------- Gain-Heavy copper plating
None .----do 0.0139 None.
larger at very low copper concentrations, but that, as None 0.0067 Do.
the copper concentration increases, the amount of the None
0.00
0.0026
0.0009
Do.
Do.
methylol thiourea which is required is not proportionately None 0.0026 Do.
increased. 0.00 0.00 Do.
Generally, it has been found that use of approximately None 0.0052 Do.
0.001 0.0006 Do.
4 mols of methylol thiourea compound per mol of cop None 0.0044 Do.
per provides essentially complete copper removal. No 0.00
None
0.0006
0.006
Do.
Do.
maximum limitation has been found as to the quantity of DMTU----------
0.00
None
0.000
0.0049
Do.
Do.
methylol thiourea which can be used and as much as 16 DMTU---------- 0.001 0.000 Do.
mols of the compounds of this invention per mol of cop 65
per have yielded completely satisfactory results. How
ever, in the interests of economy and to prevent waste it As can be seen from the data presented above, the use
is preferred to employ no more than about 10 mols of of either the mono or dimethylol thiourea derivatives
methylol thiourea compound per mol of copper contained of this invention successfully prevents copper deposition
in the iron oxide incrustations. 70 in uninhibited as well as in inhibited acid solutions. More
The amount of copper contained within the iron oxide over, these data show a surprising reduction in weight loss
incrustations may, of course, be determined beforehand of the treated metal when the mono or dimethylol thiourea
by analytical methods familiar to the art. compounds of this invention are used in conjunction with
As noted hereinabove, the methylol thiourea deriva an acid corrosion inhibitor for removing copper ion from
tives found to be suitable for use in the process of this 75 acid solutions.
8,074,825
5 6
Hot-rolled steel test strips, similar to those employed at uniform concentrations of 0.01 mol/liter of test solu
in developing the data reported in Table I, were ex tion. Copper ion, at 0.001 mol/liter, was used where
posed to 5% hydrochloric acid solutions for periods of 16 indicated, and 0.2% by weight of commercial corrosion
hours at 115 F. These acid solutions were prepared inhibitors were used as indicated. These inhibitors are
so as to contain, where indicated, 0.001 mol/liter of cop identified in Table IV by the letters “A” and “B.” In
perion, 0.01 mol/liter of a methylol thiourea compound hibitor “A” was prepared in accordance with Example
of this invention, and 0.1% by weight of a corrosion in I of U.S. Patent 2,758,970 as follows: 217 grams of a
hibitor prepared in accordance with Example II of U.S. commercial grade of dehydrogenated rosin amine (ap
Patent 2,403,153. The results of these tests are reported proximately 0.70 mole) was placed in a round-bottom
in Table II. 10 Pyrex flask. 4 moles (293 ml.) of acetone and 2.2 moles
Table II (163 m.) of 37% formaldehyde solution was then added
thereto. The mixture was slowly stirred and 0.70 mole
Methylol Moi?. Corrosion Weight, (70 mi.) of 20 Bé. hydrochloric acid was added in small
thiorea
compound
Clion inhibitor loss, sf Cul deposition
ft.2124 hrs.
increments over a period of 10 minutes. The mixture was
15 gently refluxed for 15 hours, at the end of which time the
0.039 None.
liquid was distilled to a vapor temperature of 90° C., 200
0.002 DO. ml. of distillate being obtained. The distillate contained
0.007
0.006
D0.
Do.
excess acetone plus some water and formaldehyde. The
0.0028 DO. residue in the flask consisted principally of a solution of:
O,006 Do. 20 CH-CH-CO-CE
EC
The MTU and “DMTU' are, respectively, mono CH-CH-CO-CH
methylol thiourea and dimethylol thiourea.
The results in Table II are a further demonstration which is a dark, oily, viscous material. This material was
of the ability of the methylolated thiourea compounds of 25 diluted with water to make a total weight of 620 grams.
this invention to prevent deposition of copper ion from Inhibitor “B” was prepared in accordance with U.S.
acid solutions on the metal surfaces under treatment. Patent 2,510,063 as follows: 15 moles of ethylene oxide
These results also reflect the reduced weight losses ob were reacted with dehydrogenated rosin amine to produce
tained on the treated metal when the compounds of this a compound having the general formula:
invention are used in conjunction with corrosion inhibi 30
X
?tors.
In order to illustrate the comparable copper removing RN/N
or chelating properties of the mono and dimethylol thi (CH2CH2O).H.
ourea compounds of this invention in comparison with 35
the prior art thiourea and lower alkyl substituted thiourea where R is the dehydroabietyl group, and where X is the
derivatives, there is presented below in Table III a series -(CH2CH2O)H group, and wherein the sum of m--n
of test results wherein various amounts of these thiourea is 15.
compounds were employed under otherwise identical con Table IV
ditions. Each test solution contained 5% by weight of 40
hydrochloric acid, 0.01 mol/liter of copper ion and 0.1% Methylol thiourea
compounds
Cl CorrosionWeight loss Cu deposi.
present inhibitor lbs./ft.2124 tion
by volume of a rosin amine based corrosion inhibitor such present hrs.
as described in Example I of U.S. Patent 2,758,970. All
test solutions were maintained at 160 F. and the tests Thiourea--------------- None.-- A 0.0268 None.
continued for three hours, and the test metal was SAE 45 Diethylthiourea----------
Ethylenethiourea-
do----- A.
A.
0.0429
0.0265
Do.
Do.
1010 hot-rolled steel, previously cleaned by pickling in Methylol thiourea-------do----. A. 0.035 do,
hydrochloric acid solution. Dimethylothiourea
Thiourea--------
A.
A.
0.0093
0.1042 Slight.
Do,
Table III Diethylthiourea A. 0.04.67 None
Ethylenethioure A. 0.0450 Do.
Methylol thiourea A. 0.009 Do.
Thiourea compound Weight 50 Dimethylothiourea--- A. 0.008 Do,
Thiourea--------------- B 0.742 Do.
loss, Cu deposition Diethylthiourea-- B 0,575 Do,
Ibslft.824 Ethylenethiouraa- B O. 1910 Do.
Type Molfi, hrs. Methylol thiourea B 0.050 Do.
Oimethylol thiour B 0.005 Do.
Thiourea---------- B 0.1442 Slight.
None------------------------------------- 0.0033 Heavy.
Thiourea. 0.03 0.0332 Slight. 55 Diethylthiourea------ Yes----. B
Ethylenethiourea------ Yes.---- B
0.055 None.
0.050 Do.
DO--- 0.05 0.04.08 DO. Methylol thiourea. Yes.----- B 0.002 Do.
D0------- 0.07 0.0443 Do. Dimethylol thiourea. Yes--- B 0.0050 Do,
Diethylthioure 0.05 0.010 None,
Ethylenethiourea-- 0.05 0.0361 Slight.
Diisopropylthiourea---- 0.03 Gain-Heavy copperplating
Methyol thiourea------
Do--------------
0.05
0.07
0.0025 None.
O, 0.038 Do.
From Table IV it is apparent not only that copper de
Dimethylothiourea 0.03 0.0006 DO. 60 position is prevented in acid solutions with the methylol
Do.--
DO---
0.05
0.07
0.0009
0.001
Do.
Do. lated thiourea compounds of this invention, but also that
greatly reduced corrosion loss is achieved through use of
these compounds.
The foregoing table demonstrates not only the ability Moreover, attention is directed to the increase in weight
of the methylol and dimethylol thiourea compounds of 65 loss obtained from the incorporation of inhibitor "A"
the present invention to remove copper from iron in with the three prior art thiourea compounds. These re
crustations with aqueous acid solutions, but also the sults show clearly the antagonistic effects of these par
greatly improved corrosion protection afforded by the ticular thiourea derivatives with a commercial acid cor
methylolated thioureas in comparison to the prior art rosion inhibitor.
compounds, and the complete compatibility of these com 70 The use of other acid systems for dissolving copper
pounds with organic corrosion inhibitors. containing iron oxide incrustations from ferriferous Sur
Additional tests were conducted at 200 F. for a two faces, some of which systems also contained 0.1 mol/liter
hour period utilizing SAE type 1010 hot-Tolled steel of methylol thiourea, is shown below in Table V. All
panels immersed in 5% hydrochloric acid solutions. of these solutions were run at 160 F. for 45 minutes and
Various thiourea compounds were employed in these tests 75 contained 0.01 mol/liter of copper ion.
3,074,825
Table 7
8
Acid Methylol Weight /
i-x
thiourea loss, Cu depo SC
present lbs./ft./24 sition
Type Mols, hrs.
yellor w
1.85 No.------ 3.31. Heavy.
.85 Yes.....
1.6 No.------
0.003
1.520
None.
Beavy. wherein X is selected from the group consisting of hy
1.6 0.022 None. . drogen and CH-OH and then treating the surface with the
0.62 0.845 Heavy. 0. solution to effect removal of incrustations. - -
0.62 0.002 None.
0.31 0.209 Heavy. 2. The method of claim 1 wherein the quantity of
0.31
0.67
0.002
0.004.
None.
Heavy. methylol thiourea employed is not less than about 2 mols
0.67
1.75
0.0005.
0.112
None.
Heavy.
for each mol of copper in the incrustation.
1.75 0.004 None. 3. The method of claim 1 wherein the temperature of
0.96 0.55 Heavy. the acid solution is maintained at from 75 F. to 200' F.
0.96 0.003 None 4. The method of claim 2 wherein the temperature of
the acid solution is maintained at from 75 F. to 200 F.
The data presented above demonstate that the methyl 5. The method of claim 2 wherein the quantity of
olated thiourea derivatives of this invention exhibit inhibi methylol thiourea is from 2 to 10 mols per mol of copper.
tory properties in themselves and are completely capable 20 6. The method of claim 2 wherein the quantity of
of removing copper from iron oxide incrustations found methylol thiourea is from 2 to 10 mols per mol of copper
on the internal surfaces of industrial heating equipment and, further, wherein the temperature of the acid solution
by what is believed to be a chelation process whereby the is maintained at from 75 F. to 200 F.
methylolated thiourea forms a complex with the copper 7. The method of claim 1 wherein the acid solution
ion, thereby preventing its redeposition from the acid 25 also contains an amount of an organic nitrogen-base other
solution onto the ferrous metal surfaces. than the methylol thiourea specified, which organic nitro
Although the data reported in this disclosure were gen-base is capable of inhibiting the corrosive action of
the acid on ferriferous metal. -
the results of laboratory tests, I wish it to be distinctly 8. The method of claim 2 wherein the acid solution
understood that these results have been fully confirmed as 30 also contains an amount of an organic nitrogen-base other
correct by experimental work in the field. than the methylol thiourea specified, which organic nitro
I claim: gen-base is capable of inhibiting the corrosive action of
(1. In the art of removing copper-containing iron oxide the acid on ferriferous metal. . /
incrustations from ferriferous surfaces by subjecting the
surfaces to the action of an aqueous acid solution capa 35 References Cited in the file of this patent
ble of dissolving the incrustations, the method which UNITED STATES PATENTS
comprises adding to the solution a soluble methylol thio
urea having the formula 2.959,555 Martin et al. ----------- Nov. 8, 1960

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