Unlted States Patent [19] [11] Patent Number: 4,614,600

Schilling et al. I [45] Date of Patent: Sep. 30, 1986

[54] CORROSION INHIBITORS 4,344,861 8/1982 Leg/y ................................ .. 252/8.55

4,447,269 5/1984 Sc renders et al. ....... .. 252/31l.5 X
[75] Inventors: Peter Schilling; David V. Braddon,
both of Charleston, SC. QTHER PUBLICATIONS
[73] Assigneez westvaco Corporation, New York, Foster et al, article in Industrial and Engineering Chem
NX‘ lstry, vol. 51, No. 7, Jul. 1959, pp. 825-828.
[21] APPL NO; 666,971 Primary Examiner-Herbert B. Guynn
_ Attorney, Agent, or Firm-Terry B. McDaniel; Richard
[22] Flledz Oct. 31, 1984 L_ Schmalz
[51] Int. Cl.4 ...................... .. C23F 11/04; E21B 43/27 [57] ABSTRACT
[52] US. Cl. ............................... .. 252/8.553; 252/148; . . . . . . .
252/391, 252/392, 422/12 An anti-corrosive composition is disclosed which com
[58] _ Field of Search 25’2/8 55 E’ 8 55 C prises the condensate of a polyamlne such as diethylene
""" R 392‘ 148’, 4'22/12’ triamine, triethylenetetramine or aminoethylethanol
' ’ ’ ’ amine with a 21 or 22 carbon fatty polycarboxylic acid
[56] References Cited or acid anhydride. The composition may additionally
Us. PATENT DOCUMENTS include the condensation products of the above poly
_ amines with either tall oil fatty acids or Rosin S. Propar
2,468,163 4/ 1949 Blair et al. ........................ .. 252/8.55 gyl alcohol has been found to enhance the ami_col.ro_
""" " " sive effects of the composition. The compositions are
3’107’221 10/1963 Harrisori'é't'gl‘ ‘ ' ' ' ' ' ‘ ' ' "552/8 SS'X especially useful in well drilling operations where a
3:134:759 5/1964 Kirkpatrick ct‘ 52/855 X strong inorganic acid is used to facilitate crude oil flow.
3,687,847 8/1972 Maddox et al. .... ..
3,931,029 1/1976 Dutton et al. ................ .. 252/392 X 28 Claims, N0 Drawings
 4,614,600
1 2
U.S. Pat. Nos. 3,773,675 to Heiss et al., in 3,764,543 to
CORROSION INHIBITORS Frenier et al. and in 3,809,655 to Williams.
A search of the prior art failed to uncover any prior
BACKGROUND OF THE INVENTION art reference which discloses the compositions of the
(1) Field of the Invention present invention or is especially useful in reducing the
The present invention relates to compositions and corrosive effects on metal piping by acidizing ?uids
methods for inhibiting the corrosive effects of acids on containing inorganic acids.
metal pipes. More particularly, the present invention Thus, in U.S. Pat. No. 4,344,861 to Levy, a method of
inhibiting the corrosion of metals in contact with petro
relates to compositions formed by the condensation of a
leum and petroleum fractions using bis-amides is dis
polyamine with tall oil and its derivatives and/or with closed. The bis-amides are formed by reacting one or'
particular 21 or 22 carbon unsaturated fatty acid or acid more polyamines with a dimeric acid or with a dicar
anhydrides. Such compositions have been found to be boxylic acid having from 2-12 carbon atoms. Although
especially effective at protecting metal pipes during oil no speci?c dimeric acids are listed, those produced by
well stimulation operations where a 15-30% acid solu dimerizing fatty acids of 18 carbon atoms are stated to
tion is used to increase production in oil wells or in the be of particular interest. The major product, as stated, is
other operations where ferrous metal surfaces are ex a bis-amide although imidazoles might be formed when
posed to strong acidic environments, such as pickling certain polyamines are used. Unlike the present inven
baths and industrial cleaning. tion, the corrosion inhibitors of Levy are effective
(2) Description of the Prior Art 20 against the naturally occurring corrosives in acidizing
To increase reservoir productivity by acidizing, a ?uids and not particularly effective when higher con
corrosive ?uid is pumped down into a limestone or centrations of acids are added to the acidizing ?uid to
dolomite formation to improve formation permeability. aid in the producing operation. See Tables -I, II and VII
The ?uid must etch ?ow channels and dissolve debris to to follow, wherein the dimer acid-diethylenetriamine
restore the original drainage patterns. In fracture acidiz 25 condensate of Levy is shown not to be particularly
ing, acid is pumped down the hole under a pressure effective against the corrosive action of acid concentra
greater than the formation pressure creating new chan tions of as low as 300 mg/l.
nels by fracture. Matrix acidizing is performed by in U.S. Pat. No. 3,687,847 to Maddox, Jr. et al. discloses
jecting acid at lower pressure than the formation pres a composition for inhibiting corrosion in oil wells. As
sure, enlarging the existing ?ow channels. 30 with Levy, the composition of Maddox, Jr. et al is par
Hydrochloric acid (l5—30% concentration) alone or ticularly effective with naturally occurring corrosives
blends with hydro?uoric acid or acetic acid are com such as, HZS, CO2, 02, brine, and organic acids which
monly used for this purpose, and to a lesser extent phos~ are found in natural gas. The composition is formed by
phoric acid. Most of the corrosion inhibitors which are ?rst reacting tall oil with a polyamine to yield an imid
being used to protect the steel pipes through which they azole which is then reacted with a dimeric or trimeric
are pumped into the formations are blends of amines fatty acid. The dimer or trimer is formed from a longer
such as dodecyl amines, alkyl aquinolines, alkyl pyri chain fatty acid, such as, linoleic or eleostearic, having
dines and acetylenic ethanols, with propargyl alcohol 18 carbon atoms and then condensed with a polyamine,
being the most widely used. Compositions for these e.g., imidazoline.
applications are disclosed in U.S. Pat. Nos. 3,816,322 to 40 U.S. Pat. No. 3,134,759 to Kirkpatrick et al., discloses
Griffin et al., 3,802,890 to Keeney. a corrosion inhibiting composition comprising the reac
Ferrous metals, when being formed into steel sheets, tion product of tall oil monocarboxy acids with a poly
plates, bars, etc., are subjected to elevated temperatures. amine to form an intermediate which, in turn, is reacted
Exposure to these temperatures results in the formation with only one of the carboxy groups of organic polycar
boxy acid containing at least 32 carbon atoms. The
of a coating of iron oxide on the metal, commonly
called mill scale. Before these formed materials can be
resulting product was found useful for protecting well
subjected to further processing, such as, electroplating, casings from the corrosive action of weak acids, e.g.,
galvanizing, cold rolling, etc., this scale must be re CO2, HZS, brines, weak inorganic acids, and organic
acids, and not the strong inorganic acids normally
moved. In commercial operations, this scale is removed 50 added to acidizing ?uids.
by immersing the sheet, plate or bar in a suitable acid U.S. Pat. No. 2,920,040 to Jolly, discloses a process
solution, called an acid pickling bath. The acid solution for inhibiting corrosion of ferrous metals when sub
attacks and dissolves the scale. Once the scale is dis jected to corrosive oil well ?uid HgS, CO2, and lower
solved, the acid is then free for further attack upon the organic acids wherein a polyamine is acylated with a
metal. In order to reduce this attack on the metal, corro 55 monocarboxylic acid, such as, rosin acids or fatty acids,
sion inhibitors are added to the pickling bath solution. having 8 to 22 carbon atoms. This acylated intermediate
Corrosion inhibitors are required which protect a forms a salt with an aromatic carboxylic acid.
variety of metals in contact with cleaning solutions U.S. Pat. No. 2,646,399, to Hughes, discloses a
based on a variety of acids which are used over a wide
method for inhibiting corrosion of metals in which a
temperature range. Acids most commonly used are 60 polyamine is reacted with a dibasic acid having 8 or
sulfuric and hydrochloric; acids used for specialty appli more carbon atoms to form bis-imidazoline. The com~
cations include phosphoric, sulfamic, oxalic, tartaric, position is stated to be useful in inhibiting corrosion
citric, acetic, and formic. resulting from a crude oil/brine mixture.
The combination of rosin amine, ethoxylated rosin
amine, ethyloctynol and propargyl alcohol as inhibitors 65 SUMMARY AND OBJECTS OF THE
for this application is disclosed in U.S. Pat. No. INVENTION
3,705,106 to Muzyczko et al. Other effective formula In view of the foregoing limitations and shortcomings
tions contain organic sulfur compounds as disclosed in of prior art compositions based on tall oil or other fatty
 4,614,600
3 4
acid derived products, as well as other disadvantages acid, and the concentration of the acid. The most pre
not speci?cally mentioned above, it should be apparent ferred concentrations of the various inhibitors for the
that there still exists a need in the art for an improved different acids and temperatures are found in the exam
anti-corrosive composition which is effective in acidiz ples. In use, the anti-corrosive properties of the compo
ing ?uids and which will concomittantly protect metal sitions of the present invention were observed with
pipes against the corrosive action of those strong inor
ganic acids which are employed to facilitate a crude oil respect to 1010 steel at temperatures as low as 25° C.
?ow as well as to protect against the corrosive action of and as high as 90° C. In addition, the present composi
agents which are normally present in corrosive ?uids. It tions were found to be effective against the corrosive
is, therefore, a primary objective of this invention to action of hydrochloric, phosphoric, and sulfuric acids.
ful?ll that need by providing an anti-corrosive composi With the foregoing and other objects, advantages,
tion containing the condensation product of a 21 or 22 and features of the invention that will become hereinaf
carbon polycarboxylic acid or acid anhydride with a ter apparent, the nature of the invention may be more
polyamine. clearly understood by reference to the following de
A further object of the present invention is to provide tailed description of the invention and to the appended
an anti-corrosive composition, as aforementioned, claims.
which protects ferrous metal when subjected to HCl,
H3PO4, and H2804 and which is effective over a wide DETAILED DESCRIPTION OF A PREFERRED
range of temperatures. EMBODIMENT
Still another object of this invention is to provide a
method for inhibiting the corrosive effects of acids on The anti-corrosive compositions of the present inven
metal pipes using a composition comprising a synergis tion all employ as a starting material a fatty polycarbox
tic combination of fatty acid/polyamine condensates. ylic acid or acid anhydride having 21 or 22 carbon
Brie?y described, the aforementioned objects are atoms. The polycarboxylic acids or acid anhydrid‘es
accomplished according to this invention by providing which have been found to be particularly ef?cacious
and utilizing condensates of a 21 or 22 carbon polycar starting materials for the anti-corrosive agents of the
boxylic acid or acid anhydride with a polyamine. These present invention are the 21 carbon fatty dicarboxylic
condensates may be combined with the condensates of acid (hereinafter “diacid”) and the 22 carbon fatty tri
either tall oil or Rosin-S (Rosin-S is a trademark prod carboxylic acid (hereinafter “triacid”). The diacid is
uct of Westvaco Corp. and is a medium colored, high prepared by reacting acrylic acid with conjugated lin
softening point tall oil rosin which generally comprises
84% rosin acids and 5% unsaponi?ables. It typically has oleic acid to yield the following general structural for
an acid number of 163, a softening point of 73° C., and mula:
contains 3% fatty acids) with a polyamine. Addition
ally, both propargyl alcohol and sulfonated tall oil have 35 (I)
been found to enhance further the anti-corrosive effects
of the composition of the present invention. ' CH 3(CH2) (CI-I2)yCOOH
Generally, the polycarboxylic acids employed are
diacids or triacids. The ratio of diacid to polyamine by
H COOH
weight, desirably ranges from about 1:1 to about 3:1.
The weight ratio of triacid to polyamine desirably
ranges from about 1:1 to about 3:1. Additionally, the wherein X and y are integers from 3 to 9, and X and y
amount of propargyl alcohol added is generally from together equal 12.
about 25 to about 75 parts by weight and preferably The preparation of the diacid (I) is set forth in detail
about 50 parts by weight per 100 parts by weight of the in US. Pat. No. 3,753,968 to Ward and assigned to
total corrosion inhibiting composition. When sulfonated Westvaco, the assignee of the present invention, the
tall oil is used as an enhancer, it generally ranges from disclosure of which is hereby incorporated by refer
about 10 to 30 parts per weight of the total composition ence.
and preferably is about 20 parts by weight. The triacid is prepared by a similar process as the
A mixture of diacid or triacid and Rosin-S can also diacid except that fumaric acid (instead of acrylic acid)
desireably be reacted with the polyamine. The ratio of is reacted with conjugated linoleic acid to yield the
the polyacids to the rosin should be within the range of
10:90 to 90:10 parts by weight. A preferred ratio is following general structural formula:
about 50:50 parts by weight.
Reaction products of rosin and polyamines are not 55 (11)
very soluble in strong inorganic acids such as hydro
chloric acid. However, by reacting a blend of diacid or CH 3(CI-I2) (CH2)yCOOH
triacid and rosin with a polyamine the resulting product
mixture will give a clear solution in hydrochloric acid.
COOH COOI-I
The rosin containing amidoamine blends, are the better
corrosive inhibitors at higher temperature and exhibit a
pronounced and synergistic effect with propargyl alco wherein X and y are integers from 3 to 9, and X and y
hol or other acetylenic alcohols. together equal 12.
The anti-corrosive compositions of the present inven The preparation of triacid (II) is set forth in detail in
tion are generally added to acidizing ?uid at a concen 65 British Pat. No. 1,032,363 and US. Pat. No. 3,412,056,
tration of generally between 0.01% to 10.0%, by both to Crawford.
weight, and preferably from about 0.1% to about 2.0%, The diacid (I) and triacid (II) are commonly de
by weight, depending on the temperature, the type of scribed by the general structural formula:
 4,614,600
6
enetetramine (hereinafter “TETA”) or aminoethyle
thanolamine (hereinafter “AEEA”), to form an amide
condensation product. Since two primary amino groups
are available for reacting in the above DETA and
TETA, they are more reactive than the secondary
Z Z amino groups, and it is one of the two terminal amino
groups on each polyamine which will react. When one
wherein x and y are integers from 3 to 9, x and y to mole of diacid is reacted with two moles DETA, the
gether equal 12, one Z is COOH and the remaining Z is resulting compound which is formed has the following
selected from the group consisting of H and COOH. typical structural formula:
It is not necessary to isolate linoleic acid in order to
carry out the above-described reactions. Where a multi
(IV)
acid composition such as tall oil is used the linoleic acid
component of the mixture reacts, and the remaining 15 CH3(CH2)5 (CHZ)7CONHCHZCHZNHCHCHZNHZ
mono unsaturated fatty acids present in tall oil remain
essentially unchanged except for the isomerization of
oleic acid to elaidic acid. By distilling off the reamining CONHCHZCHZNHCHZCHZNHZ
fatty acids the polycarboxylic acids are enriched in the
residue. When higher temperatures are employed, e.g., from
20
A 22 carbon fatty acid anhydride is obtained by a 480° F. to 570° F., the formation of a diimidazoline of
similar process wherein the tall oil fatty acids are heated the following typical structural formula is expected:
with maleic anhydride, in the presence of iodine‘ as
catalyst, to yield a mixture of anhydrides having a cy
clohexene ring system (cyclohexene dicarboxylic acid N-CHZ (V)
anhydride type A and a non-cyclic succinic acid anhy /
dride type B and C, carboxy alkenyl succinic anhy
dride). The conjugated linoleic acid with two double N-CH
N-CHZ 2
bonds gives the cyclohexene tricarboxylic acid anhy //
dride (III A); the oleic and elaidic acid with one double
bond gives the succinic anhydride type triacids (III B
and III C). The anhydride mixture formed includes N-CHZ
compounds having the following structural formulae: CHzCHgNI-Ig

(III A) 35 By using AEEA as the polyamine the terminal NH;

groups are substituted by —OH groups.
However, since the diacid is not obtained in 100%
purity and during the condensation reaction some of the
DETA boils off with the water of condensation, a com
plex mixture of amido amine, imidazoline, diimidazo
line, diamidoamine and condensates of higher molecular
weight are formed as the minor reaction products. In
the corrosive tests it was found that those condensates
perform best which were synthesized with diacid in
45 excess of DETA, e.g., 2.5:1 (weight basis).
The triacid or the triacid anhydrides react similarly to
the diacid. Thus, one of the primary amino groups of
' the polyamine reacts with the terminal carboxyl groups
of the triacid, i.e., the carboxyl groups of the original
50 fatty acids.
Based on the knowledge of the reaction of succinc
acid or succinic anhydride or 4-cyclohexene-1,2-dicar
boxylic acid and its anhydride and amines or poly
amines, and from infrared spectroscopic evidence it
55
appears that ?rst the two remaining carboxyl groups or
the anyhydride functionality forms an amine imide of
the structure VI A or VI B, vis:

The bicyclic Diels-Alder adduct (III A) is disclosed (VI A)

in British Pat. No. 1,032,363 and US. Pat. No. 3,412,056
both to Crawford; the “ene” adducts (III B and III C) CH3(CHZ) (CH2)7CONHCHZCHZNHCHZCHZNHZ
are disclosed in German Pat. No. 973,398 to Stein et a1.
and in US. Pat. No. 3,451,958 to Riedeman et al.
The above-identi?ed starting compounds ( I, II, III 65
A, III B and III C), namely, diacid, triacid, and their
acid anhydrides are reacted with a polyamine such as
diethylenetriamine (hereinafter “DETA”) and triethyl
 4,614, 600
7 8
-continued distillate was collected. A mixture of condensates,
namely, diacid-DETA and tall oil fatty acid (without
linoleic acid, containing mostly oleic acid and elaidic
CH - C acid) - DETA, as well as diacid-DETA-fatty acid con
densates was thereby produced.
NCHZCHZNHCHZCHZNHZ
EXAMPLE 2

0
(Diacid condensed with DETA)
The intermediate described in Example 1 was vac
This assumption is supported by the fact that water uum distilled thereby removing most of the 18 carbon
formed during the reaction is collected at lower temper atom monocarboxylic acids (mainly oleic and elaidic).
ature than when either diacid or any fatty acid is re The remaining 21 carbon dicarboxylic acid was then
acted with a polyamine. blended with DETA at a ratio of l0-30 parts by weight
Condensation products of polyamines and the above diacid to 10 parts DETA and heated to 260°—270° C.
described polycarboxylic acids and polyamines are dis
closed in U.S. Pat. No. 4,447,269 to Schilling et al. until all the distillate was collected. The resulting diacid
Corrosion inhibiting condensates of the present in - DETA condensate was then cooled to 100° C. and 100
vention are obtained when combinations of diacid or parts were diluted with 30 to 100 parts of isopropanol or
triacid and tall oil fatty acids, or other fatty acids and 20 glycol.
Rosin-S are reacted with polyamines. For example,
when 2.5 g/500 ml of diacid-DETA condensate was EXAMPLE 3
added to a fluid containing 15% hydrochloric acid at (Diacid/Rosin-S condensed with DETA)
92° C., there was a 0.0363 lbs/ft2 of weight loss after 6
hrs. Under the same conditions, there was only a 0.0297 25 10-90 parts by weight of the diacid were blended
lbs/ft2 weight loss when the above additive was pre with 90-10 parts by weight of Rosin-S. l0-30 parts of
pared from a diacid/Rosin-S blend and DETA. Simi that blend were then heated with 10 parts by weight of
larly, when 15% sulfuric acid was substituted for 15% DETA at 260°-270° C. until all the distillate was col
hydrochloric acid, there was a weight loss of 0.0842 lected. The mixture was then cooled to 100° C. and 100
lbs/ft2 using a condensate of diacid and DETA. How parts were diluted with 30 to 100 parts isopropanol.
ever, there was a weight loss of only 0.0811 lbs/ft2 when
the polyamine condensate of a diacid-tall oil fatty acid EXAMPLE 4
blend was used. The above compositions are generally (Triacid/tall oil fatty acid condensed with DETA)
diluted with either isopropanol or glycol.
The compositions of the present invention have also 35 280 parts by weight of tall oil fatty acid and 10-60
been found to exhibit a synergistic effect when either parts by weight of fumaric acid were heated to
propargyl alcohol or sulfonated tall oil were added. 200°—220° C. for 4-6 hours in the presence of a catalytic
Thus, condensates of DETA with a blend of diacid and amount of iodine. An intermediate having a 22 carbon
tall oil fatty acids were added at a rate of 75 mg/ 250 ml tri-carboxylic acid (II) as well as the unreacted tall oil
of acidizing ?uid containing 30% hydrochloric acid, the fatty acids (containing partially isomerized oleic acid,
resulting weight loss of 1010 steel was 0.0122 lbs/ft2 i.e., elaidic acid) was thereby produced. After cooling,
over a period of 24 hours at 25° C. However, when the
75 mg of additive contained a 1:1 ratio of condensates to l0-30 parts by weight of this intermediate were heated
propargyl alcohol, the resulting weight loss was only with 10 parts by weight of DETA to 260°—270° C. until
0.0084 lbs/ft2. In both tests the steel specimen used was 45 all the distillate was collected.
identical, i.e., 9 sq. in. (0.0625 sq. ft., approx. 12.5 g). EXAMPLE 5
Similarly, 2.5 g of the same condensate composition
per 500 ml of a corrosive ?uid containing 15% sulfuric (Triacid condensed with DETA)
acid resulted in a weight loss of 0.0811 lbs/ft2 of 1010
The intermediate obtained in Example 4 was distilled
steel at 92° C. after 6 hrs. However, the resulting weight 50
loss was only 0.0625 lbs/ft2 when the condensate was under reduced pressure thereby removing the monocar
combined with sulfonated tall oil fatty acid at a ratio of bo'xylic acids (mostly oleic and elaidic). 10-30 parts by
4:1. weight of the still residue was heated with 10 parts by
The practice of this invention may be more clearly weight of DETA at 260°—270° C. until all the distillate
understood from the following non-limiting illustrative was collected. After cooling to 100° C., 100 parts of the
examples. All amounts shown are by weight. condensate was diluted with 30 to 100 parts isopropa
EXAMPLE 1 nol.
(Diacid/tall oil fatty acid condensed with DETA) EXAMPLE 6
280 parts tall oil fatty acid and 10-36 parts of acrylic 60 (T riacid/Rosin-S condensed with DETA)
acid were reacted in the presence of a catalytic amount
10-90 parts by weight of the residue obtained in Ex
of iodine at 250° C. to form an intermediate. (Formula
I). The intermediate formed comprised a 21 carbon ample 5 were heated with 90-10 parts by weight of
dicarboxylic acid in addition to the unreacted tall oil Rosin-S. 10-30 parts by weight of this blend were then
fatty acids. This process is described with greater par 65 reacted with 10 parts by weight of DETA at 260°—270°
ticularity in U.S. Pat. No. 3,753,968. 10-30 parts of the C. until all the distillate was collected. The condensate
above intermediates were then reacted with 10 parts, by was cooled to 100° C. and 100 parts diluted with 30 to
weight DETA and heated to 260°~270° C. until all the 100 parts isopropanol.
 4,614,600 '
9 10
EXAMPLE 7 TABLE I-continued
CORROSION OF 1010 STEEL IN 30%
(Tricarboxylic acid anhydride condensed with DETA) Hydrochloric Acid at 25° C. (Exposure Time:
280 parts by weight of tall oil fatty acid such as L-5 (a 24 hrs., INHIBITOR DOSAGE: 75 mg/250 ml)
Westvaco designation of a tall oil fatty acid fraction Weight Loss
containing about 5% rosin consisting mostly of linoleic (lbs/sq.
ft. >< hrs)
and oleic acid) or 1483 (a Westvaco designation of a
Condensate B/Propargyl Alcohol ( 1:1) 0.00037
distillate removed from the crude diacid containing
Notes
3—5% rosin consisting mostly of oleic and elaidic acid) "The blend is the unre?ned mixture of L-5 reacted with 12% acrylic acid by weight.
were heated with 100-150 parts by weight of maleic hBlend prepared from 1483 and maleic anhydride at a ratio 5.6:].0 without iodine.
‘Blend prepared from L-S with fumaric acid at a ratio of 6.25:1.0 with iodine as
anhydride in the presence of a catalytic amount of io catalyst.
dine or without iodine for 4-10 hours at l80°-220° C. In ‘jEmpol 1010, manufactured by Emery Industries, Inc.
the presence of iodine, a mixture of anhydrides having a
cyclohexene ring system (cyclohexene dicarboxylic As seen in TABLE I, the compositions of Examples
acid anhydride type (III A) and a non-cyclic succinic 1, 2, 4, and 7 perform better than propargyl alcohol
acid anhydride type (III B and III C) were obtained. alone, condensates of tall oil fatty acids and DETA, or
When reacted without iodine, only succinic acid type condensates of dimer acid and DETA. The improved
anhydrides (III B and III C) were obtained. 10-30 parts anti-corrosive effects of the compositions of Examples 1
by weight of these anhydrides (with some unreacted 20 and 4 is even more pronounced when propargyl alco
monocarboxylic acid) were heated to 260°—270° C. until hol, a commonly used corrosion inhibitor, is mixed
all the distillate was collected. After cooling to 100° C., therewith at a 1:1 ratio.
the condensate was diluted with isopropanol. As shown
EXAMPLE 9
in Examples 1, 3, 4, and 6, blends of these tricarboxylic
acids with Rosin S or tall oil fatty acid may be prepared. 25 (Comparative tests)
EXAMPLE 8 The compositions of Examples 2, 3, 4, 6, and 7 of the
present invention were compared to condensates of
(Comparison tests) DETA and dimer acid (Empol 1010, Emery Industries,
The compositions of Examples 1, 2, 4, and 7 of the Inc.) and dimer acid/rosin blends. The tests were car
30 ried out using 2.5 g of inhibitor per 500 ml of ?uid
present invention were compared to other anti-corro
sive compositions. The corrosion tests were carried out containing 15% hydrochloric acid at 92° C. In the high
in the following manner: temperature test 500 ml acid containing the inhibitor
A 1010 steel coupon (Q-Penel Company, Cleveland, was heated in a 3-necked ?ask equipped with a con
Ohio) having about 9 in. sq. surface area and 12.5 g was 35 denser and thermometer. The steel coupon was inserted
rinsed with acetone. After drying the coupon was in in the corrosion liquid after the predetermined tempera
serted in to a glass bottle containing 250 ml acidizing ture was reached. Weight loss measurements with 1010
?uid (30% HCl) and corrosion-inhibitor. The-coupon steel were made after 6 hrs. exposure time with the
was removed, rinsed with water and re-weighed after results shown in TABLE II.
drying. v 40 TABLE II
The tests were carried out using 75 mg of inhibitor CORROSION OF 1010 STEEL IN 15% l-ICl at 92° C.
per 250 ml of acidizing ?uid. The weight loss for the (Exposure Time: 6 hrs, Inhibitor Dosage: 2.5 g/500 ml)
1010 steel coupon after 24 hours of exposure at 25° C. Weight Loss
was then determined. The results are shown in the (lbs/sq.
TABLE I. ft. X hours)
45
DIACID l550/Rosin S-DETA (l.0:l.0:l.0) 0.00495
TABLE I Condensate
CORROSION OF 1010 STEEL IN 30% C19—Dicarboxylic Acida/Rosin S- 0.00578
Hydrochloric Acid at 25° C. (Exposure Time: DETA (l.0:1.0:1.0) Condensate
24 hrs., INHIBITOR DOSAGE: 75 mg/250 ml) DIACID lSSO-DETA (2.5:1.0) Condensate 0.00605
Cgg-Tricarboxylic Acid Anhydrideb/ 0.00623
Weight Loss Rosin S-DETA (l.0:1.0:l.0) Condensate
(lbs/sq. Diacid l550-Rosin S-TETA (1.0:I.0:l.0) 0.00578
ft. >< hrs) Condensate
Controls C22——Tricarb0)tyliC Acid/ 0.00632
Tall Oil Fatty Acid~DETA (2.8:1.0) Condensate 0.00148 Rosin S-DETA (1.0:l.0:1.0) Condensate
Dimer Acidd-DETA (1.00.0) Condensate 0.00356 Cgg-Tricarboxylic Acid Anhydridec/ 0.00858
55 Rosin S-DETA (1.0:l.0:1.0) Condensate
Example 1
Cy-Tricarboxylic Acid/ 0.00885
DIACID 1550/1‘all Oil Fatty Acida-DETA 0.00051 Tall Oil Fatty Acidd-DETA (1.0:1.5:1.0)
(1.0:l.5:1.0) Condensate (A) Condensate
Example 2 Dimer Acid"-DETA (1.0:1.0) Condensate 0.01770
DIACID l550(C21—dicarboxylic acid)- 0.00071 Tall Oil Fatty Acid-DETA (2.8:l.0) Condensate 0.01870
DETA (2.5:1.0) Condensate 60 Dimer Acid‘VRosin S-DETA (1.4:l.4:l.0) 0.02422
Example 4 V Condensate
C23-—Tricarboxylic Acid/T all Oil Fatty 0.00058 Notes
Acidt-DETA (l.0:l.5:l.0) Condensate (B) “Supplied by Union Camp Corp.
Example 7 bclr-Tricarboxylic anhydride prepared from L-5 and maleic anhydride at 2.8:1.0,
with iodine as catalyst.
Cgg-Tricarboxylic Acid Anhydride/ 0.00052 65 fC33—Tricarboxylic anhydride prepared from 1483 and maleic anhydride at 2.8:l.0
Tall on Fatty Acidb-DETA (1.25:1.25=1.0) without iodine.
Condensate dBlend prepared from L6 and fumaric acid at a ratio of 6.5:l.0.
Propargyl Alcohol 0.00082 "Empol 1010, manufactured by Emery Industries, Inc.
Condensate A/Propargyl Alcohol (1:1) 0.00035
 4,614, 600
11 12
As seen in TABLE II, the compositions of the pres TABLE IV
ent invention are signi?cantly more effective anti-cor
CORROSION OF 1010 STEEL IN 15%
rosives (at least twice as effective) than conventional PHOSPHORIC ACID AT 25“ C.
dimer acid-DETA condensates or tall oil fatty acid (Exposure Time: 170-190 hrs., Inhibitor
DETA condensates, and dimer acid/Rosin S-DETA Concentration: 75 mg/250 ml)
condensates. Weight Loss
(lbs/sq.
EXAMPLE 10 ft. >< hours)
(Comparative Tests) DIACID 1550/Tall Oil Fatty Acida-DETA
10 (1.0:l.5:1.0) Condensate
0.000050
The compositions of Examples 2, 3, 5, 6, and 7 of the Czg-Tricarboxylic Acid Anhydride/ 0.000067
present invention were compared to propargyl alcohol Tall Oil Fatty Acidb-DETA (1.0:l.5:1.0)
alone as well as to the condensate of Rosin-S and Condensate
DETA. The tests were carried out as in Example 9, C22—Tricarboxylic AcidC/T all Oil Fatty Acid- 0.000067
except that the amount of inhibitor was decreased from 15 DETA (1.0:l.5:1.0) Condensate
2.5 g/500 ml to 0.5 g of amine condensate plus 0.5 g Notes
"The blend is the unre?ned mixture of L5 reacted with 12% acrylic acid (by
propargyl alcohol per 500 ml of corrosive ?uid. The weight)
results are shown in TABLE III. I’Blend prepared from 1483 and maleic anhydride at a ratio 5.6:l.0 without iodine.
cBlend prepared from L-S with l'umaric acid at a ratio of 6.25:1.0 with iodine as
TABLE III catalyst.
20
CORROSION OF 1010 STEEL IN 15% I-ICI at 92° C.
(Exposure Time: 6 hrs., Inhibitor Dosage: 0.5 g Amine
Condensate + 0.5 g Propargyl Alcohol/500 ml) EXAMPLE 12
Weight Loss (Comparative Tests)
(lbs/sq. ft. X hours)
The compositions of Examples 2, 3, and 6 of the pres
Propargyl Alcohol (1.25 g) 0.0009166
DIACID 1550/Rosin S-DETA (3.0:1.0) 0.0003166 ent invention were compared with the condensates of
Condensate Rosin S and tetraethylenetriamine (TETA) as well as
Rosin S>DETA (3.0:1.0) Condensate 0.000358 the condensates of tall oil fatty acid/Rosin S with
(Turbid)” DETA. The tests were carried out using 1 g. of inhibi
C22—Tricarboxylic Acid/Rosin 8- 0.000366 30
DETA (1.0:1.0:1.0) Condensate tor per 500 ml of corrosive ?uid containing 15% phos
Dimer Acidb/Rosin S-DETA (1.4:1.4:1.0) 0.000383 phoric acid at a temperature of 92° C. After 6 hours, the
Condensate (Turbid)” resulting weight loss to 1010 steel was measured and the
Diacid 1550/Rosin S-DETA (1.0:1.0:1.0) 0.000383
Condensate
results are shown in TABLE V.
Cgz-Tricarboxylic Acid Anhydridec/ 0.0004333 35 TABLE V
Rosin S-DETA (1.0:1.0:1.0)
Condensate CORROSION OF 1010 STEEL IN 15%
DIACID 1550-DET>A (2.5110) 0.000667 PHOSPHORIC ACID AT 92° C. (Exposure
Condensate Time: 6 hrs., Inhibitor Dosage: l g/500 ml)
C2Z—Tricarboxylic Acid- 0.000833 Weight Loss
DETA (1.0:1.0) Condensate (lbs/sq.
C19—Dicarboxylic Acidd-DETA (20:10) 000135 ft. >< hours)
Condensate
Rosin S-TETA (2.0210) Condensate (Turbid) 0.00377
Notes
I‘Not all of the reactive product is soluble in the acidic fluid.
DIACID 1550/Rosin S-DETA (1.0:l.5:1.0) 0.00620
I’Empcl I016 manufactured by Emery Industries, Inc. Condensate
"Prepared from 1483 and maleic anhydride at a ratio of 2.8:1.0 without iodine. 45 C32—Tricarboxylic Acid/Rosin S- 0.00627
dSupplied by Union Camp. Corp. DETA (1.0:1.0:l.0) Condensate
C|9—Dicarboxylic Acid/Rosin S-DETA 0.00838
Even though less than half the amount of additive (1.0:l.0:1.0) Condensate
DIACID 1550-DETA (2.5:l.0) Condensate 0.01032
was used in this example than in Example 9, the compo Tall Oil Fatty Acidb/Rosin S-DETA 0.01148
sitions of Example 10 were nonetheless more effective 50 (l.27:l.27:l.0) Condensate (Turbid)
corrosion inhibitors due to the synergistic effects which Notes
propargyl alcohol has on the condensates of the present "Supplied by Union Camp Corp.
invention. It can also be seen that the diacid/Rosin Imm oil fatty acid: L-S
S-DETA condensates of Example 1 are more effective
than the dimer acid Rosin S-DETA condensates. Rosin 55 As seen in TABLE V, the compositions of the pres
S-DETA and dimer acid-Rosin S-DETA condensates ent invention give clear solutions and are more effective
give turbid solutions whereas solutions of the conden than the condensates of tall oil fatty acid/Rosin S with
sates containing diacid/Rosin S or czg-tricarboxylic DETA. ~

acid (anhydride)/Rosin S blends are clear.

60 EXAMPLE 13
EXAMPLE 1 1 (Comparative Tests)
(Comparative Tests) The compositions of Examples 1, 4, and 7 of the pres
The compositions of Examples 1, 4, and 7 were added ent invention were tested in a corrosive ?uid containing
to a 25° C. corrosive ?uid containing 15% phosphoric 65 15% sulfuric acid at 25° C. at a rate of 0.8 g of inhibitor
acid at a rate of 75 mg/250 ml. After 170-190 hours of per 250 ml. of fluid. After 171 hours of exposure, the
exposure, the weight loss of 1010 steel was measured. weight loss of 1010 steel was determined, and the results
The results are shown in TABLE IV: are shown in TABLE VI.
 4,614,600
13 14
TABLE VI brought into contact with strong acidic ?uids, such as in
CORROSION OF 1010 STEEL IN 15%
pickling baths or industrial cleaning.
SULFURIC ACID AT 25° C. (Exposure Although only preferred embodiments are speci?
Time: 171 hrs.. Inhibitor Dosage: 0.8 g/250 ml) cally illustrated and described herein, it will be appreci
_ Weight Loss ated that many modi?cations and variations of the pres
(lbs/sq. ft. >< hours) ent invention are possible in light of the above teachings
Cgg-Tricarboxylic Acid/Tall Oil 0.000022 and within the purview of the appended claims without
Fatty Acida-DETA (1.0:1.5:1.0) departing from the spirit and intended scope of the
Condensate
Cgg-Tricarboxylic Anhydride/l'all Oil 0.000032 invention.
Fatty Acidb-DETA (1.011.510) What is claimed is:
Condensate 1. A composition for inhibiting the corrosive effects
D1AC1D 1550/Ta1l Oil Fatty AcidC-DETA 0.000036
Condensate (1.0:1.5:1.0)
of acids on steel or ferrous metal surfaces exposed to an
Notes
acidic corrosive ?uid comprising a condensate of a
"Blend is prepared from L-S with fumarie acid at a ratio o1'6.25:1.0 with iodine as 15 polyamine with a polycarboxylic acid selected from the
catalyst. group consisting of the general formula
"Blend is prepared from 1483 with maleic anhydrate at a ratio of 5.6:l.0 without
iodine.
‘The blend is the unre?ned mixture of L5 reacted with 12% acrylic acid by weight.

EXAMPLE 14 CH3(cH2)x (cl-lpycoori

(Comparative Tests)
Z Z
The compositions of examples 1, 2, 4, and 7 of the
present invention were tested under the same conditions
25 wherein x and y are integers from 3 to 9, x and y to
as Example 9 except that sulfuric acid was substituted
for hydrochloric acid. The weight loss of 1010 steel was
gether equal 12, one Z is COOH and the remaining Z is
then determined, and the results are shown in TABLE
selected from the group consisting of H and COOH, the
VII. anhydrides of said general formula and mixtures thereof
and further comprising propargyl alcohol in an amount
TABLE VII 30 of from about 25 to about 75 parts per 100 parts by
CORROSION OF 1010 STEEL IN 15% weight of the total corrosion inhibiting composition.
SULFURIC ACID AT 92° C. (Exposure 2. The corrosion inhibiting composition according to
Time: 6 hrs., Inhibitor Dosage: 2.5 g/500 ml)
claim 1 wherein said polyamine is a compound selected
Weight Loss
(lbs/sq. from the group consisting of diethylenetriamine, trieth
35
ft. >< hours) ylenetetramine, and aminoethylethanolamine.
CZ3—Tricarboxy1ic Acid/T all Oil 0.0118 3. The corrosion inhibiting composition according-to
Fatty Acid‘J-DETA (1.0:1.5:1.0) Condensate (A) claim 2 wherein 10-30 parts by weight of said polycar
DIACID l550/Tall Oil Fatty Acidb-DETA 0.0135 boxylic acid are condensed with 10 parts of diethylene
(l.0:1.5:l.0) Condensate (C) triamine.
DIACID ISSO-DETA (2.5:1.0) Condensate 0.0140
Tall Oil Fatty Acid‘DETA (2.8110) 0.0172 4. The corrosion inhibiting composition according to
Condensate (imidazoline) claim 1, wherein the condensate is formed by reacting
C33—-Tricarboxylic Anhydride/Tall Oil 0.0175 the polyamine with a blend of the polycarboxylic acid
Fatty Acida-DETA (1.0:l.5:1.0)
Condensate (B) and tall oil fatty acid wherein the blend is formed by
Dimer Acidd-DETA (1.0110) Condensate 0.0386 45 reacting 280 parts- tall oil fatty acid with 10—36 parts
Propargyl Alcohol 0.0704 acrylic acid in the presence of a catalytic amount of
Condensate A/Propargyl Alcohol (1:1) 0.00407 iodine at 250° C. said parts being parts by weight.
Condensate B/Propargyl Alcohol (1:1) 0.0051
Condensate C/Propargyl Alcohol (1:1) 0.00407 5. The corrosion inhibiting composition according to
Condensate C/Sulfonated Tall Oil Fatty 0.01042 claim 4 wherein 10 parts of diethylene triamine is con
Acid (4.0.1.0) densed with 10-30 parts of the blend having 10-90 parts
Notes of said polycarboxylic acid and 90-10 parts of tall oil
"Blend derived by reacting L-S with fumaric acid at a ratio 6.25:1 in the presence of
iodine. fatty acids said parts being parts by weight.
bUnrel'tned mixture of L-5 reacting with 12% acrylic acid by weight. 6. The corrosion inhibiting composition according to
‘Blend derived by reacting 1483 with maleic anhydride at a ratio 56:1.0
dEmpol 1010 manufactured by Emery lndustries, lnc. claim 2 wherein the condensate is formed by reacting
55
the polyamine with a blend of the polycarboxylic acid
From the foregoing, it will be appreciated that the and a tall oil rosin comprising 84% rosin acids and 5%
compositions of the present invention are at least twice unsaponi?ables wherein the weight ratio of polycarbox
as effective as the condensate of dimer acid and DETA. ylic acid to tall oil rosin is from 10:90 to 90:10.
They are also substantially more-effective than the imid 60 7. The corrosion inhibiting composition according to
azoline condensate of tall oil fatty acid and DETA. The claim 6 wherein 10 parts of diethylenetriamine is con
enhancing effect of using the compositions of Examples densed with 10-30 parts of the blend having 10-90 parts
1, 4, and 7 in a 1:1 ratio with propargyl alcohol can also of said polycarboxylic acids and 90-10 parts of a tall oil
be clearly seen. Additionally, the use of the Example 7 rosin comprising 84% rosin acids and 5% unsaponi?a
composition with sulfonated tall oil fatty acid at a ratio 65 bles said parts being parts by weight.
of 4:1 results in a highly effective anti-corrosive compo 8. The corrosion composition according to claim 1
sition. These anti-corrosive compositions can also be wherein said polycarboxylic acid is a 21 carbon dicar
used in other applications where steel or ferrous metal is boxylic acid compound of the formula:
 4,614,600
15 16
ratio of from about 1-3 to about 1 by weight, respec»
tively.
17. The method according to claim 14 wherein pro
cHacHnX (cnwcoon pargyl alcohol is added to said acids in an amount of
from about 25 to about 75 parts per 100 parts by weight
of the total of said condensation product plus said pro
COOH pargyl alcohol.
18. The method according to claim 14 wherein said
wherein x and y are integers from 3 to 9 and x and y polycarboxylic acid is a 21 carbon dicarboxylic acid
together equal 12. 10 compound of the general formula
9. The corrosion composition according to claim 8
wherein x is 5 and y is 7.
10. The composition according to claim 1 wherein
said polycarboxylic acid is a 22 carbon tricarboxylic
acid compound of the formula: cumin). (CHpycooi-i

COOH

CH3(CH2)X (clmycoon wherein x and y are integers from 3 to 9 and x and y

together equal 12.
HOOC COOH
19. The method according to claim 14 wherein said
polycarboxylic acid is a 22 carbon tricarboxylic acid
wherein x and y are integers from 3 to 9 and x and y
compound of the general formula
together equal 12.
11. The corrosion composition according to claim 10 25
wherein x is 5 and y is 7.
12. The corrosion inhibiting composition according
to claim 1 wherein said anhydride is a 22 carbon tricar
boxylic acid anhydride compound of the formula: HOOC COOH

wherein x and y are integers from 3 to 9 and x and y

together equal 12.
cnucuzix (CHZUCOOH 20. The method according to claim 14 wherein the
35 polycarboxylic acid includes a mixture of 21 carbon
dicarboxylic and 22 carbon tricarboxylic acids.
21. The method according to claim 19 including add
ing to said acids propargyl alcohol in an amount of from
wherein x and y are integers from 3 to 9; and x and y
about 25 to about 75 parts per 100 parts by weight of the
together equal 12. total of said condensation product plus said propargyl
13. The corrosion composition according to claim 12 alcohol.
wherein x is 5 and y is 7. 22. The niethod according to claim 20 including add
14. A method of protecting metals from the corrosive ing to said acids propargyl alcohol in an amount of from
effects of acids used for acidizing and fracturing in oil about 25 to about 75 parts per 100 parts by weight of the
well stimulation comprising the step of adding to said 45 total of said condensation product plus said propargyl
acids an effective amount of a condensation product of alcohol.
a polyamine with a polycarboxylic acid selected from 23. The method according to claim 14 comprising a
the group consisting of the general formula 21 carbon dicarboxylic acid anhydride.
24. The method according to claim 14 comprising a
22 carbon tricarboxylic acid anhydride.
25. The method according to claim 14 wherein the
CHs(CHz)X (CHZ)yCOOH concentration of said condensation product employed
ranges from 0.0l% to 10% by weight of the corrosive
?uid.
Z Z 55 26. The method according to claim 14 wherein the
concentration of said condensation product employed is
wherein x and y are integers from 3 to 9, x and y to about 0.1-2% by weight of the corrosive ?uid.
gether equal 12, one Z is COOH and the remaining Z is 27. The method according to claim 26 further includ
selected from the group consisting of H and COOH, the ing adding to said acids propargyl alcohol in an amount
anhydrides of said general formula and mixtures of from about 25 to about 75 parts per 100 parts by
thereof. weight of the total of said condensation product plus
15. The method according to claim 14 wherein said said propargyl alcohol.
acids used for acidizing and fracturing in oil well stimu 28. The method according to claim 27 further includ
lation are selected from the group consisting of HCl, ing adding to said acids propargyl alcohol in an amount
H3PO4, and H2804, employed alone or in combination 65 of from about 25 to about 75 parts per 100 parts by
with hydrofluoric acid or acetic acid. weight of the total of said condensation product plus
16. The method according to claim 14 wherein the said propargyl alcohol.
polycarboxylic acids and polyamine are present at a * * * * *