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Патент USA US3077459

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3,077,453
' lice
Patented Feb. 12, 1963
2
3,077,453
ware
The stannous ion is conveniently incorporated in the
inhibitor composition by employing such compounds, as
for example, stannous chloride, stannous bromide, stan
nous sul?de, stannous oxide, their hydrates and the like.
The acetylenic compounds which are synergized by
No Drawing. Filed Sept. 1., 1961, Ser- No. 135,432
4 Claims. (@Cl. 252—14'7)
the presence of the stannous ion are the acetylenic alco
hols and diols, such as for example, propargyl alcohol,
CORR?SiQN HNHIBITHGN
Billy D. (Bakes, Tulsa, 61:521., assignor to The Dow Chern
ical Company, Midland, Mich, a corporation of Dela
methylbutynol, butynediol, l-ethynylcyclohexanol, 3
The present invention relates to the prevention of cor
methyl-l-nonyn-3-ol, 2-methyl-3-butyn-2-ol, and (AC-eth
rosion of metals in contact with acids. More particu
larly the present invention relates to corrosion inhibiting 10 ynyl 2,4,6-trimethylbenzyl alcohol. Thus, in general,
acetylenic compounds having the general formula
I‘ compositions containing acetylenic or nitrogen com
pounds and tin compounds.
Many compounds have been proposed to inhibit the
’ corrosion of metals in contact with acids.
These com
pounds and compositions containing these compounds 15
wherein each R represents an independently selected radi
have proved satisfactory in limited application. How
cal of the group consisting of hydrogen, lower alkyl, i.e.,
ever, to date, no single composition has been found which
1 to 4 carbon'atoms, phenyl, substituted phenyl; or hy
is effective in preventing corrosion of metal in contact
droxy loweralkyl and the u-R’s may be fused together
with all of the industrial acids in use today. Further,
_
many of the inhibitors, excellent at low temperatures, are 20 to form a 5 or 6 membered ring. _ The amines which are effectively synergized by the ac.
ineifective at temperatures above about 80° C.
tion of stannous ion, either alone or in combination with
‘It is therefore an object of the present invention to
the acetylenic compound, are for example the mono, di
provide a new and useful composition for the prevention
and trialkyl amines having from 2 to 6 carbon atoms in
of corrosion of metals in contact with acids. It is a fur
ther object of the present invention to provide a corrosion 25 each alkyl moiety as well as the 6 membered N-hetero-v
cyclic amines, i.e., the alkylpyridines and mixtures there‘
inhibitor composition which will be effective at tempera
of. Such amines include ethylamine, diethylamine, tri~
tures as high as 150° C., and further, which composition
ethyiamine, propylamine, dipropylamine, tripropylamine,
is effective over a longer period than heretofore thought
mono, di and tributylamine, mono, di and tripentylamin'e,
possible. These and other objects will become apparent
to those skilled in the art from the following description 30 mono, di and trihexylamine, as well as their isomers such
as isopropylamine, tertiary~butylamine and the like, and
and claims.
the alkylpyridines having from 1 to 5 nuclear alkyl sub
It has now been found that the presence of the stannous
stituents per pyridine, moiety, said alkyl substituents hav
ion in conjunction with the acetylenic or amine moiety of
ing from 1 to 12 carbon atoms, and preferably those hav
an organic compound effectively inhibits the corrosion of
ing an average of 6 carbon atoms per pyridine moiety,
metal when such metal is in contact with aqueous acids.
such as a mixture of high-boiling tertiary-nitrogen-hetero
Thus, one can employ a stannous-ion-producing com
cyclic compounds having an equivalent weight of approxi
pound in combination with an acetylenic compound or
mately 170 (Alkylpyridine HR, a product of Union Car
in combination with an amine or both and obtain,
bide and Carbon (3.0.).v
I
when the inhibitor composition is mixed with an aqueous
The following examples are illustrative of the present
acid, a marked improvement in corrosion inhibition over 40
that obtained employing any one of the ingredients alone
invention but are not‘ to be construed as limiting.
or a combination of the ingredients without stannous ion.
Good results have been obtained when the inhibitor com.
position contains stannous ion in the amounts of from
as little as 2 percent by weight to about 60 percent by
weight. The amount of stannous ion which in an aqueous
Tests were run with mixtures of various acetylenic com¢
pounds and stannous chloride as hydrochloric acid inhibi
Examples 1-24
tors employing API N80 tubing (1" wide quarter segment
of 2.375" ‘outside diameter pipe, wall thickness of 0.187")
and AISI 101,0 coupons (2.75” x 1.0” x 0.12”). The
acid employed was aqueous ‘15 percent hydrochloric acid
acid composition imparts an improved eifect is from
about 0.008 percent by weight to about 0.32 percent by
weight, and preferably from about 0.08 percent by weight
and the test coupon was left in the acid for loihours,
except where indicated. The results of such tests are
to about 0.24 percent by weight based on the weight of
the aqueous acid solution.
tabulated below:
'
Concen
Concentration of Acetylenic or Alkylé‘
tration
Ex.
pyridines in Inhibitor (percent by
Stannous
No.
volume)
Ionl (per‘
weight)
1 ____ __
Metal
none ...................... -.'__-.. ..... ..
.
0.32
.
API N80___.
.
__.__(1
.4 n‘
4 MB _______________________ --
.4 propargyl alcohol (Coded PA
..
.4 butynediol (Coded BD).4 DD ___________ _, ................... __
Corrosion Rate
(° F.)
.
-
.4 PA ___________________ ._
Temp..
.
cent by
175
-
-
0.32
175
.(lbsJitJ/day).
.
Reaction rate same
as for raw (unim
hibited) acid.
D0.
0
175
0.64.
0. 32
175
0.30.
0
200
>l.0.
0. 32
200
0.19,
0
175
0.56.
0. 32
175
0.025.
4 ethyriycyclohexanol (Coded ECH) _ _
0
175
>1 .0.
,4 E CH ___________________ ... ......... ..
0.32
175
0.21.
0
175
0.15.
0.009.
0.40
.8 1:9 rrixture of MB and alkyipyridines HB (Coded KB),
0.8 above mixture _________ __
0.4 1:1 mixture of PA and H
-- ___..do _______________________ -_
0.4 1:1 mixture of BD and HB ________ __
See footnote at end of table.
I
\
-
0. 32
0
175
- 200
0.32
200
0.025,
0
175
0.013.
_
3,077,453
Concen
'
Concentration of Aeetylenlo or Alkyl-
Er.v
No.
tration
pyridines in Inhibitor (percent by
volume)
Stamens
Ion 1 (percent by
Metal
Temp.,
(° F.)
Corrosion Rate
(lbs/tt?/day)
weight)
16 ________ ._do
............................. _-
17"--- 0.6 1:1 mixture of PA and HB
0.32
175
0.00’0.
______ __
0
250
0.40.2
18 ________ -.do ................................ _.
0.16
25
0,043;
0
0.16
0
0.16
0
0.16
2.=
25
200
2.5.3
0.9 .3
0.001
200
200
200
0.0%0.a
0.220.
0.097.
1 Stannous ion was added as stannous chloride, SNClzJHzO.
2 Length of test was 4 hours.
3 Length of test was 6 hours.
Examples 25-28
Other tests were run to determine the effect ,of various
2O
_
Ex.
stannous compounds to supply the stannous 1011 in the
No.
Metal
cmmmzmtion
Inhibitor
CPmentra"
tron Stan-
V01ume)
(figregggbby
(percent by
synergistic inhibitor mixtures.
nous Ion
Temp.
(° F.)
Corrosion
a
(lbs/rm
day)
Acid __.____ 150 ml. 15 % hydrochloric acid
Temperature _. 175° F.
25 37----. Cast Iron. 0.41:1 mixture
__________ -_
Length of test. 16 hours
Metal
_____ A151 1010 coupons (2.75" x 1.0" x 0.12")
Concentration
Ex.
Concentration Stannous
pound (percent
Rate
(percent by weight)
by volum
175
‘2s_-__ 0.4 methyl bu--
. 1 PA-Propargy1 alcohol; HB-Alkylpyridines EB.
day)
.............................. --
0.0078
0.0066
30
(lbs/ft?/
'
0172
M87
175
Corrosion
Acetylenic Com-
No.
150
150
Examples 41 to 52
0. 64
The e?ect of the inhibitor system of the instant inven
Qao 35 tron was determined in acids other than hydrochloric
8%?
acid employing propargyl alcohol; propargyl alcohol and
'
stannous ion; and, propargyl alcohol, Alkylpyridines HB
and stannous ion containing inhibitor compositions.
It is to be observed that the stannic ion does not impart
any visible effect on the corrosion rate.
-
'
Examples 29-36
Volumeof acid- 150 m1.
40 Temperature __ 150° F.
Length of test _ 16 hours
Metal
Corrosion rate determinations were made to determine
the concentration of stannous ion required, and the effect
of thevarious concentrations of stannous ion in the in 45
hibitor mixture. In each test the acid contained 0.4
percent by volume of a 1:1 mixture, by volume, of
propargyl alcohol and Alkylpyridines HB (a product of
Union Carbide and Carbon (10.).
_____ _. AISI 1010 coupons (2.75 x 1.0 X 0.12")
Concen
_
_
Ex.
Acid Media,
No.
Aqueous
tration
Stannous Corrosion
Concentration Inhibitor
(perent
by volume)
- ~
(percent by volume)
Ion 1
Rate,
(percent (lbs/[Lil
by
day)
weight)
Acid ______________ __ 100 ml. 15% hydrochloric acid 50
Temperature _______ __ 200° F.
41..-.
5112804 _______ __
0.4 PA ________________ __
Length of test _____ “I 16 hours
42.".
5 HQSOJ _______ __
0.4 PA ________________ __
43.... 5152504 _______ __ 0A 1:1 mixture of PA
Metal
Concentration
Stannous I 1011
(percent by
weight)
_____d0 _________________ ._
0 16
0.0004
5
5
0.4 PA __
04 PA ________________ __
0
0. 16
0.14
0. 0055
0
0.14
5
Corrosion
0.41:1 mixture of PA
and
ate,
lbs/ltJ/day
_____do _________________ __
.
0
0.10
0.16
0. 0004
0
0.067
0 16
0.0003
0. 16
0. 24
0. 028
0- 023
.0. 32
0. 025
Examples 53 to 63
Corrosion tests were made to determine the eifect of
other amines in the inhibitor compositions of the present
Examples 37 10' 40' ‘
Corrosion tests were made to determine the effective
ness of the inhibitor systems on metals commonly en
countered invboth oil well treating and industrial clean
operations.
0.0009
0.4 PA"
0. 008
0. 016
0. 032
0.
65
0 16
0.1 PA ________________ _.
and HB.
0. 4O 60
52-_-_ 5 011300011.-- _____do _________________ __
0. 29
0. 09
0. 06
' 1 'Added as SnCl2.2H2O.
0. 034
1 Added as SnC1z.2HzO.
ing
0.0047
0.15
5
51.--- 5OH3COOH___. 0.4 1:1 mixture of PA
.
.
0.91
0 16
0
and HE.
____________ __ API N80 tubing
Ex. No.
0
'
1
--
1-
"
-'
w
Acid __________-____ 1'50 n51. 5% ‘hydrochloric’ acid
Length of test ___....__ 6 hours
invention.
The tests were the same as set forth in
Examples 1 through'Z4 and the results are set forth
70 below:
'
Acid ____..__...150 ml. aqueous 15% hydrochloric acid
Length‘ of test -. 16 ‘hours
, Temperature .__.1V75° C.
75 Metal
_____ "A151 1010 coupons
3,077,453
6
100 parts of inhibitor composition, said amine being
selected from the group consisting of alkylamines, dial
EFFECT OF THE ADDITION OF STANNOUS ION TO
VARIOUS AMINE AND AMINE-PROPARGYL ALCOHOL
MIXTURES
kylamines and trialkylarnines having from 2 to 6 carbon
atoms in each alkyl moiety and alkyl pyridines having
Concentra- Concentra
_
Ex.
No.
53 ____ __
Concentration Amine
(percent by volume)
tion
tion
Corrosion
Propargyl
Alcohol
Stamens
Ion 1 (per-
Rate
(lbs/tt?/
volume)
weight)
(percent by
cent by
0.4 ethanolamine ______ --
54
55 ____ __
0.2 ethanolarnine ______ __
59 _________ __
from 40 to 98 parts by weight and said stannous com
10 pound is employed in from 60 to 2 parts by weight re
spectively.
>1. 0
0.83
57 ____ __ 0.4 cyclobexylamino
58 ____ __ 0.2 cyclohe.\;ylamine_____
>1. 0
>1. 0
o _________________ .-
0. 89
0.4 1,2-propanedian1ine__
m
claim 1 wherein said acetylenic compound is employed in
0. 96
56 _________ “do ................. -_
60 ____ __
ay)
>1. 0
o
from 1 to 5 alkyl substituents and from 1 to 12 carbon
atoms in each substituent.
2. The corrosion inhibitor composition as set forth in
>1.0
(in
0. 57
62 ____ __ 0.2 l,2-propanedinmine._
>1. 0
63 _________ "do ................. --
0. 79
1 Stannous ion was added as stamens chloride, 81101221120.
3. The corrision inhibitor composition as set forth in
claim 1 wherein said stannous compound is employed in
from 40 to 2 parts by weight and said amine is employed
15 in from 60 to 98 parts by weight.
4. A composition consisting essentially of an aqueous
acid and from 0.008 to 0.32 part by weight of a corrosion
inhibitor composition as set forth in claim 1 per 100
parts of aqueous acid.
This application is a continuation-in-part of applica 20
tion Serial No. 736,707, ?led May 21, 1958, now aban
References Cited in the ?le of this patent
UNITED STATES PATENTS
doned.
Iclaim:
1. A corrosion inhibitor composition consisting essen
tially of from 0 to 98 parts by weight of an acetylenic 25 1,678,776
2,053,024
alcohol having the formula
R
R—0E0-(:>—0H
R
30
wherein each R represents a member selected from the
group consisting of hydrogen, lower alkyl, phenyl, cy
cloalkyl and hydroxyalkyl and wherein the a-R’s may
be joined together to form a ring, fro-m 2 to 60 parts by
weight of a compound capable of providing a stannous 35
ion, and from 98 to 0 parts ‘by weight of an amine per
Gravel et al. __________ __ July 31, 1928
Dreyfus ______________ __ Sept. 1, 1936
2,097,847
Strauch ______________ __ Nov. 2, 1937
2,472,400
2,806,067
2,814,593
2,846,294
2,913,408
2,955,083
Bond et al _____________ .... June 7,
Monroe et al. _________.._ Sept. 10,
Beiswanger et a1. _____ __ Nov. 26,
Patterson et al _________ __ Aug. 5,
\Pumpelly et a1. ______ __ Nov. 19,
Levin __________________ __ Oct. 4,
1949
1957
1957
1958
1959
1960
FOREIGN PATENTS
235,291
Switzerland ___________ __ Apr. 3, 1945
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