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Патент USA US3033791

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3,033,781
rates l9£aten
Patented May 8, 1962
2
1
pared by adding to water a mixture of dry ‘material which,
7
.
.when dissolved, will yieldp-thecopper-ammonium-car
bonate complex. The complexes,- suitable for the purposes
of the invention, contain from 4 ‘to 14 weight percent Y
3,033,781
CORROSION INHIBITOR
Charles 0. Hoover, R0. Box 4294, Corpus Christi, Tex.
No Drawing. Filed Nov. 12, 1959,'Ser. No. 852,164
12 Claims. (Cl. 208-288)
COPPfET
'
. Typical “concentrates” as disclosed in my prior patent
This invention relates to a process for preventing or
are the following.
In particular, it concerns an improvement in the cor
rosion inhibiting composition and method disclosed in
my co-pending ‘application, Serial No. 524,813, ?led July
27, 1955, now Patent No. 2,913,406, of which this ap
plication is a continuation-in-part.
'
7
EXAMPLE A
inhibiting the corrosion of metallic petroleum re?ning
equipment and to compositions employed in said process.
1.0
~
Typical concentrate in liquid form:
r
'_
Copper carbonate
‘
> I
Weight percent
‘
Y
18.5.
Ammonia (anhydrous)____y_______________ _..__
Ammonia bicarbonate
I ‘13.0
Most crude petroleums contain numerous naturally oc 15 Water
curing constituents and impurities which will cause se
‘Total
vere corrosion of the metals from which conventional
50.7
_-_. 100.0
petroleum re?ning equipment is constructed. These cor
EXAMPLE'B
rosive or corrosion-causing materials include acidic mate
rials such as hydrogen sul?de, carbon dioxide and organic 20
acids. Oxygen, which is often present, usually by reason
of air absorbed in or ‘admixed with the petroleum, is a
particularly corrosive agent, especially at the tempera
‘17.8
Another liquid concentrate:
Parts by weight
Copper carbonate
A
.
34
7
70
Carbon dioxide
subjected during heating and distillation. Salt water or 25 Ammonia
24
tures to which the crude petroleum and its fractions are
Water
10
brine (which is commonly produced with, and is usually
present in most crude oils) and salts, such as magnesium
In order to use concentrates such as the two exempli
chloride, contained in the brine, will hydrolyze or other
?ed above, they are mixed at ambient temperatures with
wise decompose during the heating and distillation proc
an aqueous alkaline medium, preferably a solution of
esses to form hydrochloric acid, which, in the presence 30 Na2CO3, to’ form what is referred to in this and in my
of water vapor and liquid water as found in equipment
prior patent as a “?nal treating solution.” This ?naltreat
such as condensers, will cause severe metallic corrosion.
ing solution may also be prepared as a dry mixture re
Also, mercaptans and other sulfur compounds, normally
quiring only the addition of water to be ready for fuse.
present in varying amounts in different types of crude
It is obvious that other dry products may be prepared
petroleums, will decompose during heating and distilla 35 which contain some part, or all, of the alkaline material
tion to form corrosive compounds including, particularly,
needed for the ?nal treating. solution plus all of the
hydrogen sul?de.
ingredients of the concentrate. Such ‘dry products may
Many types of treatment have been employed in at
be added to an‘ aqueous alkaline medium. which is more
tempts to combat such corrosion in petroleum re?ning
dilute than that required when concentrates containing
40
systems. None has proven particularly successful in
more of the alkaline material necessary forethe ?nal treat
effectively preventing corrosion although some have re
ing solution are used.
'
duced the rate of corrosion to a point where replacement
A typical ?nal treating solution may, according to my
of equipment may be kept within tolerable limits, al
prior patent,
prepared by dissolving one gallon of a
though sooner or later major parts of the equipment must
concentrate, such as that illustrated by Example A, in
45
be replaced. In the case of high sulfur crude oils, such
120 to 130 (preferably 126).;gallons of~12° Baumé-aque
as Mexican crudes, a high rate of equipment replacement
ous sodium carbonate, solution. At ambient temperatures
has been accepted as a normal operating ‘condition irre
(e.g. 25° C.)v saturated sodium carbonate. solutions con
spective of the corrosion-combating processes which have
tain about 23% NazCOg. A typical dry form of ?nal
heretofore been employed to protect such equipment.
treating solution, requiring only dilution with water prior
In the parent case referred to above, there is presented 50 to use is that exempli?ed below.
the concept of preparing a concentrated corrosion in
hibiting material. This material is referred to therein,
EXAMPLE C
and henceforth herein as the “concentrate.” This con
centrate may be in either solid or liquid form, and the
active ingredient thereof comprises an tammoniacal cop 55
per complex. The concentrate may be prepared by
bubbling carbon dioxide, and ammonia gases simulta
neously into water and thereafter adding a commercial
copper carbonate to form a coprienammonium-carbon
ate complex. Alternatively, the concentrate may be pre 60
tDry form of ?nal treating solution:
Weight percent
Ammonium
bicarbonate ____________________ __ p
Copper
carbonate
Sodium
carbonate __________ _.., _____________ __-
Total
_
~ 7
'
.
,
5.0
.5
,-.
94-.5
100.0
'
3,033,731
>
Other-examples of ?nal treating solutions, which ‘are in
liquid form are as follows:
'
EXAMPLE D
_
V
‘
I
'
V
(NaHCO3). The amount of NaI-ICO3 used (in pounds
per gallon of ?nal treating solution) and the temperature
Weight percent
Copper (as metal) ______ .._'_ ______________ __
0.0217
Ammonia
Carbon dioxide
0.032
0.023
Sodium carbonate ___________ __'__.... ______ __
Water
'
10.020
89.898
4
tions such as the composition described in my parent case
and referred to hereinabove may be stabilized by the ad
dition of small' amounts of sodium bicarbonate
to which the. ?nal treating‘solution will be stable are
directly proportional.
. '
In the following discussion, concerning the amount of
sodium bicarbonate required to stabilize ?nal treating
10 solutions, it should be appreciated that the numerical
values are given on the assumption that the aqueous
Total _____________________ _; ____ __ 100.000
alkaline solution was prepared using reagent sodium
EXAMPLE E
carbonate. Actually the sodium carbonate of commerce
I
'
‘
Weight percent
or soda ash; when exposed while stored in bulk or in
Copper (as metal) _______________________ __
0.125 15 multi-Walled bags, absorbs moisture and carbon dioxide
Ammonia
' ‘
- 0.148
from the air. There is thus formed, the more stable
Carbon dioxide
-
0.108
sodium
"
Water
~
'
'
'
89.619
Toi-a1>;;__-_7__'_-__'__¥_'__'_‘ ____ __'_'_~__'i___ ‘100.000
EXAMPLE F
I
"
Weight percent
Copper (as metal) ____; _____ __"_-__.._‘__‘__.__°
Ammonia
‘
p
1.144
1.358
Carbon dioxide":_‘__-__-_‘__"_‘__'_ _______ __j_____
0.990
Sodium ‘carbonate _.,_ __________ .... ________ __
8.340
Water"
"
~
"
"
r
_
88.168.
1 , Total '_‘___'___'_ ____ _; _____________ __ 100.000
Various alternative concentrates and ?nal treating solu
tions are discussed in the parent case audit is obvious, as
sesqui-carbonate
(Na2CO3-NaHCO3-2H2O).
Thus, it is seen ‘that such commercial materials already
Sodium'-oarbonate_____'_.._.‘.__' ____________ __‘ 10.000
20
contain‘sodium bicarbonate and will, accordingly, by
virtue of the sodium bicarbonate already present, yield
treating solutions which are more stable than treating
solutions made with pure sodium carbonate. Accord
ingly, the numerical values discussed below will be
stoichiometrically different (i.e. amount of sodium bi
carbonate required decreases) when commercial grade
material has been used. It is also apparent that one
starting with reagent grade sodium carbonate ma‘ , by the
addition of carbon dioxide to the solution, impart a cer
tain degree of stability to ?nal treating solutions.
7
Turning now to a consideration of the use of sodium bi
carbonate in treating ‘solutions prepared with sodium
carbonate, we ?nd that the amount of bicarbonate re
quired to produce stability to a ?xed temperature is a
discussed thereimthat many equivalent chemical reactions
,function only of the concentration of the sodium carbon
can be relied upon in preparation of either. Further 35 ate solution originally used in the preparation of the ?nal
more, the ‘,fconcentrate,” particularly when in solid form,
may contain‘ various other ingredients'required in the
ultimaté'forinulationof ‘the ?nal treating solution. In;
fact,‘ in‘ thei'extr'e'me case such as shown by Example C
above," the’ concentrate maybe merely a dehydrated'?nal'
treatingsolution which requires only the addition of Water
to be available for immediate use.
'
' ’It_ has?now been found that the storage life of the ?nal
, treating solution. As shown in .Table I (which appears
'in column 5) the volume of sodium carbonate solution,
of'a ?xed concentration, used per volume of 60116611‘
trate had no e?ect upon the gallons of ?nal treating solu~
tion which could be stabilized by one pound of sodium
bicarbonate. Reviewing the data in the tables it will be
seen that for a 10% solution of sodium carbonate
amounts over 0.0166 pound of sodium bicarbonate per
treating solutions ‘of the parent case at elevated tempera
pound of sodium carbonate produce stability at 120° F.;
tures?’ particularly those above 90° F; (e.g. 120° 5.,
amounts over 0.0377 (pound per pound) produce stability
150f:;F.'and 212° F.) can be lengthened; During such 45 at 150° F., and amounts over 0.137 (pound per pound)
prolonged storage, there may be precipitation of metallic
produce stability at 212° F. For a 15% sodium carbon
copper or copper oxide from the ?naltreating solution,
ate solution comparable values are 0.0198 at 120° F.,
1 thus causing the copper concentration in the remaining
7 0.0204 at, 150° F. and 0.0632 at 212° F. Finally, for a
20% sodium carbonate solution (which gives treating
50
7 operation‘ in accordance with my original invention.
solutions inherently stable at 120° F.) the comparable
Such copper precipitation can now be prevented. _
values are 0.0106 at 150° F. and 0.0384 at 212° F.
' supernatantliquid to be below that requiredfor effective ’
‘7 *Accordingly, it is an object ‘of this invention’ to provide
an‘improved corrosion inhibiting'composition, the active
ingredient of which is a copper ammonium carbonate
complex, which is chemically stable at temperatures above
A further object of thisinvention is to provide a chemi
cal composition from which copper does not precipitate
.The data tabulated in Table I demonstrate the effect
of adding sodium’ bicarbonate to ?nal treating solutions.
55 The series of experiments re?ected in the tabulation were
performed with ?nal treating solution made with the con“
centrate of Example A of the instant application. To
this concentrate was added sodium carbonate solution of
the concentration shown in column 1. In each instance,
2 samples were prepared at 2 different dilutions (i.e. vol
60
' Still another object of thisfinvention is to provide a
ume of sodium carbonate solution per volume of con
method of preparing a treating composition which is
centrate). The dilution ratios appear in column 2 and
temperature stable above 90° F.’
‘
' _
each line of column 2 has two different ratios since two
' ' atelevated temperatures.
An additional object of this invention isrto provide a
process for combating corrosion of petroleum re?ning
different experiments were performed.’ Column 3 indi
cates the number of gallons of ?nal treating solution used
equipment by adding to the crude petroleum, at it enters . 85 per pound of sodium bicarbonate and column 4 expresses
the re?ning system, a chemical composition adapted to
the same data as pounds of sodium bicarbonate per pound
effectively neutralize or inhibit the various corrosion caus
of sodium carbonate. The last 3 columns indicate
ing constituents in the crude petroleunn'which composi
whether there was any precipitate’ from either of the 2
tion‘ isychemically stable during storage at temperatures 70 samples at temperatures of 120° 'F., 150° F. and 212° F.
‘above 90° F.
r
,7
p
0
These and additional objects of the invention will be
apparent to those skilled’ in the art from a consideration
of‘the speci?cation and claims which follow.
'
’ . .. ’~‘-1Brie?y stated, ithas‘been foundthat ?nal treating solu
The minimum amount of sodium bicarbonate which is
usually necessary to produce the desired increased sta
bility may be calculated by a family of equations (one
member of the‘family being used for each of the three
75 temperature conditions) "which relate-the percent con“
aoeejai
2. The method of protecting
a 1 metallic petroleum dis;
centration of the sodium carbonate solution used in the
preparation of ?nal treating solutions to the pounds of
sodium bicarbonate required per pound of sodium car
tillation apparatus from corrosion by corrosive con
stituents contained in crude petroleumv processed in said
apparatus which comprises admixing with crude‘ petro
bonate. The use of excess sodium bicarbonate above
Table I-—-Stabzlzzatl0n of Fmal Treat-mg Solutions
Volumes of
Sodium
Carbonate
Gallons of
Final
Treating
Solution Used,
Solution
Solution
percent
Per Volume
Per Lb.
Sodium
120°
150°
of
Sodium
Carbonate
F.
F.
Concentration of
Sodium Carbonate
Pounds of
Sodium
Bicarbonate
Precipitates After 24
hours at
Per Lb.
,
.
212
.
F.
Concentrate Bicarbonate
‘ 29 and 144.“
29 and
29 and
29 and
29 and
144.-.
144.“
144.-.
144.“
29 and 144 _.
89 and 178...
89 and 178“.
89 and 178.-.
.
89 and 178__.
89 and 178.-131 and 262-131 and 262__
131 and 262__
0.137
No
No
0. 122
0. 0377
0. 0365
0. 0166
No
N0
No
No
No
N0
Yes
Yes
Yes
Yes
Yes
Yes
' No
67
0. 0163
Yes
Yes
Yes
11
0. 0632
N0
No
No
12
34
0. 0579
0 0204
No
No
No
No 7
Yes
Yes
35
0 0198
0 0384
0 0357
0 0106
No
T.P
No
No
No
Yes
Yes
No
No
No
Yes
Yes
No
Yes
Yes
0 0104
No
Yes
Yes
No
Yes
Yes
None
13
14
47
_ 131 and 262
_
8
9
29
30
66
48
131 and262_-_ ’
None
'1‘; P.—Transiti0n Point, some inherent stability.
this minimum does not adversely affect the invention.
Larger amounts may be usedup to the limit of solubility
of sodium bicarbonate in the ?nal treating solution. The
important operating requirement is that the minimum
- lenm ‘in liquid .phase as‘ it enters said apparatus a ?nal
treating solution stable to a temperautre of 120° F.
comprising aqueous sodium carbonate ‘solution having a
concentration .of “X” weight percent sodium carbonate
said Weight percent being less than '15, an‘ ammoniacal
copper, carbonatecomplex, and .sodium,bicarbonate, the
amount of sodium bicarbonate, as given by the appro
priate equation be present.
Final treating solutions meet- '
ing this requirement will be temperature stable to the tem
pounds, of sodium bicarbonate present in said ?nal treat
perature indicated‘:
A. For temperature stability to 120° F.-
at least as great» as the quantity
ing solution for each pound otsodium carbonate being
15—X
15-X ‘
Y_ 301
30,1
40 and subjecting the resulting admixture to distillation in
B. For temperature stability to 150° F.—
23.9 ——X
Y_
said
3. apparatus.
A chemical_ composition for inhibiting corrosion of
369
c. For temperature stability to 212° F.
23.9 ——X
Y_ 101.4
In all of the above equations Y=the pounds of sodi
‘um bicarbonate per pound’ of sodium carbonate required
in the final treating solution so as to make the solution
temperature stable to the temperature indicated. X =the
weight percent of NagCOgin the aqueous alkaline medi
metallic petroleum re?ning apparatus by corrosive con
stituents contained in the petroleum processed in said ap
paratus comprising aqueous sodium carbonate solution.
having a concentration of “X” weight percent sodium
carbonate said weight percent being less than 15, an 'am-,
moniacal copper carbonate complex and sodium bicar~v
bonate, the pounds of sodium bicarbonate present in said
I
composition for each pound of sodium carbonate being
50 at least as great as the quantity
'
um used in preparing the ?nal treating solution.
Treating solutions made with sodium carbonate solu
addition of bicarbonate, to at least 120° F. and there
operating conditions.
'
1'5.——'X
3,01
vsaid composition being stable tola temperature of 120° F.
4. A chemical composition, 'stab'letoa temperature of
- tions more concentrate than 15% are stable, Without the
fore Equation A above should not ‘be used where X is
greater than 15. In Equations B and C the upper limit
of X (Le. 23.9) is a. function of the'solubility of sodium
carbonate and the equations therefore cover all practical
’
‘120° 'F., for inhibiting corrosion of metallic petroleum
distillation apparatus by corrosive constituents contained
in the‘ petroleum processed in said apparatus comprising
' water; copper carbonate; ammonia; a member of the group
60‘ consisting of ammonium carbonate and ammonium 'bi
Having described my invention, what is claimed is:
l. A method of inhibiting corrosion in metallic petro
leum distillation apparatus which comprises admixing
with petroleum being distilled in said apparatus a ?nal
treating solution stable to a temperature of 120° F. 65
carbonate; sodium carbonate and sodium bicarbonate,
the pounds of sodium bicarbonate present in said com
position for each pound of sodium carbonate being at
least as great as the quantity
15—Xl
comprising aqueous sodium carbonate said weight per
301
cent being less than 15 solution having a concentration of
.where
X
equals
the
weight
percent of the aqueous sodium
“X” weight percent sodium carbonate, an ammoniacal
carbonate solution used in vthe preparation of said com;
copper carbonate complex and sodium bicarbonate, the
pounds of sodium bicarbonate present in said ?nal treat 70 position, said weight percent being less than '15.
5. A method of inhibiting corrosion in- metallic pe
ing solution for each pound of sodium carbonate being
at least as great as the quantity
15—X
301
i -
troleum distillation apparatus which comprises admixing
with petroleum being distilled in said apparatus a ?nal
treating solution stable to a temperature of 150° F. com
prising aqueous sodium carbonate solution having a con
8,033,781,
~-
7
8
,
centration of “X” weight percent sodium carbonate said
of “X” weight percent sodium carbonate, said weight per
weight percent being less than 23.9, an ammoniacal copper
cent being less than 23.9, an ammoniacal copper carbon
carbonate complex and sodium ‘bicarbonate, the pounds
ate, complex and sodium bicarbonate, the pounds of so
of sodium bicarbonate present in said ?nal treating solu
tion for each pound of sodium carbonate being at least as
great as the quantity
I
»
a
‘
dium bicarbonatepresent in said ?nal treating solution
mfor each pound/of sodium carbonate ‘being at least as great
Y
as the quantity
‘
-
23 .9-X
369
i '6. The method of protecting metallic petroleum‘ dis~> 10
tillation apparatus from corrosion by corrosive constitin
ents contained in crude petroleum processed in said ap
paratus which comprises admixing with crude petroleum
in liquid phase as it enters said ‘apparatus a ?nal treating’
solution stable to a temperature of 150° F. comprising
aqueous sodium carbonate solution having a concentration
10. The method of protecting metallic petroleum dis
tillation apparatus from corrosion by corrosive constitu
ents contained in crude petroleum processed in said ap
paratus which comprises admixing with crude petroleum
' in liquid phase as it enters said apparatus a ?nal treating
solution stable to a temperature of 212° F. comprising
aqueous sodium carbonate solution having a concentra
of “X” weight percent sodium carbonate said weight per~
tion of “X” weight percent sodium carbonate, said weight
cent being less than 23.9, an ammoniacal copper carbo
percent being less than 23.9, an ammoniacal copper car
nate complex, and sodium bicarbonate, the pounds of
bonate complex, and sodium bicarbonate, the pounds of
sodium bicarbonate present in said?nal treating solution 20 sodium bicarbonate present in said ?nal treating solution
for each pound of sodium carbonate being at least as
for each pound of sodium carbonate being at least as great
great as the quantity
-
as the quantity
23.9—X
1
'
23.9—X
101.4
.
369
and subjecting the resulting admixture to distillation in said 25, and subjecting the resulting admixture to distillation in
apparatus;
,
,1
.
7. A chemical composition, stable to a temperature of
said apparatus.
'
'
11.-A chemical composition, stable to atemperature
150° F., for inhibiting corrosion of metallic petroleum
of 212° F. for inhibiting corrosion of metallic petroleum
re?ning apparatus by corrosive constituents contained in
re?ning apparatus by corrosive constituents contained in
'vthe petroleum processed in said‘ apparatus comprising 30 the petroleum processed in said apparatus comprising
aqueous'sodium carbonate solutionhaving a concentra
aqueoussodium carbonate solution having a concentra
tion of “X” weight.percentrsodiumrcarbonate said weight
tion of “X” weight percent sodium carbonate, said weight
7 percentbeing less than 23.9, an ammoniacal copper. care
percent being less than 23.9, on ammoniacal copper car
bonate complex and, sodium bicarbonate, the pounds of
bonate complex and sodium bicarbonate, the pounds of
35
sodium bicarbonate present in said composition for each
sodium bicarbonate present in said composition for each
7 pound of sodium carbonate being at least as great as ‘the
‘quantity
,
pound of sodium carbonate being at least as great as the
quantity
'
23.9—'X
369
-
'
'
8.
chemical composition, stable to a temperature of
a, ‘150° F. for inhibiting corrosion of metallic petroleum
distillation apparatus by corrosive constituents contained
in the petroleum processed in said apparatus comprising
' water; copper carbonate; ammonia; a member of the group
consisting of ammonium carbonate and ammonium bicar
n ‘bonate; sodium carbonate ‘and sodium bicarbonate, the
‘ pounds of sodium bicarbonate present in said composition
for each pound of sodiumjca'rbonate being at least as
' great as the quantity
i
v
'
V
23.9—X
101.4
12. A'chemical composition, stable to a temperature of
212° F. for inhibiting corrosion of metallic petroleum
distillation apparatus by corrosive. constituents contained
in the petroleum processed 'in' said apparatus comprising
water; copper carbonate; ammonia; a member of the group
consisting of ammonium carbonate and ammonium bicar
bonate; sodium carbonate and sodium bicarbonate, the
pounds of‘sodium bicarbonate present in said composi
9 tion- for eachpound of sodium carbonate being at least
7 as great as the quantity
‘
'
23.9—X
'
.7 where X equals the weight percent of sodium carbonate
‘ 101.4
- where X equals the weight percent of the aqueous sodium
in the aqueous solution’, usedtin'thejpreparation of said 55
carbonate solution used in the preparation of said com
composition said weight percent being less than 23.9.
position, said weight percent being less than 23.9.
'9.‘ A methodrof inhibiting corrosion in metallic petro
leum distillation apparatuswhich comprises admixing with
Referencesi'Cited in the ?le of this patent
petroleum being distilled in said apparatus a ?nal treat!
V
UNITED STATES PATENTS
ing solution stable to a temperature of 212° F. comprising 60
aqueous sodium carbonate solution having a concentration
2,913,406 , ' Hoover ___,___,__V___'_TV___ Nov. 17, 1959
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent. No. $033,781
May BV 1962
Charles 0. Hoover
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below .
67, strike out "said weight
Column 5, lines 66 and
5"; same column, line 68? after
percent being less than 1
"carbonate" insert -— sai d
15
weight percent being less than
-—.
Signed and sealed this 28th day of August 1962.
(SEAL)
Attest:
ESTON G. JOHNSON
A ttesting Officer
DAVID L. LADD
Commissioner of Patents
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