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Патент USA US3041145

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Patented June 26, 1-962
line corrosion inhibitor. Brie?y, the invention comprises
a method for improving the contacting efficiency of aque
ous alkaline scrubbing solutions for the removal of acidic
gases from normally vgaseous streams by maintaining in
the absorption, medium a relatively small concentration
Joseph F. Chittum, Whittier, Edgar James Owens, El
Sobrante, and John B. Armstrong, Taft, Calif, assign
ors to California Research Corporation, San Francisco,
Calif., a corporation of Delaware
of petroleum sulfonates, preferably in combination with
straight-chain amides, and desirably added in conjunction
No Drawing. Filed Sept. 30, 1959, Ser. No. 843,378
6 Claims. (Cl. 23-4))
with an imidazoline corrosion inhibitor formulation.
The petroleum sulfonates useful in the process of. this
This invention relates to improvements in processes for 10 invention include by-product sodium sul-fonates having a
molecular weight in the range 350-500. Alkyl aryl sul
the removal of carbon dioxide and hydrogen sul?de from
fonates having a molecular weight in the range 400-450
gaseous streams using an aqueous alkaline solution. In
are particularly preferred. Such materials may be pre
particular the invention is concerned with means for im
pared, for example, by treating a solvent re?ned hydro
proving the rate of absorption and regeneration of the
aforesaid mildly acidic gases in a hot aqueous potassium 15 carbon fraction of suitable boiling range, containing mono
carbonate scrubbing medium.
nuclear alkyl aryl hydrocarbons having one alkyl chain
of 15 to 30 carbon atoms, e.g., a spray oil or white oil,
Many processes are commercially practiced for the re
with concentrated sulfuric acid to produce the sulfonic
moval of CO2 and/ or H28 from normally gaseous streams,
acid derivatives. The sulfonic acids are then neutralized
such as natural gas, byproduct hydrogen, synthesis gas,
and the like. In general, these processes comprise con 20 with sodium hydroxide and extracted with alcohol-water
to produce the petroleum sulfonates of this invention.
tinuously circulating an aqueous scrubbing solution con
These petroleum sulfonates are surface-active materials,
taining an alkanolamine or an alkali-metal carbonate,
and they may induce some foaming of the aqueous car
phosphate, or other salt between an absorption zone
bonate solution as a result of altering‘ the surface tension
wherein the impure gas is contacted with the solution and
a regeneration zone wherein absorbed gases are liberated 25 of the solution. It is this froth and small bubble forma
from the solution. A recently developed process using an
aqueous potassium carbonate solution offers considerable
process'and equipment economies where it is not required
that the carbon dioxide, for example, be removed to an
extremely low residual level.
In the commercial practice of such a process it was
found that among the ‘drawbacks to this system were an
extremely high corrosion rate on carbon steel equipment
and unusually low contacting e?iciencies in the absorp
tion and regeneration columns. Contacting e?iciency may
be de?ned as the number of theoretical or equilibrium
contacting stages required to perform a desired separa
tion divided by the actual number of contacting stages
tion which is believed to result in the greatly improved -
contacting efficiencies observed, since the area of contact
bet-ween the gas and liquid phases is thereby greatly ex
tended. Thus, the improved results of this invention are
30 obtained by inducing conditions opposite to what is com
monly viewed as good engineering practice. That is, the
formation of foams and froths is generally avoided in
contacting apparatus due to the prevailing opinion that
such conditions lead to poor performance, ?ooding, en~
trainment, and like problems. We have found in the prac
tice of our invention that the only problem of this type
requiring consideration is entrainment and that this is
readily corrected by installing simple demisting devices.
The petroleum sulfonates are continuously or inter
required, in the case of a tray-type column; or in the
case of a packed column the el?ciency is the number of 40 mittently added to the circulating carbonate solution as
required to provide a concentration therein of from 20
equilibrium. contacting stages multiplied by the height of
packing equivalent to a theoreticallstage and ‘divided by
the actual packing height required. E?’iciencies of 20-35
percent are commonly observed and are considered ac
ceptable in most commercial vapor-liquid contacting
to 2000 parts per million by weight, or more, but prefer
ably 200-1000 p.p.»rn.
The action of the sulfonates is enhanced when straight
chain amides are also added to the carbonate solution.
processes. However, when using a potassium carbonate
The amides themselves exhibit some surfactant properties,
solution containing 25-40 weight percent potassium car
but they apparently serve primarily to stabilize the sul
bonate for removing CO2 and H28 from natural gas, con
fonate-induced foam or to toughen the bubble ?lm. The
tacting el?ciencies of only 25-10 percent were observed. 50 straight-chain amides employed. are desirably para?inc
The expense involved in providing su?icient contacting
and contain 12-20, preferably about 18, carbon atoms
equipment to compensate for these low ef?ciencies lessens
to the molecule. Such amides are commercially avail
the economic attractiveness of the process.
able, or they may be conveniently prepared from the
The low efficiencies may be attributed to the poor mass
corresponding carboxylic acids by reaction with ammonia.
‘transfer characteristics of CO2 and H28 in the carbonate 55 The bene?cial interaction between the amides and sul
solution and to ine?icient contacting of the vapor and
fonates is observed when the mole ratio of amide to
liquid in the columns. Thus, when in a laboratory test
sulfonate is between about 1:9 and 3:1. Preferably these
gas was bubbled through a 30 percent potassium carbon
materials are added together in the range of proportions
ate solution at the temperatures employed in the absorp
indicated to provide a total concentration of the com
tion and regeneration columns, only relatively large bub 60 posite of about 200-1500 ppm. in the aqueous carbonate
> bles were ‘formed. These observations may be explained
in terms of the unusual surface tension properties of the
As indicated earlier, the hot concentrated potassium
carbonate solution. ‘We have found that by adding to the
carbonate-bicarbonate solution is quite corrosive to car;
solution a small amount of certain petroleum sulfonates,
bon steels. The use of potassium dichromate has been
described further hereinafter, the properties of the solution
recommended in the literature as a corrosion inhibitor.
are su?iciently altered such that relatively small bubbles
However, when treating gases containing H28, it was
are formed and the contacting e?iciency is markedly im
found that the dichromate was reduced to insoluble chro
mium oxides which precipitated from solution. Other
The activity of the petroleum sulfonates in this respect
corrosion inhibitors, such as ferrocyanide-type com
is enhanced by also incorporating in the scrubbing solu
pounds, were found to be oxidized to insoluble pre
tion certain straight-chain amides of relatively high molec 70 cipitates by the action of a small amount of oxygen in
ular weight. Desirably, the ingredients are added to'ther
the gas treated. Small quantities of oxygen may be
solution in a formulation which also contains an imidazo
introduced into natural gas, for example, due to air leak
In another test carried out under the same conditions
age in the vacuum gas gathering system and when the
gas is separated from oil in ?eld tanks. Similarly, syn
thesis gas produced by combustion reforming may con
tain small quantities of residual oxygen. We have found,
as the above example, but adding only the petroleum sul~
fonate without amides or corrosion inhibitor, a compar
able increase in tray e?iciency was observed, but the cor~
rosion rate remained high.
Although our invention has particular utility in‘ render
ing operable the hot potassium carbonate process for re
that a particularly effective corrosion inhibitor which is
non-reactive either with oxygen or H28 may be prepared
from castor oil and diethylenetriamine. The principal
reaction product and active ingredient is 1-aminoethyl-2~
(hydroxyheptadecanyl)-imidazoline; that is, the imidaz
moving COZ from gases, and has been described with
particular reference thereto, it is believed that the sulfon
oline derivative of ricinoleic acid. However, since cas 10 ates, amides and imidazoline additives disclosed herein
tor oil is not pure ricinoleic acid, there are some other
will be found equally valuable for use in similar gas con
nitrogen derivatives and by-products present in the for
mulation. Consequently, ‘the corrosion inhibitor is best
tacting processes. Thus, the addition of the petroleum
An additive formulation was prepared having the fol
selected from the group consisting of CO2 and H28 from a
gaseous stream containing at least one of said gases using
an aqueous potassium carbonate scrubbing solution con
sulfonates and straight-chain amides, alone or in combi
nation, may provide an vinexpensive means of increasing
identi?ed simply as the imidazoline reaction product of
castor oil and diethylenetriamine. The imidazoline com 15 the capacity of existing gas puri?cation systems, such as
pound is usefully employed as a corrosion inhibitor in
those employing an alkanolamine reagent. Likewise, the
the aqueous carbonate system in concentrations between
castor oil imidazoline has been shown to be a highly effec
200 and 2000 ppm, preferably 300 to 1500 ppm.
tive corrosion inhibitor in a number of applications.
The corrosion inhibitor and the surface-active agents
We claim:
have a cooperative action in performing their separate 20
1. In a process for the removal of mildly acidic gases
functions. Thus, the surfactants enhance the ability of
selected from the group consisting of CO2 and H28 from
the imidazoline corrosion inhibitor to adhere to and sub
a gaseous stream containing at least one of said gases
stantially coat the?metal surfaces as a molecular ?lm.
using an aqueous potassium carbonate scrubbing solution
Without the surfactants the ?lm is less tightly bound to
continuously circulated between an absorption zone and a
the metal, and higher concentrations of the inhibitor 25 regeneration Zone, the method of improving the contact
must be used. Likewise, it is believed that the ricinoleic
ing e?iciency of said solution which comprises main
imidazoline in some way contributes to the alteration
taining in said circulating solution a minor concentration
of the surface tension of the carbonate solution.
of above about 20 ppm. of sodium petroleum sulfonates .
having a molecular weight in the range 350-500.
2. In a process for the removal of mildly acidic gases
lowing approximate composition by weight:
Table 1
tinuously circulated between an absorption zone and a re
generation zone, the method of improving the contacting
Imidazoline (castor oil-diethylenetriamine) _______ __ 30
Petroleum sulfonates, 400—450 M.W _____________ __ 20
C18 straight-chain amides ______________________ __ 15
e?iciency of said solution which comprises maintaining
in said circulating solution a minor concentration of so
dium petroleum sulfonates together with straight-chain
alcohol ____________________________ __ 25
_____ __~ ______________________________ ___
amides su?icient to cause a stable froth.
3. In a process for the removal of carbon dioxide and
The irnidazoline used was the reaction product of cas
tor oil and diethylenetriamine. Isopropyl alcohol was
hydrogen sul?de from a normally gaseous hydrocarbon
stream using an aqueous potassium carbonate solution
selected as the carrier solvent as a matter of convenience.
continuously circulated between an absorption zone and a
Other solvents, such as methanol, may also be used. The
regeneration zone, the method of improving the contact
small amount of water serves to improve the ?uidity of
ing ef?ciency of said solution which comprises maintain
the mixture. In some applications a small amount of
ing in said circulating solution a minor concentration of
an alkyl aromatic oil may also be incorporated in the
above about 20 ppm. of sodium petroleum sulfonates
having a molecular weight in the range 350-500.
-This formulation was added to a 301' weight percent
4. The process of claim 3 wherein said petroleum sul
solution of potassium carbonate in water to provide an 50 fonates are added together with straight-chain amides hav
imidazoline concentration of about 1000 ppm, and a
ing 18 carbon atoms to the molecule, the molecular ratio
concentration of combined amides and sulfonates of
of said amides to said sulfonates being within the range
about 1150 p.p.m. The solution was used to scrub CO2
1:9 and 3:1.
and H28 from natural gas at a contacting rate of about
5. The process of claim 3 wherein said petroleum sulfon
2500 standard cubic feet of gas per hour per gallon per
ates are added together with an imidazoline corrosion in
minute of circulating solution. Operating conditions are
presented in Table II, which also vshows the results
obtained with and without the additive.
Table II
hibitor and, straight-chain amides, the whole of said sul
fonates, imidazolines, and amides being dissolved in an iso
propyl alcohol carrier.
6. The process of claim 5 wherein said corrosion in
60 hibitor comprises the imidazoline reaction product of
castor oil and diethylenetriamine, and the concentration
of said imidazoline is maintained between 300 and 2000
Percent 002 in Natural Gas Feed ____________ __
9. 3
Percent 002 in Natural Gas Ei?uent.
3. 5
2. 9
Absorber Pressure, p.s.i.g ................. ._
Absorber Temperature, °F___
Regonerator Pressure, p.s .i.g. . _
15. 4
14. 6
References Cited in the ?le of this patent
Regenerator Temperature, ° F. _ . _
Absorber, Tray Ef?eiency, percen
s. 5
7. 8
Sperr ________________ ___ Aug. 4, 1931
Corrosion Rate on Carbon Steel, mils/year_ _ ._
Buc __________________ __ Feb. 2, 1932
Rosenstein ___________ ___ Jan. 30’, 1945
Fischer _______________ __ Jan. 8, 1957
Benson et
Regenerator, Tray E?ieieney, percent.
The absorption and regeneration zones were conven
tional bubble-cap tray columns.
_________ __ May 12, 1959
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