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2,408.52‘?v
on PREVENT
PCESSES FOR REDUCING
FOAM
HG
assignor to
Calif”
Louis T. Morison, Albambra,
DeL, a
l’etrolite Corporation, Ltd, Wilmington,
corporation of Delaware
No Drawing. Application January 1, 1944.
Serial No. 516,707
'
‘7 Claims. (Ci. 252-—321)
2
tain ether linkages, as well as morev than one
.
This invention relates to a process for reduc
ing or destroying foam or inhibiting its forma
tion, in compositions of either aqueous or non
aqueous nature.
.
.
,
amino nitrogen atom.
amino nitrogen - atom” is
The phrase "basic
(“Unsaturated
used in its conventional sense.
groups, ornogatlve groups, if substituted for one
,
.
or more of'the hydrogens of ammonia, reduce
the basicity of the nitrogen atom to a remark
able degree. In general, the'presence of one nega
tive group linked on the nitrogen is su?icient to
Foams occur as undesirable, incidental features
in many industrial processes. The theory of their
formation‘ is not highly developed; so that hy
potheses on which foam reduction or destruction
processes might be based are difficult to formu 10 destroy the ordinary basic properties.”- Textbook
of Organic Chemistry, Richter, second edition,
consequence, foam-destroying agents
are usually devised for use in the case of par
. ticular iqamsand are not applicable broadly to
Reference to an amine and the subsequent
amino compounds is intended to include the salts
and the anhydro base, as well as the hydrated
foam problems.
‘I have discovered a novel process of reducing or 15
’ base. Both the anhydro base and the hydrated
destroying foams and of preventing their forma
base are obviously present'when an aqueous sys- .
tio'n, which appears to be relatively general in
tem is being subjected to the reagent or when the
reagent is used as a water solution or dispersion.
applicability, in that it may be used on compo
sitions comprising aqueous materials or solutions;
on compositions comprising non-aqueous mate 20 (“In an aqueous solution of the amine,
hydro base, R-NHz, the iwdrated base,
rials, such as hydrocarbon liquids; and on com
positions comprising mixtures of aqueous and
Q
.
RF'NHB-OH
the an- -
non-aqueous media. My process consists‘ in sub
letting a foaming or potentially-foaming com
and the two ions are all present.” Richter, s. v..
position to the action of a small proportion of a 25
page 252.)
reagent or anti-foamer of the kind subsequently
described, thereby causing the foaming proper
ties of the liquid to be diminished, suppressed or
In applying my process to the reduc
'
A description of certain high molal monocar
boxy acids, and more particularly those common
ly referred to as detergent-forming monocarboxy
acids, appears in U. S. Patent No. 2,324,490. For
convenience, the following description is substan
tion or destruction of a foam, the reagent is 30 tially a verbatim ‘form of the same subject-matter
poured or sprayed‘or dripped into the body of
as it appears in said patent.
foam on top the liquid, as desired; and the foam
It is well known that certain monocarboxy or—
breaks and is destroyed or reduced, substantially
ganic acids containing eight carbon atoms‘ or
more, and-not more than 32 carbon atoms, are
reagent. In applying my process to the preven 35 characterized
by the fact ' hat they combine with
tion of foaming, the reagent is admixed, in some
soap or soap-like materials.
at once, as a consequence of such addition of said
predetermined small proportion, with a potential
ly-foaming liquid, by any desired or suitable pro
cedure. The ability of the system to foam is de
stroyed or at least materially reduced by such ad
dition of said reagent.
.
The reagents employed in the present process
consist of basic acylated poiy-aminoalcohols in
. alkali -to produce
These detergent-forming acids include fatty
acids, resin acids, petroleum acids, etc. For the
sake of convenience, these acids will be indi
40 cated by theformula R.COOH. Certain deriva
tives of detergent-forming acids react with alkali
to produce soap or soap-like materials, and are
the obvious equivalent of the unchanged or un
which an acyloxy radical, derived from a deter
modified detergent-forming acids. For instance,
gent-forming acid having from 8 to 32 carbon 45 instead of fatty acids one might employ the chic
to a basic nitrogen atom by a
rinated fatty acids. Instead of the resin acids,
one might employ the hydrogenated resin acids.
carbon atom chain, or a carbon atom chain which
Instead of naphthenic» acids, one might employ
is interrupted at least once by an oxygen atom.
The aminoalcohols have more than one amino 50 brominated naphthenic acids, etc.
The fatty acids are of the type commonly re
radical, for that matter, more than one basic
fatty acids; and of course, this
amino radical. The compounds herein contem
’ ferred to as higher
is also true in regard to derivatives of the kind
plated as anti-foamers are well known compounds
and are produced by conventional procedures. -, > indicated, insofar that such derivatives are ob
tained from higher fatty acids. The petroleum
the compounds herein con
Stated another way, aminoalcohols which con 55
. templated are esters of
8,408,537
3
acids include ‘not only naturally-occurring naph
thenic acids, but also acids obtained by the oxi
dation of wax, para?in, etc. Such acids may
have as many as 32 carbon atoms. For instance,
see U. 8. Patent No. 2,242,837, dated May 20,
1941, toShields.
.
I
I have found that the composition of matter
herein described and employed as the anti-foamer I‘
of my process,’ is preferably derived from unsatu
rated fatty acids having 18 carbonatoms. Such 10
unsaturated fatty acids include oleic acid, ricin- '
oleic acid, linoleic acid, linolenic acid, etc. One
Ody,’ and
8.
slightly more effective. than the simple acylated
tonseed oil, soyabean oil, etc.
15
is not particularly water-dispersible, it may still
foamer is obtained from unsaturated fatty acids,
be possible to employ it in
and more especially, unsaturated fatty acids con
20
potassium cyanide and saponifying the product 25
obtained. Such/ products or mixtures thereof,
having at least/8 and‘ not more than 32 carbon
essentially to either one of the two following type
atoms and having at least one carboxyl group, or
formulas:
_
.
the equivalent thereof, are suitable as
30
forming monocarb
HO CsHa
’
alcohols of higher molecular weight formed in the
catalytic hydrogenation of carbon monoxide.
35
As is well known. one need not use the high
acid, such as a fatty acid, for in
The anti-foaming agent employed in the pres
ent process consists of a basic poly-'aminoalcohol
Aminoalcohol esters of the
kind herein contemplated are described in U. 8.
Patent No. 2,259,704, dated October 21, 1941, to
Monson and Anderson.
In light of what has
‘
necessary to include a list of reactants and re
H O C|H|
CsH4OH
H0 03H‘
CIH‘O CsH
CIHIOH
\ncmiocimN/
acyl halide. the ~anhydride,
ester, amide, etc., . 40
,
may be employed.
CrHcOH
N CaHcO CaHaN
oimon
As stated above. triethanolamine may be Poly
merized to produce the polyaminoalcohol which is
subsequently to be acylated. It is apparent from
an inspection of the above formulas that they
represent dimeric and trimeric polymerized
forms of triethanolamine. It has also been
stated above that triethanolamine may be poly
merized simply by heating. After determining
‘the average molecular weight of such mixture, I
combine the same with castor oil in the propor
tion ofl pound mole of castor oil for 3 pound
C. for approxi
, mately 6 to 25 hours, until reaction is complete,
as indicated by the disappearance of all of the
triricinolein present in the castor oil. If tri
sodium hydroxide or iron.
_
_
Some of the acylated amino bodies contem
plated for use in my process vare freely dispersible
in water in the free state. ‘Presumably,
tems comprise the reagent in the form of a base,
i. e., a substituted ammonium compound. In
other instances, the free forms of the reagents are
substantially water-insoluble, but the salt forms
(e. g., the acetates) are very water-:dispersible. 75
assess? '
.
‘ill
-
.
in the concentrated form, or it maybe diluted
' " marhablye?ective for ‘destroying or reducing a
with a suitable‘solvent. I have frequently ‘found
preventing roams, I‘ have additionally discovei
that their edectiveness. is sometimes somewl
. water to constitute a satisfactory solvent, because
of its availability and negligible cost; but in some . enhanced by admixing with them varying p1
cases I have used non-aqueous solvents. such as 5' portions of other materials. For. example, in 1
aromatic petroleum. solvent, in preparing‘ re‘
agents which were eiiective when used for the
purpose of reducing or destroying foams or pre- -
ventlng their formation.
Depending on the
choice of acylated amino body and its molecular 10
weight, the solubility may be expected to range .
from ready water-solubility in the free state to
substantial water-insolubility. As stated above,
the salts, and speci?cally the acetates, generally
show improved water-solubility over the simple
acylatedamino bodies; and I have in some cases
obtained the best results by using salt forms of
the acylated amino bodies which possess appre
case of the Diesel fuel. foam problem referred
above, a mixture oiapproximately equal pi
portions of my reagent and sulionated castor
was also‘ found to be eg?ective' in reducing i
foaming propensity of the hydrocarbon mater.‘
In the. case of the copper absorbent solution :
ferred to above, the use of equal
of my:
agent and drastically oxidized castor oil i
found to be e?ective. >
’
_'
‘
‘In operating the process of my invention, r
may add the anti-foaming reagent to the co
position having foaming tendencies-before foa
ing occurs, in which case the reagent opera
to prevent progressive foam formation; or -1
are commonly effective in proportions of the or 20 reagent may be added ‘to the foaming liquid,
which case it acts to destroy or reduce the to:
der of 10 to 50 parts per' million, their solubility
already present. The reagent ‘may be added l
in the foaming. .Or potentially foaming, composi
diluted, or diluted by water or some suita
tion may be entirely diil‘erent from their __appar=
non-aqueous solvent, such as petroleum dis1
ent solubility in bulk, in either water or oil. Un
doubtedly, they have some~ solubility in both 25 lates, etc. In the'case of a foamingiiquid, it rr
ciable water-solubility. Because such ‘reagents
media, within the concentration range employed.
I desire to point out that the superiority of
the reagent contemplated in my process is based
upon its ability to reduce o; destroy foam, or to
be most desirable to make a solution or dispersi
of my reagent, and spray or sprinkle such so
tion or dispersion over the head of foam prese
.If su?lcient turbulence exists in the vesselcc
prevent foam formation, in certain foaming or 30 taining the foaming liquid, it maysumce mer
-.to add the undiluted reagent to the system
potentially foaming compositions more advan
one operation and at one time. In the case
tageously and at lower cost thanis possible with
foam prevention, addition of. the reagent to 1
other reagents or processes. In certain instances.
liquid system may be by any suitable means a
it has been .found to destroy or reduce foams
4 or prevent their formation, which foams werev 35 injection may be continuous or intermittent,
required. A proportioning pump may be used
not economically or effectively reducible or pre
inject the reagent ‘into the composition, if 1
ventable by any other known means‘. .
sired. In all cases, the proportion of-‘my ,reage
In one application of my process, an ‘aqueous
required to effect foam destruction or reducti
composition comprising an alkaline hypochlorite
bleaching solution produced such a copiousfoam 4.1.0 or foam prevention, is only a very small fracti
of thevolume of liquid present in the foaming
during manufacture that thelatter interfered
potentially foaming, composition.
with the handling of the solution. Addition oi‘
The e?ectiveness of my reagent resides in p:
as little as 25ml. of a reagent comprising a ma
in the use of proper proportions thereof. '1
terial of the kind above-recited was sumcient
to destroy or reduce the head of foam on 8,000 45 correct amounts to be employed may readily
gallons‘ of the liquid. The proportion of reagent
to foaming liquid approximated 1 to 1.200000.
In a second application of my process, a 1,000
determined by subjecting any desirable test vi
umes of the learning, or potentially foamii
composition to accurately me:
61 small v
umes of the reagent, and observing the resu
known as Diesel fuel, had ‘become contaminated 50 of such additions, especially after shaking. l5
barrel tank of petroleum hydrocarbon distillate,
in some manner in the re?nery, to such extent
that it was impossible to load it into tank trucks
without having the foam come-out of the ?lling
shaking the container and contents will give ‘i
added information as to whether the anti-roan
I will prevent or suppress foaming over a peri
of time. Ii’ the proportions of reagent to be e1
hatch when the truck was only-partially loaded.‘
Introducing 10 gallons of a reagent comprising the 55 ployed are very small, it may be desirable
determine the optimum proportions of foami
material herein described resulted-‘in the pro
liquid and anti-foamer by introducing the lat‘
duction of a Diesel fuel which was loaded expe
into the sample in thetest container, in the to:
ditously into said tank trucks, without any foam
ing dimculty.
The ratio of reagentto foaming. - I of a solution in a suitable solvent.
' system here was approximately 1 to 4,000.
‘
a
In a third instance, 800,000 gallons of copper
ammonium acetate solution, employed in vthe
puri?cation oi’ butadiene in synthetic rubber
manui’actura'had become so contaminated, in an
Such pm
on dure, which increases the accuracy of the adi
tion, requires that a companion test he conduct
, using an equal volume of solvent, to prove tl
' the e?'ect observed is due to theantiq-foamer a
- not to the solvent in which it was added.
unknown manner, that the gasrecovery process 65 In‘summary, attention is directed to the i’:
that the amino compounds herein contemplai
could not be operated. The solution foamed out
the top of the tower‘when heat was applied to ‘ are polyamino in type. They have free hydro:
recover the respective dissolved _ hydrocarbon
radicals present. There must be present one e
currence of the radical RCO which is the a1
gases. In this instance, use of 1 part of a reagent
comprising. a material of ‘the kind above de 70 radical of a monocarboxy detergent-forming a<
scribed. to 80,000 parts of the copper solution
having at least 8 .and not more than 32 carb
produced immediate and complete reduction and
atoms, and the amino nitrogen atoms must
destruction of-the foam, and served effectively to
basic, i.'e., free from direct linkage with an u
prevent its regeneration.
.
e the above described reagents are re
saturated or negative radical such as an a
75 radical or an
1 real.
8,408,887
‘
'
~
1
7
i
.
8 t
Throughout this specification I have shown
that my process is equally applicable ,to systems
in which a foam is already in existence and to
HQCaHc
systems which are potentially foaming composi
_
canon
0,1140 OlHCN/
H0 01B:
and
tions, in that they have the, property of produc
ing .foams when agitated or mixed with air or
some other suitable gas. In the claims appended
hereto‘ I'have mentioned only the destruction or
‘reduction of foams, on theunderstanding that
' '
canon ’
OIHQOH
no'oim
CIHaO czmN/
0.3.0 cmm/
1 destruction, reduction and prevention are sub
HOOlHa
10
stantially identical, it being impossible to deter?
‘
'
,
cimon
canon
'
in which one hydroxyl hydrogen atom has been I
‘replaced by RCO,_ the ‘acylradical of a higher
fatty acid; said amine compound being selected
the initial laminae of foam, or whether such ini- ' from the class consisting of the anhydro base. the
‘
tial laminae are destroyed by the reagent before 15 hydrated base, and salts.‘ \
‘subsequent laminae of su?icient stability to pro
3. A process for-destroying or reducing foam,
characterized by subjecting a foaming composi
duce a foam can be superimposed, thereon.~ By
"foaming composition" in'such claims, I mean
‘ tion to the action of a reagent comprising abesic
- acylated polyaminoalcohol; said acylated poly
a composition which is either actually foaming,
mine in the prevention process whether the re~
agent does, in ‘fact, prevent the formation of
or which is capable of producing a foam under 20 aminoalcohol being a member of the class con
suitable conditions.
sisting of
_
'
In most instances, my reagent is e?'ective to
the extent that it destroys an existing foam sub
BOCsHc
stantially completely. In some instances; such,
for example, as when the proportions of liquid
and anti-foamer are quite widely removed from
I
'
NCrK|OOIH(N/
HOCnHe
and
-.
CaBAOH
C’HQOH
v
-
optimum proportions. the foam reduction may
CsHeOH
be slow, or it may even be incomplete.- I intend
that this description and my invention relate
nocun
c=mocimN< ‘
v
\NC:H4O C8HAN<
ClHeOH
both to complete destruction and topartial re-,
duction of foams.
nocani/
appear, as shown by the foregoing examples, to
vary widely. However, I wish-to limit my inven
tion to the use of amounts of anti-foamer com
prising 1% or less of the foaming system. Usu
‘
canon
.
compound being selected from the class consist
51213 of the anhydro base, the hydrated base. and
ally, the amounts required will-be between 0.1%
and 0.0001 %.
'
in which one hydroxyl hydrogen atom has been
replaced by RCO, the acyl radical of a higher
fatty acid having 18 carbon atoms; said amino
The proportions of reagent required to be used I
ts
.
4. ‘Al-process for destroying or reducing ‘foam,
'
characterized by subjecting a foaming composi
Having thus described-my invention, what I
claim as new and desire to secure by Letters 40 tion to the action of a reagent comprising a basic‘
Patent‘ is:
‘
acylated polyaminoalcoh'ol; said acylated poly
_
. aminoalcohol being
l. A process for destroying or reducing foam,
characterized by subjecting a foaming composi
sisting of
tion to the action of a reagent comprising a basic
acylated polyaminoalcohol: said acylated poly
HO CaHl
'
HO Colic
and
V
clmon
0:300]!
c?mon
¢
Canton
' CIHIOOIHGN/
aminoalcohol being a member of the class con
11° "
'
45
sisting of.
1100,13.
a member of the class con
‘
,
V
H0 0334
50
ciHeOC?IN/
'
canon
01800 C|H|N<
>NCIB¢0 OeEsN<Cs?'eOH
00810.8
B0 0.18‘ '
and
‘
'
in which one hydroxyl hydrogen atom has been
canon
noon!‘
'
_
HOC,
'
|
I
65 replaced by R00. the acyl radical of an unsat
urated higher fatty acid having 18 carbon atoms:
said amino compound being selected-from the
Cf?QdCsHeN -
CgHeOQgHg
_
I
I
' class consisting of the anhydro base, the hydrated '
CQHeOH
base. and salts.
.CaHeOH
'
‘
60' v5. A process for destroying or reducing foam,
in which one hydroxyl hydrogen atom has been ' characterized by subjecting a foaming composi
replaced by R00, the acyl radical of a monocar
tion to the action of a reagent comprising a basic
acylated polyaminoalcohol; said acyiated poly- ‘
boxy detergent-forming acid having at least 8
aminoalcohol being a member of the class con
and not more than 32 carbon atoms; said amino
'
compound being selected from the class consist 65 sisting of
ing of the anhydro base, the hydrated base, and _
salts; said amino compound being selected from
the class consisting of the anhydro base, the hy
drated base, and salts.
_
. ‘
~
)
HOCIH‘
'
2. A process for destroying or ‘reducing foam, 70
characterized by subjecting a foaming composi
and -
083403
tion to the action of a reagent comprising a basic
HO can
acylated polyaminoalcohol; said acylated poly-l
p
CsHcO OlH
N CaHoO cimN/
aminoalcohol being, a member of the class con
sisting of
‘018403
CcgeOCgHqN/
,
H0021!‘
CIH‘OH
0134013
'
2,1508, 527
Y. -
in which one hydroxyl hydrogen atom has
2
ing of the anhydro base, the hydrated base, e1
salts.
'1. A process for destroying or reducing fool
characterized by subjecting s foaming compo:
n
replaced by the oleyl radical; said amino com—
pound being selected from the class consistingv of
the enhydro base, the hydrated base, and salts.
6. A process for destroying or reducing foam,
characterized by subjecting a iosming
:----='
tion to the action of a reagent comprising s basic
tion to the action of a reagent comprising a. be:
ecyleted polyaminoalcohol; said acylated poly
sisting of
acyleted polyoalcchol; said acylated pol
oslcohoi being a member of the class co:
-
-
oelcohol being a member of the c :e con»
aistim; of
HO CIHG -
.
'
CsBcOH
CQHGOCSEeN/
HO On Q
'
.
end
CQHtOH
13
.
HQCyHl
EOCaHc
\ C|H6°H
'
CIHQOH _
-
CgH¢OE
CsHAOCaH
canto cm
CsmOCaH
'
.N/
' CgHcOCsH
-
' HOCaEc
camoim
HOCaHt
_
\
‘
canton
\UQHQOH
in which one hydroxyl hydrogen atom has he
t
in which one hydroxyl hydrogen atom has bee
replaced by'the ricinoleyl radical; said amino
compound being selected from the class consist
20 replaced by the linoleyl radical; said amino 001
pound being selected from the class consisting
the anhydro base, the hydrated base, and se;
'
LOUIS T._MONSON
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