Note: Descriptions are shown in the official language in which they were submitted.
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BACKGROUND OF T~IE INVENTION
l. Field of the Invention
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The invention is related to a surface active material,
a defoamer. More particularly, this invention provides
a defoamer and process for preparing same which controls ;
the foam in high strength acid media from petroIeum products.
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; 2. Description of the Prior Art
Conventional defoamers contain sulfonated tall oil-
~` fatty acids. Some are produced from a refined oleic
` 10 acid while others are produced from tall oil. The primary
application o~ these defoamers is in the phosphate industry -
to control the foam in the digestion and concentration
" , stages of wet-process phosphoric acid manufacture. In
'; recent years cost of conventional defoamers has drastically
increased because of the high cost of raw materials
;~ utilized in their manufacture. Therefore, what is needed
` and what has been invented by us is a novel defoamer
`, which is not only low in cost but is also more effective
, than the conventional defoamers being marketed.
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Accordingly, one aspect of the invention provides a de-
foamer for controlling the foam in high strength acid media com-
prising a majority of a sulfonated fatty acid having the formula
CnH2n+lCOOH where n is an integer of from 1 to 38 or including
at least one double bond and having the formula CnH2n lCOOH where
n is an integer of from 2 to 40, and a minority of a long chain
alcohol containing from about 4 carbon atoms to about 20 carbon
atoms, the ratio of said alcohol to said sulfonated fatty acid
being from approximately 0.025 to about 0.750 by weight, and a
10 nonionic additive having the formula R-O(R')nR" wherein R' is an
alkylene oxide, R is hydrocarbyl or hydroxyhydrocarbyl, R" is
. hydrocarbyl or hydroxyhydrocarbyl, and n is an integer of from 1
to about 200.
Another aspect of the invention provides a process for
preparing a defoamer for controlling the foam in high strength -
acid media comprising mixing a majority of a sulfonated fatty ~ `
acid having the formula CnH2n+lCOOH where n is an integer of from
1 to 38 or including at least one double bond and having the
formula CnH2n lCOOH where n is an integer of from 2 to 40, and a
minority of a long chain alcohol containing from about 4 carbon
atoms to about 20 carbon atoms, the ratio of said alcohol to said
sulfonated fatty acid being from approximately 0.025 to about
0.750 by weight, and a nonionic additive having the formula :
R-O(R')nRI' wherein R' is alkylene oxide, R and R" is hydrocarbyl
or hydroxyhydrocarbyl, and n is an integer of from 1 to about
200. :
A further aspect of the invention provides a defoamer
for controlling the foam in high strength acid media comprising
a majority of a sulfonated tall oil and a minority of a long
chain alcohol containing from about 4 carbon atoms to about 20
carbon atoms, the ratio of said alcohol to said sulfonated tall
oil being from approximately 0.025 to about 0.750, and a nonionic
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additive having a formula R-O(R')nR" wherein R is hydrocarbyl or
hydroxyhydrocarbyl, R' is alkylene oxide, R" is hydrocarbyl or
hydroxyhydrocarbyl, and n is an integer of from 1 to about 200.
Thus, the invention affords a defoamer and process for
preparing same for controlling the foam in high strength acid
media using petroleum products which comprises a majority of a
sulfonated tall oil and/or fatty acid and a minority of a long
chain alcohol and a nonionic additive having the formula R-O(R')n~
R" wherein R' is an alkylene oxide, R and R" is hydrocarbyl or
hydroxyhydrocarbyl, and n is from 1 to about 200.
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DETAILI~D DESCRIPTION OF T~IE INVENTION
~he compositlon of matter of this invention is a
defoamer for controlling the foam in high strength acid
media which broadly comprises a majority of a fatty acid,
or resin acid, or a tall oil and a minority of a long
chain alcohol and a nonionic additive. The fatty acid
may be mixed with resin acid. The mixture, generally
known as tall oil ( a by product from sulfate woodpulp
digestion consisting mainly of resin acids and fatty
acids), may contain from about 0.1 wt% to about 99.9 r
wt% of the resin acid. Therefore, the defoamer may :~
alæo broadly comprise a majority of a resin, ~-hich
preferably has been sulfonated, and a minority of a long
chain alcohol. If the fatty acid or the resin acid
is going to be utilized alone, in a preferred embodiment
of the invention, the fatty acid is the most preferred.
As was previously mentioned, tall oil is the
natural mixture of resin acids and of fatty acids
~together with nonacetic compounds) which is obtained
by acidifying the black liquor skimmings of the
alkaline paper industry. Crude tall oil is refined
by solvent extraction and~or distillation. The more ;;
refined the product, the higher the fatty acid content
as shown in the following: .
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Product Fatty Acid ~esin Acids Unsaponified
- . (%) ~%) . (%)
Crude Tall Oil 18 28 54
Single Distilled 90 6.5 2.7
Double Distilled 99 0.5 0.4
Tall oil by-products, such as tall oil heads and tall
oil pitch, are also used as defoamers. Heads contain
about 74.5 wt.% fatty acid, 25 wt.% resin acids, and
0.5 wt~ unsaponifiçd. Pitch contain approximately
34.0 wt% fatty acid, 36 wt.% resin acid, and 25.0
wt% unsaponified. These products are obtained from
the still bottoms (crudes left over after refinement), and
etc. The fatty acids are usually present as terpenes,
esters; they can be either natural or synthetic, and
may also be substituted with hydroxy or keto groups.
Fatty acids are a large group of organic, monobasic
acids derived from hydrocarbons and may be saturated
or unsaturated. In a preferred embodiment of the
invention, the fatty acids are a large group of aliphatic
monocarboxylic acid. The saturated fatty acids (e.g.
B formic, acetic, palmitic, stearic, etc.) have the cmp~crial
formula CnH2n+lCOOH where n i8 an integer of from 1 to
38, or Cn H2n 2 where n may have the same range of values.
; The unsaturated fatty acids have at least one double bond
and may have the following emperical formulas: CnH2n lCOOH
- or CnH2n_3COOH, or CnH2n_4O2 (acetylene acids, sorbic acid,
linoleic acid, oleic, etc); and CnH2n 5COOH or CnH2n 6
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(linolinic acid, etc). In the foregoing emperical formulas
for unsaturated acids n may be between 2 and 40, more
preferably n is between 10 and 30.
Resins are the oxidation or polymerization products
of the terpenes, and consist of mixtures of aromatic
acids and esters which are insoluble in water, soluble
in alcohol, ether or essential oils. Rosin is the
resin remaining after distilling turpentine from the
exudation of various species of pines(e.g. pinus
palustris). It contains from about 80 to 90 wt.% of
abietic acid ~C20H302) and its anhydride- ''
The fatty acid, resin acid or tall oil is
'' sulfonated by mixing it with a mixture of SO3 and SO2
i at a temperature of between about -20F and 212F. A
preferred temperature is room temperature ~i.e. about 72F). ~ -
The SO3 is much too reactive alone; therefore, SO2 is
utilized to pacify the reaction. The SO2 doesn't entex
into the reaction of the SO3 and oil but merely acts as
a diluent and coolant for the strong oxidizing tendencies
of the SO3. The alcohol is used to disperse and/or dissolve
the acid sludge. The alcohol not only disperses the
sludge but also permits the formation of a synergistic
product to produce a defoamer which is several'fold more
effective than the fatty acid, resin acid, tall oil or the
sulfonate of these compounds or the alcohol alone.
The alcohol may be any alcohol that is soluble in the
sulfonated oil. Preferably the alcohol may be any straight
or branched cycle or linear long chain alcohol having
bet~een about 4 and 20 carbon atoms. More preferably the
alcohol has between about 8 and 14 carbon atoms. Most
preferably the alcohol is dodecyl alcohol.'
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The nonionic additive preferably has the formula
R-O(R')nR" whcrcin R' is an alkyl~nc oxide, R and R"
is either a hydrocarbyl or hydroxyhydrocarbyl, and
n is an integer of from 1 to about 200. M~re preferably
the nonionic additive is polyoxyalkene alkyl ether or
hydrocarbyloxy poly ~Alkeneoxy) alcohol, wherein the
polyoxyalkene group has from about 2 to about 10 carbon
atoms, the alkyl radical includes from about 1 to
about 16 carbon atoms, the hydrocarbyloxy group contains
from about 1 to about 50 carbon atoms and is preferably
selected from the group consisting of hydroxyanthracene
hydroxy naphthalene and hydroxy phenyl, the alkeneoxy
group has from about 2 to about 10 carbon atoms, and
the alcohol comprises from about 1 to about 10 carbon
atoms. Most preferably the nonionic additive is selected
from the group consisting of tridecyloxypoly (ethyleneoxy)
ethanol and octylphenoxypoly (ethyleneoxy) ethanol. The
nonionic additive preferably comprises from about 0.10
wt % to about 50 wt % of the defoamer; more preferably
the defoamer has from about 1 to about 8 wt % of the
additive, more preferably the defoamer comprises about 4
wt % of the additive.
The sulfonation ratio of SO3 to oil may broadly be
from about 0.025:1 to about 0.60:1. The more preferred
sulf~nation ratio of SO3 to oil is from between about
0.10:1 to about 0.3:1, most preferably, the ratio is about
0.25:1.
The ratio of alcohol to the sulfonated oil may broadly
be from about 0.025:1 to about 0.75.1. The more preferred
ratio of alcohol to sulfonated oil is from between about
0.025:1 to about 0.50:1; most preferably, the ratio is
- about 0.38:1.
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- In the process for preparing the defoamer the fatty
acid, or the resin acid, or the tall oil is preferably
sulfonated wlth a minority of SO3 dissolved in a majority
of SO2. The mixing ratio of SO3 to SO2 may be any suitable
ratio such that S02 quiesces the reactive SO3. Preferably
SO3 and SO2 are mixed in a ratio of from approximately
l:l to about 1:10. During the course of the reaction of
either the fatty acid, the resin acid, or the tall oil
and the SO3, 52 mixture, the temperature decreases. The
mixture is preferably allowed to react from between about
15 minutes and ~O minutes whereafter the reacted product
is a mixture of sulfonated fatty acid, a sulfonated resin
acid, or a sulfonated tall oil (depending on starting
compound), and an acid sludge. The alcohol is subsequently
added to the sulfonated compound to disperse the sludge.
After the admixing of the alcohol to the sulfonated
compound, the mixture is blended from between about 15 mins.
and 90 minutes. Subsequently the nonionic additive is
mixed with the sulfonated compound and alcohol mixture
and blended for at least 15 minutes to insure a homogeneous
mixture. It should be noted that the 90 minute upper
limitation on the reaction time of the compound and SO3,
S2 mixture, and the sulfonated compound and alcohol
mixture is not to be construed as an unduly limitation.
Longer reaction times would be superfluous because the
reactions are completed after about 15 minutes. It should
also be noted that there is no particular importance in
- ~whether the alcohol is added to the sulfonated compound
prior to the nonionic additive, or vice versa.
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In the following is set forth examples of our invention
which are given by way of illustrations and not by limit-
ations. The specific concentrations, temperatures, times,
compounds, etc., set forth in these examples are not to
.. S be construed to unduly limit the scope of the invention.
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EXAMPLE 1 r
Four hundred grams of refined tall oil were sulfonated
at room temperature with 130 gms of liquid SO3 dissolved
in 680 gms of liquid SO2. During the course of the reaction,
the temperature decreased to -10F. The mixture was
allowed to react for lS minutes at which time the temperature
rose to 70F. The product was then heated to 100F to
strip residual SO2. The reacted product was a mixture of
sulfonated tall oil and sludge. Dodecyl alcohol was
added to the mixture to disperse the sludge. The alcohol
was added in a ratio of 300 grams of alcohol to 530 grams
of sulfonated tall oil. The mixture was blended for
15 minutes at 100F. to insure complete dispersion of
the sludge. Subsequently 6.0 yrams of a nonionic additive
(tridecyloxypoly (ethyleneoxy) ethanol are added to the
product. An acceptable alternative is to add the
alcohol and/or the nonionic additive along with the tall
oil before sulfonation. The product was then neutralized
to pH7 with caustic. Water was added to the neutralized
sulfonate to produce a product containing about 40% sulfonate.
Neutralizatîon is not absolutely necessary in the preferred
embodiment of the invention but is preferred for shipping
purposes.
This defoamer was added periodically to a reactor
having a continuous flow of phosphate rock, 60% H2SO4,
and recycled phosphoric acid (25% P2O5) in order to control
the foaming. This defoamer was proved to be superior to
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conventional defoamers on a cost/ton of P2O5 basis and de-
foamer ,requirements/ton of P2O5 as evidenced, in the following
Table I:
Table I
Defoamer Requirements Cost per Ton
per ton P2O5 (lbs./ton) P2O5 ($)
~ Applicants' 1.16 .26
; Defoamer
Conventional Defoamers
Brand A 4.00 0.70
Brand B 2.87 0.65
Brand C 4.68 1.24
Brand D 6.62 1.16
Brand E 4.18 6.94
Brand F 9.60 1.63
Brand G 4.66 0.98
EXAMPLE 2
Four hundred grams of oleic acid were sulfonated at
room temperature with 130 grams of liquid SO3 dissolved
in 650 grams of liquid SO2. During the course of the
reaction, the temperature decreased to -10F. The
mixture was allowed to react for 15 minutes at which time
the temperature rose to 85F. The product was then heated
to 140F to strip residual SO2. The reacted product was
a mixture of sulfonated oleic acid and acid sludge.
Dodecyl alcohol was added to the product. The alcohol
was added in a ratio of 250 grams alcohol to 530 grams
of sulfonate. The mixture was agitated for 30 minutes
to insure a homogenous product. Subsequently 6 grams of
octylphenoxypoly (ethyleneoxy) ethanol are added. The
mixture is then preferably neutralized to pH7 with caustic.
~ Enough water is preferably added to the neutralized mixture
', to produce a product containing about 40~ sulfonate.
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Subsequently the defoamer was tested and compared to con-
ventional d~foamers in accordance with Example I and sim-
ilar Results were found.
EXAMPLE 3
Four hundred grams of a tall oil product containing
about 55% tall oil resins and about 40% polyterpenes
were sulfonated at room temperature with 120 grams of
liquid SO3 dissolved in 600 grams of liquid SO2. During
the course of the reaction, the temperature dropped to
-0F. The mixture was allowed to react for 15 minutes
at which time the temperature of the mixture rose to
60F after which the product is heated to 120F to flash ~;
off any residual SO2. The reacted product was a
mixture of sulfonated tall oil and acid sludge. Dodecyl
alcohol was added to the mixture to disperse the
sludge. The alcohol was added in a ratio of 350 grams
of alcohol to 520 grams of the sulfonate. The mixture
was stirred at room temperature for 15 minutes to insure
complete dispersion of the sludge. Subsequently 10
grams of tridecyloxypoly (ethyleneoxy) ethanol were
added. Subsequently the defoamer was tested and compared
to conventional defoamers in accordance with EXAMPLE I
and similar results were found.
EXPLMPLE 4
~epeat Example I but substitute oleic acid for
the tall oil, then substitute resin acid for tall oil,
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then substitute non-sulfonated oleic acid and non-
sulfonated resin acid to be admixed with the alcohol,
find similar results in all cases.
EXAMPLE 5
Repeat Examples 1-4, but vary the mixing ratios
of SO3 to the selected compound ~fatty acid, resin
acid, or tall oil) in 0.005 increments between 0.025
and 0.600 and find similar results.
EXAMPLE 6
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Repeat Examples 1-5 but vary the type of alcohol
(both straight chain and branched) linear or cyclic
in 1 carbon atom increments between 4 carbon atoms and 20
carbon atoms and find similar results.
EXAM2LE 7
Repeat Examples 1-6 but vary the sulfonation
temperature when sulfonating in increments of 5F
between -20F and 212F and find similar results.
EX~MPLE 8
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Repeat Examples 1-6 but vary the mixing ratio of
the alcohol to the sulfonated compound in increments of
0.005 between 0.025 and 0.750 and find similar results.
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EX~MPLE 9
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Repeat Examples 1-8 but vary the mixing ratio
of the SO3 to SO2 when sulfonating in increments of 1:1
between l:l to 1:10 and find similar results.
EXAMPLE 10
Repeat Examples 1-9 but lower the reaction time of
SO3 and SO2, and the agitation time of sulfonated compound
and alcohol to 15 minutes and find similar results.
EXAMPLE ll
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Repeat Examples l-10 but vary n in increments of
l between 1 to 38 in the fatty acid having the formula
CnH2n+lCOOH, in the fatty acid having the formula
CnH2n lCOOH, in the fatty acid having the formula
CnH2nO2, in the fatty acid having the formula CnH2n lCOOH
or C H2 3COOH or CnH2n-42 or CnH2n-5C n 2n-6
find similar results in all cases.
EXAMPLE 12
Admixed the fatty acid of Example 11 ~and repeat
Examples l-10) with resin acid, vary the wt% of resin
acid in the fatty acid in increments of 5wt% between
.l wt% to 99.9 wt% and find similar results in all
cases.
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EX~IPL~ 13 :
Repeat Examples 1-12 but vary the procedure in
accordance with the following: vary the amount of the .
. additive in increments of 0.5 wt % between about 0.10
wt ~ to about 50 wt % of the defoamer; vary the type of
surfactant utilizing the formula R-O(R')nR" wherein R'
is an alkylene oxide and R and R" is hydrocarbyl or hydroxy-
hydrocarbyl, n is from 1 to about 200: vary n in
increments of 1, vary the hydrocarbonyl, the hydrocarbyl,
the hydroxyhydrocarbyl in 1 carbon atoms increments
between 1 carbon atom to about 50 carbon.atoms; use
nonylphenoxypoly (ethyleneoxy) ethanol or polyoxyethylene .
(2) oleyl ether as the additive, all belonging to the
family of compounds called alkoxypoly (ethyleneoxy)
ethanols or generally derivatives of ether, ethylene
oxide. Find similar results. .
EXAMPLE 14
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Take the sulfonated tall oil of EXAMPLE 1, the .
nonionic additive of EXAMPLE 1, and the alcohol of
EXAMPLE 1 and test the defoamer requirements of each
and synergistically compare with the defoamer of EXAMPLE .
1. Find the following synergistic results:
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Table 2
Defoamer Requirements Cost t~
per ton P2O5 P2O5(~) -
Sulfonated tall oil 7.52 1.88
Alcohol 6.03 1.20 -
Sulfonated oil-alcohol . ~:
mixture 2.59 .58
Sulfonated oil-nonionic
:10 additive mixture 2.49 .52 .
Applicants' Defoamer 1.16 0.26
EXAMPLE 15
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RRpeat EXAMPLE 14 in accordance with each procedure
of EXAMPLES 2-13 and find the similar results given in
EXAMPLE 14.
.. While the present invention has been described herein
with reference to particular embodiments thereof, and
specific examples, a latitude of modifications, various
- changes and substitutions are intended in the foregoing
. 20: disclosure, and in some instances some features of the
invention will be employed without a corresponding use
of other features without departing from the scope of
the invention as set forth.
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