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Патент USA US3031507

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3,031,497
United States Patent "ice
2
1
,
Patented Apr. 241, 1962
several possible explanations of this phenomenon the
3,031,497
following is one of the simplest Ways‘ of representing it.
.
PREPARATION OF BARIUM SULFONATES
Loren A. Bryan, Railway, and Charles Burke Miles, West
(1)
’
H2O
AeOH + Ba(OH)z —> AcO‘—Ba—OH + H20
?eld, N.J., assignors to FMC Corporatioma corpora
tion of Delaware
(2)
.
H2O
AcO~Ba-—OH + BMOH); -——> AcOBaOBaOH -l- H1O
Filed Apr. 23, 1959, Ser. No. 808,368
10 Claims.
(Cl. 260—5ll4) ’
Basic salts may be prepared in a number of ways.
This invention relates to an improved process for the
One well known method is to use a weakly acid promoter
preparation of barium sulfonates by a reaction of organ 1.0 such as a phenol. In this case the Reaction 2 would be
ic sulfonic acids or sulfonates with barium silicates. The
represented as follows:
barium silicates are prepared by the decomposition of
(25,)
insoluble barium compounds with a ‘source of silicon
~
_.
'
7
H2O
Ac0—Ba-OE + BMOHM + HA ——-» A‘cOBaOBaOA + 221,0
dioxide, and the residual silicon dioxide containing mate
rials from the reaction of Organic sulfonic acids and 15 '_In the above fonnulas AcOI-I is an oil-soluble organic
sulfonates with barium silicates is recycled as this source
acid and HA is a weakly acidic material such as a phenol.
of silicon dioxide.
Barium salts of organic sulfonic acids have found wide
.
The above ‘products can be ‘treated with an acid gas,
such as CO2. This is a stronger acid than HA in the
application as‘articles of commerce in ‘substantial torn
presence or" water and causes the release (of HA’. or
The barium saltsof organic sulfonic acids are 20 neutralization of the free hydroxyl group:
nagles.
‘'
useful as paint additives, insecticides, rust preventa
tives and detergents. in motor oils. The oil-soluble barium
salts of organic sulfonic acids have been found to be
especially useful as additives for the improvement of
lubricating oils. These oil-soluble barium salts of organic
(3)
.
¢
.
~
I
ZAoO BaOBaOH + coir-e» (A00 m0 B8)2CO3 + 1110 I
sulfonic acids have dispersant properties and prevent
ring sticking and deposition of lacquer on pistons and
other functional parts in gasoline and diesel engines.
The preparation of sulfonic acids in the opt-grading
of petroleum oils by treatment of the oil with strong
30
sulfuric acid or oleum has been common practice in the
oil re?ning industry for several years.~ The resulting
petroleum sulfonic acids of molecular weight lower than
(4a)
AcOBaOBaOAl-H2O+CO2~>HA+
AcOBaOBaOCO2l-I
(4b)
2AcOBaOBaOA+HzO+CO2+ 2HA+
(AcOB aOBa) 2CO3
The ?nal neutral product as shown in Equations 3, 4a
and 4b would contain ‘four equivalents of metal for an
about 350 are water-soluble and are called “green acids.”
' equivalent of the'organic acid radical, AcO. ' The per
The sulfonic acids’ of higher molecular weight are "called 35 formance of these salts when added to lubricating oils as
“mahogany acids,” and upon neutralization form oil
dispersants (detergents) improves as their metalcontent
increases,-and the chemical ‘combination of several equiv
soluble salts.
‘ '
The barium petroleum sul-fonates may be classi?ed as
alents of metal for each equivalent of organic acid to give
“neutral salts” or “basic salts.” The latter class contains
an oil-soluble product makes it possible to obtain a con
an fexcess of barium over that required for the‘neutral 40 centrate which can be added in much smaller vproportions
.
to a lubricant and still obtain the same metal content and
The “neutral” salts have heretofore been produced by
performance as would be present if larger amounts of a
neutralization of sulfonic acids or by a metathesis reac
normal'or neutral salt of the acid were added.
tion with a sodium "sulfonate. In general, the barium
All of these processes require the use "of barium hy
. compounds used for neutralization of the sulfonic acids 45 droxide 0r barium‘ oxide as a source of barium and, by
are barium oxide or barium hydroxide. Forthe prepara
present commercial methods, ‘these compounds are fairly
tion of a barium sulfonate from a salt of an organicysul
expensive. Barium occurs naturally in‘such insoluble
salt and has some titratable alkalinity.
fonic acid two methods are known.
A barium halide
such asBaClz‘is'reacted with sodium sulfonateinjthe
presence of water in a metathesis that yields barium sul
50
ores as barite (BaSOQ and Wither-ite (BaCOa). Barite
ore is commercially available in large. amounts. The
present commercial process for producingbarium ‘hy
fonate and sodium-halide. Another reaction involves the ~
droxide or barium oxide from barite involves many
displacement of ammonia from anammonium 'sulfonate
operations and ‘results in substantial production costs.
It involves decomposing the barium sulfate by heating
by a basic bariurn'compound. ' In general, the barium
compounds used in any of these reactions are barium
with coke in a rotary kiln furnace to produce barium sul';_ ’
oxide or barium hydroxide. ‘v; Barium oxide hydrates 55 ?de according to the following reaction:
vreadily and ‘is lower in unit cost than the hydroxide. This
is one reason why it is used. Barium oxide can be
(5)
BaSO4+‘2C—> BaS+2CO2 "
slurried in oil and then reacted with sulfonic acid in the
The barium sul?de is leached from the kiln product and
presence of water. Barium oxide can also be dissolved
in methanol and reacted with sulfonic acid to produce 60 converted to BaCOs by reaction with soda ash or carbon
dioxide. The barium carbonate is decomposed with
barium snlfonates. Water or alcohol is necessary .‘for
practically all of these reactions. Water may be added‘as .
. water or as water of crystallization in'bariurn ‘hydroxide.
The “basic” salts are saltsof barium and an organic
carbon to give barium oxide in an electric~arc or. fuel
?red furnace as follows:
‘
'
'
acid in which the amount of barium combined is sub 65
stantially in excess of the stoichiom'etric amount required ' The barium oxidev is hydrated to obtain barium hydroxide. to prepare the neutralsalt' of the acid. While there ‘are
3,031,497
3
An object of our invention is the production of barium
salts of sulfonic acids by reaction with barium silicates.
which contains most of the excess reacted barium in a
form that is water-soluble. The theoretical equation for
this reaction with BaSO; as a starting material is as
A further object of our invention is a new and im
proved process for the production of neutral barium
sulfonates from the neutralization of sulfonic acids with
follows:
-
‘
water-insoluble barium silicates or barium silicates con
(7)
taining water-soluble barium values.
This polybarium silicate so produced reacts with an
organic sulfonic ‘acid as follows:
(8)
Another object of our invention is a new and improved
process for the production of neutral barium sulfonates
by a metathesis reaction of sodium sulfonates with bari
um silicates containing water-soluble barium values.
Another object of our invention is a new and im
proved process for the production of basic barium sul
The BaOSiOz residue is water-insoluble, but it likewise
fonates by the reaction of neutral barium sulfonates ‘
reacts with an organic sulfonic acid as follows:
with barium silicates containing water-soluble barium 15 (9)
values.
A still further object ‘of our invention is a new and
economical process for the continuous production of
The polybarium silicate also undergoes metathesis
barium salts of sulfonic acids by the decomposition of
with organic sulfonates as follows:
an insoluble barium-containing mineral with a source of 20
silicon dioxide to give a barium silicate, reacting the
(me)
barium silicate with a sulfonic acid or a sulfonate to
give a barium salt of a sulfonic acid and a silicon di- 1
2B?0.si02 + 2ArSO3Na + 21101 —>
H20
(ArSOa)2Ba + BaO.SiO2 + ZNaCl + 1110
oxide-containing residue and recycling this residue as a
source of silicon dioxide.
25
Various other objects and advantages of our inven
or
(10b)
tion will appear as this description proceeds.
H20
aBaosioi + 2ArSOrNH4 ———>
Y
We have discovered that in a simple two-step reac
(ArSOalzBa + BaO.SiOz + 2NH3 + H1O
tion, in step one an insoluble barium-containing mineral
such as barite can be decomposed by heating with a 30
The organic sulfonates will react further with the bari
source of silicon ‘dioxide to "give a barium'silicate con
um silicate residue in the presence of mineral acid to
taining water-soluble barium values. This barium sili
form neutral barium sulfonates as follows:
.
cate containing water-soluble barium values is for con
venience hereinafter sometimes called polybarium sili
(11)
cate. This polybarium silicate in step two can be re 35
acted with an organic sulfonic acid directly to give, a
neutral barium sulfonate and either a silicon dioxide
residue or a barium silicate residue. The barium silicate
The polybarium silicate also reacts with neutral barium
residues differ from polybarium silicate in that a portion
sulfonates in the presence of phenolic promoters as‘ fol
of the available barium has been removed by a prior
reaction. The barium silicate residue can be likewise
reacted with an organic sulfonic acid to give a neutral
(12)
barium sulfonate and a silicon dioxide residue. The
polybarium silicate can also be reacted with a salt of a
sulfonic acid by a metathesis reaction to give a neutral 45
barium sulfonate and a barium silicate residue. Also,
neutral barium sulfonate prepared in any manner can be
Upon treatment of the above product with an acid gas
reacted with polybarium silicate, in the presence of a
such as CO2 the promoter‘ is released similar tov Equa
promoter, if desired, to 7 give basic barium sulfonates
tions 4a and 4!) according to the following:
lows:
‘
.
"
-
-
'
and barium silicate residues. The barium silicate residues
can be further reacted with organic sulfonic acids as
noted above or with other strong acids or they can be
recycled along with the silicon dioxide residues as the
source of silicon dioxide‘ in the original decomposition
reaction.
‘‘
The promoter may be recovered and reused.
55
FIGURE 1 is a diagrammatic ?ow sheet of the cyclic
process for preparing barium salts of organic sulfonic
'
The B'aO.'SiO2 and the SiO;,, residues may be recycled
as a source of silicon dioxide as follows:
acids according to our invention.
As therein illustrated, polybarium silicate containing
soluble barium values is prepared by heating a barium
60
containing mineral with a source of silicon dioxide at
a temperature between 1300 and 1500“ C. This poly
barium silicate is reacted with various sulfonic acids or
Varying amounts of BaSO; may be used in excess of the
sulfonates according to processes A, B, C, D or E to
produce neutral or basic barium sulfonates and the un 65 2 to 1 ratio of barium to silicon shown, with increasing
yields of water-soluble barium values. However, if
reactedv barium values and silicon dioxide are recycled
and reused in the process.
, ,
amounts in excess of a 2.7 to 1 ratio are used di?iculties
are encountered in that the barium silicate produced
The polybariumv silicate containing water-soluble bari
undergoes sintering or fusion which results in a product
um values is prepared by decomposing insoluble barium
; which
is di?lcult to react. Inasmuch as the insoluble
_
containing compounds such, as barium sulfate, barium 70 barium
silicate can be recycled, high yields of water
carbonate, barium sul?te, 'etc., with a source of silicon
soluble barium values can be obtained without the use
dioxide by heating at temperatures of between 1300 and
of a high. barium tosilicong'ratio.
1500” C. for the required period of time. If an excess
The reaction to produce barium silicate containing
of barium over a barium to silicon ratio of 1 to 1 ‘ is
. utlized in the feed material, a barium silicate will result 75
water-soluble barium values from other barium com
pounds is similar as shown in the following. equations
3,031,497
.
5
phenol, alkylated phenols such as, for example, cresol,
utlizing barium carbonate and barium sul?te as start
ing materials:
" (16)’
6
.
xylenol, p-ethyl phenol, diethylphenols, n-propylphenols,
'
di-isopropylphenols, p-t-butylphenol, p-t-amylphenol, p
cyclopentylphenol, sec-:hexylphenols, n-heptylphenols, di
2BaCO3 +:SiO2-> 2BaO.SiO2+2COz
isobutylphenols, 3,5,5-trimethyl-n-hexylphenols, octyl
phenols, n-decylphenols, cetylphenols, etc.; ary1~substi
tuted phenols, ve.g.,phenylphenol, diphenylphenol, etc.;
polyhydroxy ‘aromatic compounds such as alizarin, quin
izarin,‘ or polyhydroxbenzenes, e.g., hydroquinone, cate
In the ?ow sheet, Reaction 7 or i4 and/or 15 takes
place in the kiln. Process A is that of Reaction 8 or 8 10 chol, pyrogallol, etc.; monohydroxynaphthalenes, e.g. al
pha-naphthol, beta-naphthol; polyhydroxynaphthalenes,
and 9, Process B is that of Reactions 10a and 10b, Proc
ess C is that of ReactionslZ and 13, Process D is that of ‘ ve.g. naphthohydroquinone, naphthoresorcinol, etc.; the
alkylated polyhydroxy aromatic compounds such as octyl
Reaction 9, and Process E is that of Reaction 11. Op
catechols, mono>(t_ri-isobutyl)-pyrogallols, etc.; substi
tionally Processes A and C can be combined in one
operation. The recycling steps are those of Reactions 15 tuted phenols such as p-nitrophenol, picric acid, o-chloro—
>14 and '15.
phenol, t-butylchlorophenols, p-nitro-o-chlorophenol, p
>
aminophenol, etc.; lower molecular weight hydroxy aro
matic carboxylic acids such as salicylic acid, chlorosali
As organic sulfonic acids, we may use any sulfonic acid
having an organic radical attached thereto. This radical
‘can be either aliphatic or cyclic. We prefer to use oil
cylic acids, di-isopropyl salicylic acids, gallic acid, 4-hy
soluble sulfonic acids derived from hydrocarbons having 20 droxy-l-naphthoic acid, etc.; lower molecular weight aro
matic sulfonic acids such as p-cresol sulfonic acid, p-t
at least 18 carbon atoms.
I
'
butylphenol sulfonic acid, beta~naphthol alpha-sulfonic
The following are speci?c examples of oil-soluble sul
acid, etc.; and lower molecular weight aromatic acids.
vtonic acids which may be used. For every "sulfonic acid
We prefer octyl " phenol and barium octylphenoxide'as
enumerated it is intended that the barium salt thereof is
also illustrated.
25
Such sulfonic acids are mahogany sul
promoters.
The acidic material used for treating the organic barium
‘toni'c acids; petrolatum sulfonic acids; mono- and poly
‘wax-substituted sulfonic and polysulfonic acids; sulfonic
complex to liberate part or all of the promoter and re
duce the alkalinity of the complex may be a, liquid or a
and polysulfonic acids of aromatic compounds, for ex
ample, naphthalene, benzene, diphenyl ether, ‘naphthalene -
gas. The liquids can include hydrochloric, sulfuric, nitric,
carbonic,v etc, acids; the gases, hydrogen chloride, ‘sulfur
disul?de, diphenyl amine, thiophene, 'alpha-chloronaph
dioxide, carbon dioxide, air (because of its carbon dioxide
. thalene, etc.; substituted sulfonic acids suchas cetylchloro
content), nitrogen dioxide, hydrogen sul?de, nitrogen tri
oxide, sulfonyl chloride, chlorine dioxide, hydrogen selen
benzene sulfonic acids, cetylphenyl monosul?de sulfonic
acids, cetoxycaprylbenzene sulfonic-acids, dicethylthian
threne disulfonic acid, Vdilauryl beta-naphthol sulfonic
acids, dicapryl nitronaphthalene sulfonic acids, aliphatic
ide, boron trifluoride, carbon disul?de, and carbon oxy
35 sul?de.
urated para?'in wax sulfonic acids, hydroxy-substituted
para?in wax sulionic acids, tetraisobutylene sulfonic acids,
tetra-amylene sulfonic acids, chloro-substituted para?in
‘wax sulfonic acids, nitroso parai‘?n wax sulfonic acids,
etc.; cycloaliphatic sulfonic acids such as petroleum naph
We prefer gaseous carbon dioxide as a readily
available acidic blowing agent.
sulfonic acids such as para?‘in wax sulfonic acids, unsat
4:0
Barite can be decomposed with silicon dioxide-contain
ing materials without fusion and in high yields in batch or
continuous furnaces, such as rotary kilns, by the use of a
critically ‘controlled slightly reducing atmosphere in the
kiln, so that only small amounts, up to 2% of BaS, are
formed in thekiln reaction product and by the use of a
‘thene' sulfonic acids, cetyl~cyclopentyl sulfonic acids,
barium to silicon ratio of the kiln feed material of from
lauryl cyclohexyl sulfonic acids, bis-(diisobutyl) cyclo
2.2 to 1 to 2.7 ml. .Conversions can be increased fur
hexyl sulfonic acids, mono- or poly-wax substituted cyclo- '
45 ther, with a decrease in occurrence of fusion by pelletiz
hexyl sulfonic acids, etc.
ing the kiln charge’ and by recycling barium silicate or
From the above oil-soluble sulfonic acids, the so-called
silicon dioxide produced by the sulfonating steps, with
petroleum sulfonic acids are both readily available and
provisions for a bleed to avoid'build-up of contaminants.
‘admirably adapted to our process. A variety of sulfonic
The barium silicate process can utilize barite feeds of
acids are produced in the upgrading of lubricating oil
various qualities, but best barium e?iciency is obtained
and their speci?c chemical structures will vary according
when a relatively high-grade barite is used. The desirable
to the type‘of oil being treated .and the extent of treat
kiln feed composition is a Ba/Si molar ratio of 2.5, or
ment with‘the sulfonating agent. In this process, we are
"about 10% Si02 by weight. A high-grade barite (93%
dealing with sulfonic acids having suf?ciently high molec
ular weight to be classi?ed as mahogany acids. These ' 55 or more BaSOQ requires addition of a substantial amount
of SiO2, which can be obtained 'by recycling monobarium
acids range in molecular weight from about 350 upwards.
silicate or SiOz residue, thus permitting also recovery of
While it is not possible to de?ne rigidly these waterin
most of the barium values in the residue. .
'
Y '
soluble acids on the basis of ionization constants, their
Theoretically the reactions .for the barium silicate proc
effective acidity is at least greater than that of oil-soluble
monoalkyl phenols, such as octylphenol. While we have 60 ess, utilizing recycled monobarium silicate,~can be written
as follows:
'
' limited our examples to the higher molecular weight
“mahogany acids,” described as “oil-soluble” and as hav
ing “oil-soluble salts,” there is no intent to exclude the so
calledt‘green acids” of molecular weight below 350 which
If it is desired to produce a barium 65
sulfonate or": one of these “green acids,” this is within the
In practice, however, complete decomposition of barite
scope of our invention. In addition, any of the other
is not obtained, so that the polybarium silicate contains
enumerated sulfonic acids are likewise operable in our‘
some BaSOg which remains unreacted and is recycled
V are water-soluble.
process.
I
.
In the metathesis reaction, the various alkali metal or 70
ammonium salts of the above acids can be used as start
ing materials.
'
i
‘
The phenolic compounds‘ or their barium salts serving
with the residue.
'
The reaction ‘conditions for the production of the vari
ous barium salts of sulionic acids varyfsomewhat and
will bev discussed individually as Processes A and‘ D
(Equations 8. and 9), Processes B and E (Equations 10a,
as promoters in the production of “basic” barium )sul- '‘ 10b and Ill) and Process C (Equations 12 and 13) are
fonates are illustrated by the following speci?c examples: 75 described.
a
3,031,497
7
8
REACTION, CONDITIONS FOR PROCESSES
form neutral barium sulfonates and a residue of silica.
A AND D
In general, the reaction medium will consist of a non
aqueous phase comprising a hydrocarbon mixture boiling
from about 70° C. upwards to hydrocarbon oils exempli
?ed by SAE 30 motor oil or mixtures thereof containing
the dissolved sulfonic acid, and an aqueous phase in in
timate contact with the polybarium silicate and the oil
phase. Other polar solvents capable of dissolving barium
values may be used to replace all or part of the water.
The quantity of barium used is'based on the available
barium in the polybarium silicate or barium silicate residue
REACTION CONDITIONS FOR PROCESS C
The reaction can be carried out in mineral spirits or
other solvents such as petroleum naphtha, xylene, toluene,
ethylbenzene, propylbenzene, butylbenzene, etc.
The time required for the preparation of the metal
complex will range from about 2 to 5 hr. or more depend—
ing upon the batch size and dehydration time. In addi
tion the product may be blown for 1-5 hr. with an acid
gas to neutralize the excess alkalinity of the complex
that is‘ leachable from the barium silicate with hydro
chloric acid. About one equivalent of available barium 15 and liberate all or at least most of the promoter, if such
is desired. The time required is dependent upon batch
is used for each equivalent of sulfonic acid to form the
size, rate of input of the gas and temperature. It has
neutral salt. When more than one equivalent of available
been found that 3 hr. are, generally sufficient to complete
barium is used, the product may be basic unless the
the reaction and dehydration, with an additional 3 hr.
reaction time is suitably controlled. If less than one
equivalent of available barium per equivalent of sulfonic 20 of mild blowing at elevated temperature with moist car
bon dioxide su?icient to neutralize the product.
acid is used, the product will be more acidic than the
The temperature for cooking of the ingredients is ap
neutral salt because of the barium de?ciency. It is prefer
proximately 100° C. and is controlled by the re?ux of the
able to use a slight excess of available barium, perhaps 5
‘Water. During the dehydration step the temperature
to 10% so that the total charge corresponds to 105 to
1>10% of the theoretical amount required, to produce the 25 ranges from about 100° C. to about 165° C. or higher,
Reaction periods ranging from 1.25 to 4.5 hours for
depending upon the boiling range of the solvent.
Three basic procedures have been used for the prepara
> neutralization and removal of the water represent the
tion of basic salts and will be listed as Methods 1,. 2 and
neutral salt.
>
range used, The preferred time is not over two hours
with up to about, one hour for neutralization and the
‘remainder for dehydration of the reaction mixture.
'It is convenient to work at the re?ux temperature of
the reaction mixture. Lower temperatures could .be used
with additional time expenditures. Dehydration tempera
tures range from about 100° C. to about 165° C., the
higher temperature being su?‘icient to remove substantially
all of the water, although temperatures of up to 180° C.
3, respectively.
~
Method 1.—The organic sulfonic acid (50% in oil) or
its barium salt, the promoter, and solvent, i.e. mineral
spirits, are placed in a reaction vessel equipped with stirrer,
thermometer, re?ux condenser ‘and heating means and
warmed where necessary to provide a homogeneous solu
tion. The polybarium silicate and water are added and
the mixture is re?uxed for about 2 hours at about 100° C.
A water trap is inserted between the reaction vessel and
condenser and the mixture dehydrated by increasing the
are permissible, provided the hydrocarbon solvent is suf
heat gradually to about 160° C. When the dehydration
?ciently high boiling to remain Within the reaction vessel.
A solution of the organic sulfonic. acid in a hydrocar 40 is complete the material is removed and ?ltered or option
ally blown with carbon dioxide for about three hours
bon solvent is placed in a reaction vessel ?tted with heat
with the temperature maintained in the range of 135—l50°
ing means, stirrer, thermometer and re?ux condenser.
C. and then ?ltered. The promoter liberated when the
Water and polybarium silicate (or barium silicate residue)
blowing with carbon dioxide step is used, may be re
containing su?‘icient. available barium to neutralize the
sulfonic acid are added. The stirred mixture is heated 45 covered.
Method 2.—The organic sulfonic acid, promoter and
under re?ux for 0.5 to 3.0 hours. A water trap is then
inserted between the reaction vessel and the re?ux con
denser and the temperature gradually increased to eifect
removal of the water. When the dehydration is complet
solvent such as mineral spirits are placed in the reactor
and warmed to provide a homogeneous solution. Then
water and enough polybarium silicate are- added to neu
ed, the hot mixture is ?ltered to remove residual inert 50 tralize the sulfonic acid, assuming that the total available
barium (water-soluble plus acid-soluble) will react with
material.
the sulfonic acid. The mixture is re?uxed for 1‘ hr.,
REACTION CONDITIONS FOR PROCESSES
cooled to about '80" C., the remainder of the polybarium
B AND E
silicate added, and heating continued at the re?ux tem
Polybarium silicate is reacted with an alkali metal 55 perature for 1 hr. The temperature is then increased to
effect dehydration. After dehydration heating is con
saltof an organic sulfonic acid in the presence of water
tinued for 1 hr. at ISO-160° C., and the processing com
and one equivalent of a mineral acid, such as hydro
pleted ‘as described under Method 1.
chloric acid or nitric acid, under the same conditions of
Method 3.—This operation involves the use of barium
solvents and temperatures-as outlined above. When a
sodium sulfonate is utilized as the alkali metal sulfona-te, 60 silicate residues left over from a previous preparation of
a basic or neutral salt to prepare neutral barium sul
the sodium sulfonate in a hydrocarbon or other solvent
fonate by Process D which is then processed according
is reacted with the barium silicate in the presence of a
to Method 1.
mineral acid and water at elevated temperatures until
The following examples illustrate our invention. It
substantially all of the sodium in the sulfonate molecule
has been displaced by the barium from the barium silicate. 65 is understood, however, that these examples are illustra
tive only and to enable one skilled in the art to practice
The barium silicate should contain a BaOzSiO2 ratio
our invention. They are not to be considered as limiting
ranging from 0.l:l.0 to about 3.0:l.0 or greater and
preferably from about l.0:1.0 to 3.0:1.0.
When an am
in any fashion the scope of our invention. .
The speci?c organic sulfonic acid used in our examples
monium sulfonate is substituted for the alkali metal sul
tonate, the mineral acid can be omitted if the BaOzSiOZ 70 is “Petronic Acid” produced by L. Sonneborn Sons, Inc.
ratio is above ‘1.0:1.0, and the reaction proceeds with ' This acid consists of 50% of a mahogany petroleum sul
simultaneous dehydration and evolution of ‘ammonia, and
the formation of a barium silicate residue.
>
.
Alkali metal sulfonates also react with barium silicate
residues and mineral acid under the same conditions to
fonic acid (a primarily-aliphatic,v saturated-hydrocarbon
sultonic acid mix with an average of approximately 25
carbon atoms), 48.5% mineral oil, 1% water and up to
i 0.5% sulfuric acid. This acid has an acid number of‘79
3,031,497
.
9’
10
general conditions as outlined above under the heading
mg. KOH/ gram and a molecular weight of 440 to 460.
All weights are calculated on the active acid content.
Examples According to Processes A and D
, “Reaction Conditions for Process C.”
Examples of processing according to Method 1 are‘
given in Tables III and IV. In this series various com
binations of starting ingredients are shown together with
the best combinations of materials to get efficient utiliza—
tion of the barium. On the‘ basis of the results, Examples
12and 13, in' which barium “Petronate” with octylphenol
esses A and D” are tabulated.
'
.
-'
'
as promoter reacted with 'polybarium silicate, gave the
Table I gives the reactant variations for Examples 1-5;
M10 highest metal ratio and ranked second in barium, e?i
Table II gives the results.
' .
5
In the following tables the results of examples of the
process conducted according to the methods outlined
above under the teaching “Reaction Conditions for Proc
TABLE r
Quantities of Reactants Used in ‘the Preparation of
Barium Sulfonates
Polybarium‘Silicate (Process A)
Available Ba
Example No.
“Petronic Acid”
Percent
EquivJ
Weight
of BaO
gm.
in 2 gms.
.4
. 010a
.4,
. 0103
Equiv.
—
_
weigh
Barium silicate
‘Weight Equiv'. Mineral
weight '
spirits
in gms.
0. 030
0; 100
19.
65.
1 Added solvents in girls.
Water >
39
20
20
50
0. 159
0. 091
15.4
8. 76
Mineral
oil
Barium Silicate Resid ues (Process D)!
5. 42
33. 6
20. 2
. 0100
. 0090
. 0096
0. 054
0. 303
0. 194
1 Residues from the preparation of basic salts.
2 Product as received, 50% active in mineral oil.
TABLE II
Barium "Petr0nates”
REACTION CONDITIONS AND RESULTS
Fresh Polybarium Silicate
Barium'usage
Product
Example No.
Time in
-
hrs.
Weight
in g‘ms.
Percent
‘
Ba
“Petronic Acid”v '
Available, ‘'Reacted,
equiv.
I
equiv.
Percent
’ Added
equiv.
7
~
53
neutral
rzed
0. 039
> 25
130'
09
102
93
100
ciency. Examples 6 and 7, in which “Petronic Acid”
As shown by Table II, the polybarium silicate reacted,
with barium octylphenate as promoter reacted with poly
readily with va slight excess of “Petronic Acid” to give
barium silicate, gave the second highest metal ratio and
up all of the available barium (Example 2‘). > A similar
the highest barium e?iciency. The amount of water
result was obtained (Example 3) in which the barium
silicate residue released all of its available barium to 60 soluble barium in these cases was less than in the'pre
vious examples and may have had a direct bearing on
form a nearly neutral barium‘ “Petronate.” The removal
the metal ratio and barium ef?ciency. In Examples 8
of the barium from barium silicate residues was slightly
and 9, when barium “Petronate” with barium oc‘tylphe
less e?'icient in two other examples (Examples 4 and 5)
mate as promoter was allowed to react with the poly
due to the use of larger batches with shorter time for the
reaction to go to completion. When a substantial excess 65 barium silicate, the results were inconsistent with fair to
poor metal ratio and mediocre barium e?icicncy. In
of barium was available (Example 1), as basic barium
Examples 10 and 11, when “Petronic Acid” with octyl
‘_‘Petronate” was formed readily and a barium silicate
. phenol as promoter was reacted with polybarium silicate,
residue resulted. This barium silicate residue was reused
the metal ratios were poor although in Example 10 this '
as the barium silicate source in Example 3.
was probably due to the small excess of barium present.
.Even under these adverse‘conditions, however, a sub
Examples According to Process C
stantial reaction occurred. Example 14 represents the
preparation of a basic barium sulfonate by reacting poly
Methods 1, 2 and 3
The following examples were performed under the
75
barium silicate with a sulfonic acid without the use of a
promoter.
'
l
3,031,497
TABLE HI
Basic Salts Prepared by Method 1. Reactants
_
Reactant quantities
Added solvents
Example
Acid or salt
((3.)1
Polybarium
.
6 ....... .- “Petronic Acid” __________________ _;
7
_____d0_-
8 _______ _.
9
Barium “Petronate” ______________ __
_-___do_-
10 ______ __
11
__.__d0__
12 ______ __
13
Barium “Petronate” ______________ __
___--d0__
14 ______ __
9.95
15. 4
9.95
15. 4
9. 27
7.02
39. 8
“Petronic Acid” __________________ __
Dialkyl benzene sulfonic acid _____ __
Promoter ‘ v
silicate (g.)
'
((3.)
.
Barium octylphenoxide?n;
5. 34
d
5.34
4. 68
76. 7
9.90
17. 9
8. 68
'
Water
Mineral
(g.)
spirits (g.)
39
20
39
20
20
16
60
22
. 12
10
60
33.6
65.8
.1
60
20
39.0
90. 7
.1
60
.......... -_
39.4
82. 7
.1
60 __________ __
80.1
216.
76
2 46
1 Material was used in solution of oil or lighter hydrocarbon solvent; values given for barium “Petronate” were found by analysis.
9 Mineral 011.
TABLE IV
Basic Salts Prepared by Method 1. Conditions
and Results
Equivalents of reactants
Example
Reaction type sulfonate
promoter
Time (hr.)
Sulfonate
uble poly-
Percent of
water sol
uble Ba
Metal
ratio 1
Water-sol-
Promoter
Cook
CO3 blow
reacted
barium
silicate
Acid- D1118 salt ............. -_
. 030
. 063
.7018
2. 1
0
2. 55
94
---_d0 ...... __
.' 030
. 063
. 018
4. 5
0
2. 54
94
Salt plus salt-
. 025
.0287
.015
4.0
0
2. 03 -
.10
.330
.059
3. 2
3.0
.030
. 0356
.020
11.0
. 10
.400
. 059
2.8
. 10
.329
.059
2.8
3.0
3. 31
77
.10
.20
.300
1.18
.059
3.0
5.0
3.0
0
> 3. 25
2. 23
80
38
___._do _____ __
Acid plus acid"
_____do _____ __
Salt plus acid__
.--__do_.-._______ __ Acid____-_______.____-______
0
2. 8
65
' 2. 94
36
1. 50
127
1. 89
47
1 Ratio of barium equivalents to sulfonlc acid equivalents in the product.
TABLE V
Basic Salts Prepared by Method 2, Conditions and Results
Equivalents of reactants
Solvents (g)
Reaction time (hr.)
'
Example
.
-
Water-
Octyl-
“Petronic
soluble
phenol
Acid”
polybarium promoter
-
Water
Mineral
spirits
Mineral
oil 1
‘
Percent
Metal >
of water
ratio 1
Cook
GOzblOW
soluble Ba
reacted
silicate
0.10
0. 10
0. 1O
0. 396
0. 396
0. 50
0.10
0.40
0. 10
0. 10
0. 10
0. 10
0. 40
0. 30
0. 30
0.50
0.059
0. 059
0.059
60. 0
60.0
60.0
0
0
20.0
94
94
94
2. 8
3. 8
3. 5
2. 8
2. 7
2. 8
2. 66
3. 53
2. 93
67
89
59
0.059
60.0
20.0
94
3.0
2. 8 -
2.90
72
0.059
0.059
0. 059
0. 059
34.0
60. 0
26. O
42. 5
20. 0
20.0
20. 0
20.0
94
94
94
94
3. 5
4. 0
4. 2
3.8
3. 0
2.8
2. 6
2. 8
2. 47
2. 33
2. 84
2. 70
61
78
95
54
r 1 Comprises solvent for .“Petronic Acid” plus 61 g. light mineral oil.
_ 2 Ratio of barium equivalents to sulfonic acid equivalents in thcgproduct.
mols H2O per equivalent of Water-soluble barium) were
Examples of the use of Method 2 are given in Table
used with 0.30, 0.40 and 0.50 equivalents of water-soluble
V. By the use of Method 2, no independent preparation
of barium salts as starting materials is necessary. The 60 barium. vUnder these conditions, Example 18 was best
with a metal ratio of 2.90 and 72% e?iciency of the bar
“Petronic Acid,” and, optionally, the phenol as promoter,
ium. In Example 17 the metal ratio was approximately
are placed in the reaction vessel with sufficient polybarium
the same as in Example 18 but the barium e?iciency was
silicate to neutralize all of the “Petronic Acid.” The
lower. In Example 20 the barium efficiency was a little
“Petronic Acid” is strong enough to react with both the
acid- and water-soluble barium present in the polybarium 65 higher but the metal ratio was substantially lower. In
Examples 21, 19 and 22, 0.3, 0.4‘ and 0.5 equivalents of
silicate. After about 1 hr. of re?ux the remainder of the
water-soluble barium, respectively, were used with about
poly‘oarium silicate is added to provide the additional
4.7 mols of water per equivalent of water-soluble barium.
barium for increasing the metal ratio. Examples 15 and
Example 21 was the best with the highest metal ratio and
16 represent identical runs except that in 16 heating was
continued for 1 hr. after the dehydration step prior to 70 barium e?iciency. The larger excesses of barium in Ex
amples 19 and 22 yielded slightly lower metal ratios and
blowing with carbon dioxide. The 1 hr. of heating after
the e?iciencies were relatively low.
dehydration was used in all the succeeding examples. In
Examples 17 through 22 the effects of varying the amounts
1 EXAMPLE 23
of polybariumrsilicate and Water added are shown. In
Examples 20, 18 and 17, 60 grams of water (6.7 to 11.0 75 This example illustrates the practice of the invention ac
3,031,497
14
,
cording to Method 3 of, Proce'ssC. A barium silicate’
silicon ratio to 2.5 ‘to 1. This feed composition was at
residue was used whichhad resulted from the reaction of a
tained as follows:
polybarium silicate with sultonic ‘acid in the preparation
.
of a basic sulfonate. It contained 69.1% available barium
calculated as BaO. 33.6 grams of this residue containing
.,
Mols of barium
m
.
I
.
present
From fresh barite _____ __»_ __________________ __ 2.24
From recycled BaSO4 residue _____________ __-_->_ 0.26
0.303 equivalent of available barium was reacted with 202
grams (0.300equivalent.) of a sulfonic acid (“-Petronic”
' '
Mols of silicon
acid) in mineral oil in the presence'of 175 grams of min
eral spirits and 60 grams of water. The nearly neutral
barium sullfonate produced‘was separated from the sili 10 From SiOB content of fresh barite ________ ________ 0.13’
From recycled residue _____ -i. ______________ __ 0.87
ceous residue. It contained 0.259 equivalent of combined
Total
._......
_ ‘1.00
barium corresponding to an 86% recovery of the available
barium values in the original barium silicate residue. An
The
polybarium
silicate
produced
was
reacted
with
or
aliquot of the barium sulfonate solution containing 0.100
ganic
'sulfonic
acid
derivatives
as
in
any
of
the
preceding
equivalent of sulfonate and 0.086 equivalent of combined
Total
~
»-
~
I
--
-
‘
___
>
2.50
present
examples with comparable results.
'
The above examples are illustrative, but are not to be
considered as limitations of our invention, the scope of
barium was then reacted in the presence of 0.059 equiva
lent of octyl-phenol promoter with polybarium silicate
containing 0.329 equivalent of water soluble barium ac
which is to be determined by the appended claims.
cording to Example 12. The basic barium sulfonate ob
tained from this reaction contained 0.331 equivalent of 20 We claim: I
l. The process of producing barium salts of organic,
combined barium corresponding to a metal ratio of 3.31.
sulfonic acids from organic sulfonic acid derivatives
The recovery of water soluble barium from the poly
selected from the group consisting of oil-soluble'organic
barium silicate was 75% ‘and the barium’ silicate residue
~ sulfonic acids derived'from hydrocarbons'having at least
was reacted with sulfonic acid to make additional neutral
'18 carbon atoms and ammonium and alkali metal salts
thereof‘ and‘ insoluble barium compounds selected from
the group consisting of barium sulfate, barium sul?te and
barium sulfonate as in the ?rst step of this example.
EXAMPLE 24
barium carbonate, which comprises decomposing said .
insoluble barium compounds by heating with a source of
silicon dioxide at a temperature between 1300” and 1500°
Barite ore obtained from Missouri and analyzing
C., said insoluble barium compounds and the source of
silicon dioxide being present in a barium to silicon ratio
of from 1.1 to l, to 3 to 1 to produce a polybarium sili
96.5% 'BaSO4, 2.5% SiO-Z' and 0.5% Fe203 was ground
to —100 mesh in a hammer-mill and mixed with silica
?our (—200 mesh, 96.2% SiO2). 2% of a 50% calcium
lignosulfate slurry in the form of a 12.5% solution was
cate, reacting said polybarium silicate with said sulfonic
sprayed on the dry powder to act as a binder and the 35 acid derivative in the presence of water and a hydro
carbon solvent at re?uxing temperatures, recovering said
whole mixed in a pug mill.. The amounts of barite and ‘
.barium salts of organic sulfonic acids and a silicon di
silica ?our were adjusted so that the mixture contained
' oxide-containing residue and recycling said residue as a
a barium to silicon ratio of 2.5 to 1 by molecular equiva
source of silicon dioxide.
lents.
2. The process of claim 1 wherein said organic sulfonic
This mixture was fed into va rotary kiln 35’ long with 21 40
acid derivatives are mahogany petroleum sulfonic acid
1A2" pitch per foot and a 30” shell diameter lined with a
_70% alumina refractory brick 41/2” thick. The kiln was
derivatives.
I
'
v
_
“
.
I
‘
>
?tted with means to control the rate of admission of air
3. The process of claim, 1 wherein said polybarium
so that the proper atmospheric control within the kiln
silicate is reacted with a petroleum sulfonic acid in the
could be maintained vand a gas burner burning natural gas 45 presence of water and a’ hydrocarbon solvent and the
was used to ?re the kiln. The material exit of the rotary
barium salt of the petroleum sulfonic acid is further re
kiln was a spill gate adjustable to allow only product to
acted with said polybarium silicate and a promoter
flow through. The exhaust gases from the kiln were con_
selected from the group consisting of phenols and barium
phenolates.
tinuously analyzed, and the gas and air adjusted to main
tain an exhaust gas concentration of hydrogen of 2% to 50
4. The process of claim 1 wherein said silicon dioxide
2.5% and a temperature in the hottest zone of 14000 C. to
containing residue recovered contains residual barium
1450“ C.
values and is further reacted with a petroleum sulfonic
The mixture was fed into the kiln at a rate of 150
acid in the presence of water and a hydrocarbon solvent,
~ lbs./hr., allowing pelletization to occur in the back end
to recover further barium salts of petroleum sulfonic
of the kiln. The decomposition of barite averaged about 55 acids and a silicon dioxide-containing residue.
80%. The polybarium silicate product produced con
5. The process of claim 1 wherein said silicon dioxide
tained water-soluble barium values and some undecome
containing residue recovered contains residual‘ barium
values and is further reacted with a mineral acid in the
vposed B21804.
The polybarium silicate produced was reacted with
“Petronic Acid” in the same manneras described in Ex‘
ample 3. Upon ?ltration of the hot- neutral barium sul-‘
60
presence of vwater to recover ‘the residual barium values
as water soluble barium salts of said mineral acid and
, a silicon dioxide-containing residue.
fonate solution a residue was obtained which consisted '
6. The process’ of claim 1‘ wherein said polybarium sili
primarily of SiO2 and BaSO4 in a ratio of approximately
cate is reacted with an alkali metal petroleum sulfonate
1.1 mol of SiOz to 0.3 mol of undecomposed BaSO4.
in the presence of a mineral acid, water and a hydro
This residue can be recycled to replace the silica ?our in 65 carbon solvent.
whole or in part.
7. The process of claim 6 wherein said silicon dioxide
containing residue contains residual barium values and
EYAMPLE 25
The same procedures as in Example 24 were followed, 70
except that the kiln feed was a mixture of silicon dioxide
containing residue as obtained from Example 24 and
barite. A continuous operation was e?ected by recycling
the silicon dioxide-containing residue and adding su?i
cient barite containing 96.5% BaSO4 to bring the bariur‘n/ 75
is further reacted with an alkali metal petroleum sul
fonate in the presence of a mineral acid, water and a
hydrocarbon solvent.
8. The process of claim 1 wherein said polybarium
silicate is reacted with an ammonium petroleum sul
_ fonate in the presence of water and a hydrocarbon sol
vent.
'
9. The process of claim 8 wherein said silicon dioxide- 0
3,031,497
15
16
containing residue contains residual barium values and
- carbon solvent at re?uxing temperatures, recovering said
is further reacted with an alkali metal petroleum sul
fonate in the presence of a mineral acid, water and a
barium salts of mahogany petroleum sulfonic acids and
a silicon dioxide-containing residue, and recycling said
hydrocarbon solvent.
residue as a source of silicon dioxide.
10. The process of producing barium salts of mahog
any petroleum sulfonic acids from (1) mahogany petro
leium sulfonic acid derivatives selected from the group
consisting of the free acids, and ammonium and alkali
metal salts thereof, and (2) insoluble Kbarite, which com
prises decomposing said barite by heating with a source 10
of silicon dioxide at a temperature between 1300° and
15000 C., said barite and said source of silicon dioxide
being present in a barium to silicon ratio of from 2.2 to 1
to 2.7 to 1 to produce a polybarium silicate, reacting said
polybarium silicate with said mahogany petroleum sul 15
fonic acid derivative in the presence of Water and a hydro
References Cited in the ?le of this patent
UNITED STATES PATENTS .
2,483,800
2,846,466
Zimmer et a1 ___________ __ Oct. 4, 1949
Crosby _______________ __ Aug, 5, 1958
2,856,360
Schlicht ______________ __ Oct. 14, 1958
797,409
Great Britain __________ .._ July 2, 1958
FOREIGN PATENTS
OTHER REFERENCES
Mellor: “Comp. Treat. on Inorg. and Theor. Chem,”
vol. 6, pages 353, 371 (1925).
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