Dec. 20, 1955 C. E.

JOHNSON ET AL 2,727,920
OXIDATION OF MERCAPTANS TO SULFONIC ACIDS
Filed April 20, 195l

183.d1S

&Iv,HoN30*xo

OZ
 United States Patent Office ;
(Ind. Eng. Chemn. 32, 950-953 (i940) ) and disulfides
are produced by catalytic oxidation of the mercaptides
2,727,920 in the caustic-solutizer solutions as described by J. P.
OX DATION OF MERCAPANS TO SULFONC O'Donnell (The Oil and Gas journal, pp. 45-47 (July
ACDS 1, 1944). As stated above, an object of this inven
Carl E. Johason, Griifith, and William F. Wolff, Hana
tion is the avoidance of such intermediate steps for the
mond, Ind., assignors to Standard Oii Company, Chi production of disulfides and the provision, instead, of a
cago, Ill., a corporation of Indiana direct process of oxidizing mercaptains to organic sul
fonic acids while at the same time avoiding the described
Application April 20, 1951, Seria No. 222,984 () difficulties encountered by known processes.
19 Caims. (C. 260-53) Yet another object of the invention is the provision of
a process for producing organic sulfonic acids in high
yield and highly purified condition wherein air or oxy
This invention relates to an improved process for pre s to gen alone is consumed in the oxidation of mercaptains
paring organic sulfonic acids. It has particular refer the said acids, and wherein catalyst and/or reaction
ence to improvements in a process of catalytic oxidation medium are recyclable and are not consumed by the
of organic sulfur compounds having the general formula oxidation reaction. The invention has for other objects
Such other advantages or results as will be found to ob
RSH wherein R can be an alkyl, aralkyl, or cycloalkyl tain in the specification and claims hereinafter made.
radical. 20 Briefiy, this invention comprises the introduction of
A known process for the preparation of organic sul relatively small quantities of feed stock consisting of a
fonic acids by the oxidation of mercaptains is disclosed Saturated hydrocarbon thiol into relatively large quanti
and claimed in a U. S. patent to Proell et al., 2,505.910 ties of a liquid reaction medium containing nitrogen oxide
issued May 2, 1950. In this process a gas containing catalyst and absorbed oxygen and effecting an oxida
free oxygen is flowed into contact with a non-tertiary mer tion of the said thiol to a sulfonic acid in the presence
captain is the presence of a catalyst selected from the of the said catalyst and also a promoter compound. Hy
group consisting of NO2, N2O3, N2O4, N2O5, which may drocarbon thiols in which the sulfhydryl group is linked
be generated in the reaction zone by nitric acid. In the to a non-tertiary hydrocarbon is much preferred as feed
patented process air is charged to a reactor containing Stock, these thiols providing high, almost theoretical,
the Inercaptain for a considerable period, in one example 30 yields of the corresponding sulfonic acids. In order
45 minutes, before oxygen absorption occurs and before to avoid prolonged induction periods or explosive or un
any reaction product is obtained. During this period even reaction rates, it is essential to form in situ or to
the mercaptain turns a bright red, presumably due to the add to the said medium, either just before introduction
formation of a mercaptan-nitrogen oxide complex. When of
oxidation of the mercaptain in this complex eventually 35 introduction of feed stock, a minute quantityorof
the feed stock or simultaneously therewith just after
a pro
occurs, it occurs with almost explosive violence. The moter that will initiate the reaction and will continue
Sulfonic acid products of the patented process range in col to promote the oxidation of each increment of intro
or from dark brown to pale yellow and must be further duced thiol.
treated by a separate oxidizing step employing, for ex
annple, nitric acid, to remove the color and odor bodies 40 lictThe said promoter is an intermediate oxidation prod
of a mercaptain; the term "intermediate oxidation
remaining in this product. product' does not include the ultimate products, either
it is a primary object of the present invention to pro the sulfur oxides or the carbon oxides, but does include
vide an improved process for the production of sulfonic Substances, such as sulfur, that will produce an inter
acids in a direct single-step oxidation whereby substan
tially colorless Sulfonic acids substantially free of par mediate oxidation product of a mercaptain under initial
reaction conditions. The promoter can be an organic
tially-oxidized contaminants are produced. polysulfide, sulfoxide, disulfoxide, disulfone or sulfonic
It is another object of this invention to provide a proc acid. The organic polysulfide is a compound having the
eSS for the production of sulfonic acids by the oxida formula
tion of mercaptains while avoiding the violence of the icals andRSnR' n is
wherein R and R' are hydrocarbon rad
an integer between one and six inclusive
reaction above-described and obviating the difficulty of 50 and in which R and
containing the reacting mass in conventional apparatus. more preferably are theR' same are preferably the same and
as the hydrocarbon rad
It is yet another object of the present invention to ical of the feed stock and in which n is preferably 2.
provide a process for the direct oxidation of mercaptans The other oxidation products have the formulas,
to organic sulfonic acids without the necessity of oxidiz
ing mercaptain feed stocks by an intermediate step to 55 and R' areRSOOSR,
RSOSR", RSO4R, and RHSO3, in which R
hydrocarbon radicals.
organic disulfides. Organic disulfides can be oxidized Minute amounts of this promoter will immediately ini
by a gas containing free oxygen in the presence of a tiate reaction of added hydrocarbon thiol that has been
catalyst Selected from the group NO2, N2O3, NaO4 and introduced into a liquid medium containing a nitrogen
N2O5 as taught in Proeil et al., 2,433,395. The product oxide catalyst and oxygen or oxygen-containing gas.
of this process uniformly resulted in the production of 60 These minute amounts
"a pale, reddish-brown colored product” which had to a very Small quantity of can be supplied by introducing
mercaptain into a nitric acid so
be bleached with concentrated nitric acid in a separate lution of oxygen and subjecting the mercaptain to a pro
Step in order to remove color and odor bodies. Our longed induction period. The mercaptain will then re
co-pending application Ser. No. 205,902 filed January act with explosive violence but this very small amount
13, 1951, now Patent No. 2,697,722, has for its object will exert no disturbing effect and will nevertheless sup
the production of an improved organic sulfonic acid ply enough of Some oxidation product to promote the
product in a single step by direct oxidation of disulfides. oxidation reaction.
Sually, however, these organic disulfides are obtained Once the reaction is initiated by the introduction of
indirectly from mercaptains. This is especially true in Some promoter, reaction will thereafter continues smooth
the petroleum refining art wherein petroleum distillates ly, apparently because the promoter, being an oxidation
are desulfurized by extraction of distillates with caustic product of the mercaptain, is always present once the oxi
Solutizer Solutions as described by D. A. Yabroff et al. dation has begun. Thus one can explain this continued
 2,727,920
3 4.
promotion of oxidation, without, however, limiting the petroleum fractions derivedbefrom
stock for our process can obtined from the various
sulfur-bearing crude
invention to any solely theoretical considerations, on the
basis that, for example, the disulfide promoter is self oils. A petroleum fraction in, for example, the gasoline
range, can be extracted with a caustic solution which will
regenerable since it initiates a reaction that continues to remove mercaptains from the said fraction. The caustic
produce promoter disulfides as an intermediate product 5
solution can be stripped with open steam and the mercap
even though the initially introduced promoter disulfide tans collected as a distillate fraction. These mercaptan
may itself be oxidized. In the absence of the promoter, feed stocks can be fractionated so that only a single mer
added hydrocarbon thiol will react with the nitrogen oxide captain is oxidized, or a mixture of mercaptans can be
catalyst and will form a complex with all the catalyst, this employed. .?
complex being an explosive, red compound that will oxi 0.
dize to sulfonic acid only after a prolonged induction Mercaptains suitable for feed stock can be prepared syn
period. The hydrocarbon thiol-nitrogen oxide complex thetically, for example, by the addition of hydrogen sul
as indicated by a red coloration appears to be momentarily fide to olefins.
formed even when promoter compound is present; but The oxidation products may be recovered from the reac
this observed red color of the complex rapidly disappears. tion mixture by various methods which will vary with
In carrying out our invention we slowly add a saturated the nature of the individual product mixture. Such meth
hydrocarbon thiol in which, preferably, the sulfhydryl ods as extraction with solvents, fractional crystallization,
group is linked to a non-tertiary carbon atom, the said distillation and the like may be used.
In the accompanying drawing the single figure is a
thiol being a mercaptain having the formula RSH in which 20 schematic
R can be an alkyl, cycloalkyl, or aralkyl radical, to an flow diagram illustrating a preferred arrange
aqueous solution of nitric acid containing by weight from ment of apparatus suitable for carrying out the process
10 to about 70 per cent and preferably from 35 to about of invention.
50 percent of nitric acid under pressure of oxygen con Referring now to the drawing, a continuous process set
taining gas at a pressure between about 1 and 20 atmos up to produce about four tons a day of mixed alkanesul
pheres, the introduced hydrocarbon thiol compound or fonic acid is described. Air is passed at a rate of about
the aqueous reaction medium containing initially a very 14,500 standard cubic feet per hour from a source 10
minor quantity of a selected mercaptan-oxidation-product through a line 11 in which can be disposed a drier (not
promoter. The oxidizing reaction mixture is cooled, pref shown) and is forced into an oxygen absorber 12 which
erably by an extraneous cooling medium, to a reaction 30 consists of a packed tower about twenty feet high. The
packing can be for example, hurdles or Raschig rings.
temperature between about 10 and 130 C. and prefer The tower is maintained at a pressure of aboutfifty pounds
ably between 20 and 60° C. While the ratio of nitric per square inch gage. Nitric acid is flowed at a rate of
acid to introduced and hence substantially instantaneously about 98 pounds per hour (on an anhydrous basis) under
oxidized mercaptain is of no critical importance it is prefe pressure into valved line 13 from a source 14 and through
erable to maintain a ratio of about 0.1 to 10 mols of
ntric acid per mol of the oxidized mercaptain and more arial, recycle line 15, wherein it admixes with recycled mate
preferably from 0.1 to 0.8 mol of nitric acid per mol of cycledandliquid into the absorber 12. The nitric acid and re
is sprayed from a distributor 16 disposed
the oxidized mercaptain or sulfonic acid in the circulat above the packing in the extreme upper portion of tower
ing system. Of course the instantaneous ratio of nitric 12. Nitric acid, recycle liquid, and the introduced air
acid to introduced mercaptan will be very high. On the 40 flow concurrently down over the packing. The admixed
other hand, since introduced air or oxygen is the only con
sumed reactant the ultimate ratio of introduced mercap to 60 C.liquid is maintained at a temperature between 15
gas and
tan to nitric acid is beyond practical measurement. The mixed liquids containing recycle material and
If the process is performed batchwise, upon comple nitric acid collect in the separating zone 17 at the bottom
tion of the introduction of mercaptain the reaction mix 45 of
ture is then stripped with an inert gas. If the process is sorbed column
the 12. The solution will contain oxygen ab
during passage through the packed tower. In addi
performed in continuous manner nitric acid containing tion to providing for absorption of oxygen the foregoing
organic sulfonic acid can be removed from the oxidation treatment will also effect an oxidation of any reduced
systern preferably at a rate approximating the rate of in nitrogen oxides, e.g. nitric oxide, formed during the oxi
troduction of mercaptain into the system, and be stripped 50 dation of sulfides. Gas which has separated from the liq
with an inert gas preferably at temperatures between uids in the separator zone 17 will flow from the tower 12
about 80 and 150° C. Water and nitric acid will thus through a line 18 in which is disposed cooler 19 into a
be stripped from the sulfonic acid which can be obtained separator 20 containing baffles or other conventional sep
by this process in yields as high as 98 to 99 percent of arating means and will be vented from the separator 20
theoretical and which will be found to be of improved 55 through valved line 21. Liquid separated in the separator
color and purity. The acids are quite low in sulfate con 20 will be returned to the valved line 22 to the bath of liq
tent, and in reducing-impurities as indicated by their per uidin separator17.
manganate number, having dess than one-fourth the im The solution of nitric acid containing absorbed oxygen
purities displayed by sulfonic acids produced by the known and recycle liquids is withdrawn from the tower 12 at a
processes. rate of approximately 200,000 pounds per hour through
Feed stocks that are especially suitable for charging to a valved line 23 and is pumped therefrom through valved
this process are those saturated non-tertiary hydrocarbon line 24 by a pump 25 disposed therein to oxidation re
thiols having an alkyl group such, for example, as methyl, actor 26.
isopropyl, secondary butyl, amyl, lauryl, hexadecyl, octo Feed stock in the present preferred embodiment is a
decyl and the like. Suitable cycloalkyl groups include 65 mixed mercaptain consisting of primary and secondary
cyclopentyl, methylcyclopentyl, cyclohexyl and the like. alkyl mercaptains having from one to about 6 carbon
A suitable aralkyl radical is the benzyl group. atoms per molecule and obtained as previously described
When the present process was operated with a tertiary herein by steam distillation of a caustic solution of mer
mercaptain, tertiary butyl mercaptan, reaction proceeded captides derived from caustic extraction of a petroleum
to give, in addition to about a 30% yield of a water naphtha. The mixture is substantially free of naphtha
Soluble, apparently sulfonic-acid product, an uncharac and phenolic materials. The average molecular weight
terized, highly lacrimatory heterogeneous product, insol is about 62 corresponding to ethyl mercaptan. The feed
uble in water. Oxygen consumption during thhe reaction stock is flowed under pressure at a rate of 196 pounds
was low and would account for only partial oxidation of per hour from a source 27 through valved line 28 into the
the converted mercaptain to sulfonic acid. - line 24 and thence into the said oxidation reactor 26. The
An industrial source of considerable volume of feed
 2,727,920
5 6
reactor 26 is a coil which can be about 5 to 10 feet in The following examples serve to illustrate the present
length and is surrounded by cooling water in a jacket 29 invention with respect to the oxidation of two mercaptains
having a conventional water inlet 30 and outlet 31. that are available in commercial quantities in refineries.
About 100 cubic centimeters of diethyl disulfide are Example I
delivered from a source 27a through valved line 28a into
line 28 just upstream of its junction with line 24 and is Nitric acid was circulated by a stainless steel circulating
fed with the initial portion of the aforesaid feed stock into pump through a glass spray chamber maintained under an
the said oxidation reactor 26 and the solution of oxygen in oxygen pressure of between 2 and about 5 pounds per
aqueous nitric acid contained therein.
Oxidation of the feed stock mercaptains is accomplished 0. oxygen was gauge.
square inch The nitric acid containing absorbed
flowed from the spray chamber through a
almost instantaneously in the reactor 26. Observation Inixing and reaction zone and then was returned to the
of the reaction in the laboratory indicates a slight tempo said chamber. The system contained a total of 1.4 gram
rary formation of the red nitrate-mercaptain complex but mols of nitric acid. Isopropyl mercaptan was slowly
this disappears almost immediately. Absorption of oxy added to the aqueous nitric acid solution, which had a
gen begins the moment the disulfide promoter is added. 5 concentration of about 41 percent, until about 5 milli
The reaction is, of course, exothermic and therefore cool meters of the mercaptain had been added. No reaction
ing is employed to maintain temperatures below about was obtained and no absorption of oxygen was observed.
100 C. and preferably between about 15° C. and 60° C. A few drops of methyl disulfide were then added to the
Liquid product is flowed from the oxidation reactor and system. After 24 minutes, oxidation of mercaptain and
is recycled through the line 15 to the oxygen absorber 20 consumption of oxygen began. Reaction was not initi
12. The reaction product will contain a yield of sul ated immediately upon introduction of promoter because
fonic acids of about 95 mol percent of the introduced it was not introduced with the first portions of mercap
feed stock. It will also contain nitric acid depleted of tan and consequently an accumulation of complex was
oxygen and to a lesser degree some water and nitrogen permitted which presumably must be destroyed to per
oxides. It is recycled to the oxygen absorber solely for mit reaction to proceed. Once the oxidation had begun
the purpose of restoring the oxygen content of the acidic the mercaptain was steadily and slowly added to the nitric
liquid reaction medium, an amount of oxygen having acid, 100 milliliters of isoproply mercaptain being added
been consumed in the oxidation reactor about stoichio over a period of about one hour. Oxidation of the mer
metrically equivalent to the weight of introduced and oxi captain appeared to occur almost immediately upon addi
dized feed stock. tion to the nitric acid. The consumption of free oxygen
Product containing nitric acid with which it is bound 30 was substantially equivalent to the mol weight of con
in a loose complex is withdrawn from the described proc verted ethyl mercaptan. The product was withdrawn and
ess from a point at the junction of valved lines 23 and 24 stripped with nitrogen to remove nitric acid and water,
and is pumped at a rate of 50 gallons per hour through
a valved line 32 by a pump 33 into an upper portion of taineda colorless,
and odorless propane-2-sulfonic acid was ob
in 92.5 percent of theoretical yield. The sulfonic
stripper colunm 34. The product liquid which is main acid contained only 0.18 percent sulfuric acid.
tained at a temperature between about 80 and 140 C. Example II
and at a mild pressure flows down over hurdles or Raschig
rings of said stripper column in countercurrent contact Aqueous nitric acid in about 41 percent concentration
with an inert gas which is flowed under pressure from a 40 was circulated through the apparatus described in Exam
Source 35 through valved line 36 into the stripper 34 at a ple I. Before addition of any mercaptan 5 milliliters of
point near the base thereof. The inert gas is discharged ethyl disulfide were introduced into the circulating nitric
into the column from a distributor 37 disposed directly acid under nitrogen pressure. Thereafter 100 milliliters
beneath the packing. The inert gas strips nitrogen oxides of ethyl mercaptain were slowly introduced into the sys
from the countercurrently flowing product liquid and flows tem. The ethyl mercaptam oxidized substantially imme
out of the stripper through a line 39, through a cooler diately upon introduction; addition of mercaptain and
40 disposed therein, and into a scrubber 41 wherein the oxidation thereof was completed in a period of 50 min
inert gas and stripped nitrogen oxides are scrubbed with utes. The consumption of free oxygen was substantially
water introduced through line 42. Inert gas is liberated equivalent to the weight of converted ethyl mrecaptan.
through vented line 43. Aqueous solution of nitrogen After stripping the water and nitric acid from the prod
oxides, being essentially a dilute solution of nitric acid, is uct an odorless and colorless ethane sulfonic acid was ob
withdrawn through valved line 44. This dilute nitric tained having a specific gravity of 1.360.
acid can be returned to the oxidation system and be Example III
added to the nitric acid in valved line 13 or it can be
concentrated prior to its return to the said system. It A few drops of mixed alkane sulfonic acids having a
may contain a very minor amount of sulfonic acid carried molecular weight about equivalent to that of ethane sul
over with the stripping gas stream and so it is preferable fonic acid and containing both this acid and some meth
to reemploy the dilute acid in the process. ane- and propane-Sulfonic acid, were added to a dilute
Sulfonic acid from which bonded nitric acid or nitro solution of nitric acid having a nitric acid content of 41
gen oxides have been removed by the said stripper 34 is percent and under pressure of an oxygen-containing gas
withdrawn from a settling zone 46 in the bottom of 60 of approximately atmospheric. Isopropyl mercaptain was
column 34 through a valved line 47 at a rate of about 330 thereafter slowly added to a relatively large volume of
pounds per hour and is delivered to storage means 48. the aqueous nitric acid solution containing the sulfonic
The sulfonic acid will be between 95 and 100 percent pure acid while maintaining a temperature of slightly above
and will display a specific gravity of about 1.355 at 22 room temperature and a deep red color was rapidly
C. and a permanganate number of between about 10 and formed and was rapidly dissipated with resultant oxida
20 as compared to 60 for the products of prior art proc tion of the isopropyl mercaptan and solution of the prod
esses. These permanganate numbers are relative only and uct in the aqueous nitric acid solution.
are determined by titration with a standard permanganate The experiment was repeated under the same conditions
Solution of a diluted aliquot of the sulfonic acid to an
endpoint at which the pink coloration of permanganate moter the using same reactants with the exception that no pro
was added to the aqueous nitric acid solution.
remains in the titrated solution. The permanganate num No reaction whatsoever was observed.
ber is defined by the following expression:
Example IV
cc. of KMnOX1000 In this example it is shown that the mercaptan-oxida
PN= of acid)xpercentage concentration of acid 75 tion-product promoter can be formed in situ in the re
 7 8
action zone. The oxidation apparatus described in the radicals and n is an integer between one and six inclu
foregoing examples contained 170 milliliters of 41 percent sive.
nitric acid and the acid was under a pressure of 5 pounds 8. The process of claim 7 wherein n is 2.
per square inch gauge of oxygen. To this aqueous nitric 9. The process of claim 7 wherein n is 2 and R and
acid solution only 5 milliliters of isopropyl mercaptain R" represent alkyl groups.
10. A process for the production of an organic sul
was added. The system was maintained at a tempera fonic acid, the said process comprising the steps of slowly .
ture of 30 C. There was no evidence of any imme introducing into a large volume of an aqueous solution
diate reaction of the mercaptan. After a period of 50
minutes a slight brown coloration was observed in a 0 of nitric acid containing absorbed free oxygen a saturated
hydrocarbon thiol wherein the sulfhydryl group is linked
small oil layer and a slight pink color was observed to a non-tertiary carbon atom while maintaining at any
after an additional 15 minutes. This pink color deep moment the aqueous nitric acid solution in multimolar
ened and became red after an additional 50 minutes. excess with respect to introduced thiol, introducing into
After 125 minutes had elapsed from the initial addition the reaction zone substantially
of mercaptan, during which period no oxygen was ab initial introduction of mercaptaincontemporaneously a small amount
with
of an
sorbed, a sudden reaction occurred with evolution of intermediate mercaptan-oxidation product selected from
red fumes, oxygen was absorbed, and the red color dis
appeared. After this reaction, additional mercaptan was the ides,
group consisting of hydrocarbon polysulfides, sulfox
disulfoxides, disulfones and sulfonic acids, cooling
added and oxidation proceeded smoothly.
It is noted that even this small amount of mercaptan 20 the oxidizing reaction mixture to maintain the temper
ature of the said mixture between 10 and 130 C,
reacted with some violence and it would be highly un effecting oxidation of the said thiol, recycling the aqueous
feasible to add any really substantial amount of mer
captan to the nitric acid solution because of the explosion oxygen toofabsorb
solution nitric acid to contact a gas containing free
therein free oxygen substantially equiva
that would ensue. Thus the example demonstrates not lent to the amount of oxidized thiol and restore the
only the fact that the promoter can be produced in situ oxygen content of the solution depleted by the oxidation
if a small amount of mercaptain is held in the acid of the thiol, recycling the aqueous nitric acid solution
solution for a long time but also it illustrates the pro to the reaction zone, and recovering a sulfonic acid so
longed induction period that is encountered unless a
promoter is introduced initially with the mercaptain feed. produced. 11. A process for the production of an organic sul
The invention therefore encompasses not only the proc fonic acid, the said process comprising, slowly introduc
ess of oxidizing mercaptains in which oxidation is ini
tiated by the addition of an organic mercaptan-oxida group saturated
ing a
is linked
hydrocarbon thiol wherein the sulfhydryl
to a non-tertiary carbon atom into a
tion product but also the oxidation process when the relatively large body of aqueous solution of nitric acid
oxidation product is formed in situ; either procedure is containing absorbed free
suitable (for it will ensure the constant presence of action zone substantially oxygen, introducing into the re
the promoter compound during the oxidation process) introduction of the thiol a catalytic amount ofwith
contemporaneously initial
so long as the order of addition is of mercaptan to rela mediate thiol-oxidation-product promoter, cooling theinter an
oxi
tively large volumes of oxidizing medium thus providing dizing reaction mixture to maintain the temperature of
a colorless and odorless product substantially free of the said mixture between 10 and 130 C, effecting re
contaminating partial oxidation products.
The term "catalytic' used in the claims is defined in 40 aaction between the oxygen and said thiol, and recovering
sulfonic acid so produced.
Webster's New International Dictionary, Second Edition 12. The process of claim 11 in which the interme
(1934). Unabridged, page 421, as follows: “Catalytic, diate mercaptan-oxidation product is selected from the
adj., Pertaining * * * to, * * * or causing, catalysis.” group consisting of hydrocarbon polysulfides, sulfoxides,
Having described our invention, we claim: 45 disulfoxides, disulfones, and sulfonic acids.
1. A process for the production of sulfonic acid, which 13. The process of claim 11 wherein the saturated
process comprises introducing, in an oxidation reaction
zone, a saturated hydrocarbon thiol into an aqueous hydrocarbon thiol is an alkane thiol.
14. A process for the production of sulfonic acid which
solution of nitric acid containing absorbed oxygen, main process
taining a substantial instantaneous excess of said solu 50 wherein comprises the
slowly introducing an alkane thiol
sulfhydryl group is linked to a non-tertiary
tion with respect to said thiol in said zone, effecting oxi carbon atom into a relatively large volume of an aque
dation of said thiol in the presence of a catalytic amount ous reaction medium - containing absorbed free oxygen
of an intermediate mercaptan-oxidation product, and re and nitric acid and effecting substantially instantaneous
covering a sulfonic acid so produced. oxidation of the introduced thiol at a temperature be
2. A process for the production of an organic sulfonic
acid, which process comprises slowly introducing sa satu tween about 20 and 60° C., introducing, substantially
simultaneously with the initial introduction of thiol into
rated hydrocarbon thiol, having the formula RSH in the aqueous medium, a catalytic amount of an effectively
which R is selected from the group consisting of alkyl, self-regenerable promoter compound having the formula
aralkyl, and cycloalkyl radicals, into an aqueous solu RSnR' wherein R and R' are hydrocarbon radicals and n
tion of nitric acid containing absorbed oxygen, said solu 60 is an integer between 1 and 6 inclusive, and recovering
tion being present in substantial excess with respect to a sulfonic acid so produced.
said thiol, effecting oxidation of the said thiol in the 15. A process for the production of an organic sulfonic
presence of a catalytic amount of an intermediate mer acid, the said process comprising; slowly introducing into
captan-oxidation-product promoter, and recovering a sul an aqueous solution of nitric acid containing from 10 to
fonic acid so produced.
3. The process of claim 2 in which the said mercaptan 65 70% by weight of acid and absorbed free oxygen an
alkyl mercaptain wherein the sulfhydryl group is linked
oxidation product is a hydrocarbon sulfoxide. to a non-tertiary carbon atom, while maintaining at any
4. The process of claim 2 in which the said mercaptan moment the aqueous nitric acid solution in substantial
oxidation product is a hydrocarbon disulfoxide. excess with respect to introduced thiol; introducing into
5. The process of claim 2 in which the said mercaptan the reaction zone as a promoter substantially contem
oxidation product is a hydrocarbon disulfone. poraneously with the initial introduction of mercaptain a
6. The process of claim 2 in which the said mercaptan catalytic amount of alkyl disulfide and effecting rapid
oxidation product is a hydrocarbon sulfonic acid. oxidation of the mercaptain by the said absorbed free
7. The process of claim 2 in which the said mercaptan oxygen; cooling the oxidizing reaction mixture to main
oxidation product is a hydrocarbon polysulfide having 75 tain the temperature of said mixture between 20 and
the formula RSnR' wherein R and R are hydrocarbon
 2,727,920
50° C.; effecting oxidation of the said thiol; recycling
the aqueous solution of nitric acid to the contact, under
a pressure of at least about one atmosphere, of a gas
containing free oxygen to absorb therein free oxygen
substantially equivalent to the amount of oxidized thici
and restore the oxygen content of the solution depleted
by the oxidation of the thiol; recycling the aqueous nitric
acid solution; and recovering a sulfonic acid so produced.
16. The process of claim 15 in which the aqueous nitric
acid containing the said produced sulfonic acid is stripped 0
with an inert gas from the said sulfonic acid.
17. The process of claim 15 in which the aqueous nitric
acid containing the said produced sulfonic acid is stripped
with an inert gas at a temperature between about 80
and 150 C. from the said sulfonic acid.
18. A cyclic recirculatory process for the manufacture
of a sulfonic acid, which process comprises absorbing
free oxygen in an absorption zone in aqueous nitric
acid having a nitric acid concentration within the range
of about 10 to about 70 weight percent, thereafter cir 20
culating oxygen-enriched aqueous nitric acid thus pro
duced to a thiol oxidation zone, introducing a saturated
hydrocarbon thiol wherein the sulfhydryl group is linked
to a non-tertiary carbon atom into said thiol oxidation
zone and into said nitric acid solution at Such a rate
as to maintain a substantial instantaneous excess of said
10
nitric acid solution with respect to said thiol, effecting
oxidation of said thiol while maintaining an oxidation
reaction temperature between about 10 C. and about
130 C., withdrawing oxidation reaction mixture from
said thiol oxidation zone; thereafter circulating oxida
tion reaction mixture from said thiol oxidation Zone
through said absorption zone, restoring the free oxygen
content of said mixture in said absorption Zone, recir
culating at least an aliquot of oxidation reaction mix
ture from said absorption zone to said thiol oxidation
zone and recovering sulfonic acid produced by the oxi
dation of said thiol.
19. The process of claim 18 wherein the oxidation re
action temperature is between about 20 C. and about
5 60° C:
References Cited in the file of this patent
UNITED STATES PATENTS
1925, 191 Keller ---------------- Sept. 5, 1933
2,204,210 Farlow ----------------- June 11, 1940
2,433,396 Proell ----------------- Dec. 30, 1947
2,489,318 Proel ----------------- Nov. 29, 1949
2,502,618 Proell ---------------- Apr. 4, 1950
2,505,910 Proell et al. ------------ Aug. 2, 1950
2,567,399 Proell ---------------- Sept. 11, 1951