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SULFONATION
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Part #1 What is sulfonation
Types f sulfonation
Classification of sulfonates Procedures for preparing sulfonates
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SULFONATION
Sulfonation is the introduction of a sulfonic acidgroup (–SO3H), or the corresponding salt or
sulfonyl halide group into an organic compound
Types Of Sulfonation Include
! Sulfochlorination
" Halosulfonation
3 Sulfo#idation
$ Sulfoal%ylation
& Sulfoacylation
' Sulfoarylation
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CLASSIFICATION OF
SULFONATES
liphatic and alicyclic
romatic Hetrocyclic
*sulfonates
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PROCEDURES FOR
PREPARING SULFONATES! Treatment of an organic compound +ith SO"
" Treatment +ith a compound of SO"
3 Condensation and polymeriation methods$ O#idation of an organic already containing
sulfur in a lo+er state of o#idation such as
-SH
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SULFATION
.n/ol/es the placement of the –OSO"OH group on
car0on, yielding an acid sulfate (-OSO"OH) , or of
the –SO$* group 0et+een t+o car0ons, formingthe sulfate -OSO"OH
Sulfatoal%ylationdesignates introduction of a
sulfated al%yl group into an organic compound
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CLASSIFICATION OF
SULFATES
Sulfated al%anes
lcohol sulfatesCyclic sulfates
Sulfated car0ohydrates
Sulfated nitrogenous polysachrides
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SULFONATING AND SULFATING AGENTS
Sulfur trioide and co!pounds! Sulfur trio#ide, oleum, concentrated sulfuric acid (SO3 plus
+ater)
" Chlorosulfonic acid (SO3 plus HCl)
3 Sulfur trio#ide adducts +ith organic compound
$ Sulfamic acid . The sulfur dio#ide group! Sulfurous acid, metallic sulfates
" Sulfur dio#ide +ith chlorine
3 Sulfur dio#ide +ith o#ygen . Sulfoal"ylatin# a#ent! Sulfomethylating agents
" sulfoethylating agents
3 1iscellaneous al%ylating agents
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C$E%ICAL AND P$&SICAL
FACTORS IN SULFONATION AND
SULFATION
When employing SO3 or its compound for
sulfonation and sulfation, important /aria0les
determining the rate of reaction are! Concentration of SO3 in sulfonating agent
" Chemical structure of organic compound
3 Time in relation to temperature and reagentstrength
$ Catalyst
& sol/ents
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CONCENTRATION OF SO'
To carry sulfonation and sulfation, it isnecessary to maintain the SO3 concentrationin the sulfonating agent at a certainminimum le/el
SO3 itself employed
! .nitial stage of sulfonation is completedrapidly
" 2ut sulfonic acid produced react +ith SO3
toformm comple#
. Sulfonating organic acid +ith SO3! .nitial reaction product is acyl sulfate
" e#t it is con/erted to sulfonate
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$&DRATES OF SO' Hydrates of SO3 are usually the solution of SO3 in
+ater
Water has a great affinity for SO3
.n this system it regarded as 0ase +hich in proportion to its concentration tend to neutralie
the acidic SO3
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PROCEDURE FOR
CO%PLETING SULFONATION
se of e#cess acid
Physical remo/al of +ater
Chemical remo/al of +ater
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C$E%ICAL STRUCTURE
romatic hydrocar0ons as a class are easilysulfonated
Su0stitution of hydrocar0on ring +ith hydro#al
or amino groups, or +ith successi/e al%ylgroups, increases the ease of sulfonation Halogen, nitro, car0onyl, and sulfonyl groups
ma%e sulfonation more difficult
Ortho para directing groups facilitatesulfonation, +hile meta directing groups hindersulfonation
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TI%E(TE%PERATURE(
REAGENT STRENGT$
To attain ma#imum efficiency in comercial
sulfonation the reaction time must 0e reduced to
minimum compata0le +ith product yield
-eaction rate is appro#imately dou0led 0y !45Crise in temp
1a#imum reaction rate is achie/ed +ith stronger
reagent
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CATAL&ST AND
SULFONATION AIDS
C)an#in# orientation
! The addition of mercury changes the orientation in anum0er of aromatic sulfonation reactions
" The form of mercury employed is immaterial
3 n organic mercurial intermediate is formed$ Catalytic effect functions for disulfonation
& 1ercury is utilied only +hen using oleum or SO3as sulfonating agent
' 1ercury effects the orientation of 0enoic acid, phthalic anhydride,naphthol, nitro0eneneetc
6 1ercury is also utilied in some cases to increaseyield in sulfonation 0ut +ithout changing orientation
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CATAL&ST
7acilitating reaction
! The addition of catalyst sometimes allo+s the
use of lo+er temperatures, impro/e yield,
acceleration reaction . .nhi0iting side reactions
! sulfone formation in case of aromatic
sulfonation can 0e a/oided 0y adding acetic acid
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SOL*ENTS
8#cess acid
Chlorinated sol/ents
9i:uid SO"
:ueous sol/ents 1iscellaneous sol/ents
Sol/ent sta0ility
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+INETICS OF SULFONATION
romatic sulfonation is a eelectrophilic su0stitutionreaction
Sulfonation is a re/ersi0le process
-eaction temperature in certain cases ha/e an
important influence on position of entering group Sulfur tri o#ide has a tendency to form comple# +ith
sulfonic acid
With sulfuric acid formation of +ater slo+s the
reaction With sulfur high speed of reaction is a pro0lem
We ha/e different rate e:uations +ith differentsulfonating agents
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%EC$ANIS% OF REACTION
Eelectrophilic substitution
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ARO%ATIC SULFONATION
Without sulfur trio#ide
.ntermediate compound is electrically neutral
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THERMODYNAMICS Heats effects encountered in sulfonation are of
great importance
;epending upon the reaction in/ol/ed and
upon ho+ it is conducted, net effect may /ary+idely from highly e#othermic o/er a short
period of time to endothermic o/er a long
period
Some reactions are e#hothermic in initial stage
0ut endothermic in final stage
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WITH SO3 AND ITS
COMPOUNDS
With SO3 and its compounds it is con/enientto calculate the net heat effect in any
particular sulfonation 0y using SO3 /apouras reference point reasons are
! 1ore heat is e/ol/ed in sulfonation +ith thisreagent then +ith any other group
" ll th compound of SO3 used as sulfonating
agents can 0e made from it 0y directe#othermic reaction +ith the materialforming the compound
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HEAT OF SULFONATION et heat e/ol/ed can 0e calculated from the
follo+ing e:uation
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DESULFONATIONREACTIONS romatic sulfonates are hydrolytically desulfonated 0y
heating in a:ueous acid medium
This re/erse reaction generally proceeds in rapidly andin good yield especially in the presence of mineral acid
+hich accelerates the reaction catalytically .t is proportional to hydrogen ion acti/ity of solution
7or each !4>C rise in temperature the reaction /elocityof hydrolysis increases "&*3& times and same +ith
molar increase in acid concentration With increase ring methylation desulfonation
temperature lo+ers
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DESULFONATION Sulfonation follo+ed 0y desulfonation has
0een used to separate mi#tures of aromaticcompounds not easily separa0le 0y sulfonation
;esulfonation is a tool in studying thechemical structure of commercial sulfonated petroleum fractions from lu0ricating oil range
Sulfonation*desulfonation is a useful tool for
preparing ortho isomer deri/ati/e of 0enene seful in ra+ material and +aste reco/ery
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WORKING-UP PROCEDURES There are different factors that ma%e the final
product separation a time consuming process
! Presence of e#cess acid
" nreacted starting material
3 Occurrence of side reactions . Some commercial sulfonation apply
stoichiometric amounts of reagents and
product can 0e used after neutraliation . .n some cases e/en +ith e#cess acid more
seperation is not re:uired
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SEPARATION PROCESSES
Dilution ,it) ,ater This method is often applied +hen using e#cess acid
or oleum and yield free sulfonic acid .ts use is 0ased on the %no+ledge that many sulfonic
acid are relati/ely insolu0le in sulfuric acid ofintermediate strength o0taina0le 0y suita0le dilutionof reaction mi#ture +ith +ater
pplied for th separation of
! Hydrocar0on sulfonic acids
" ;isulfonic acid of anthra:uinone3 Sulfonated aromatic amines
$ Sulfonated fatty oils
& romatic sulfonyl chlorides
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SEPARATION PROCESSES Saltin# out The method yields the sulfonate salt 0y the addition
of a:ueous aCl to the acid reaction mi#ture
The desired sulfonate salt is usually only slightlysolu0le in the dilute acid medium and oftencrystallies from it in good yieldit is used inseperation of
! Sulfonate dye intermediates
" Sulfonated fatty oils3 8fficiently employed to o0tain highly +ater solu0le
sulfonate salts
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SEPARATION PROCESSES
eutraliation +ith lime The procedure in/ol/es treatment of diluted reaction
mi#ture +ith Ca(OH)" or CaCO3 to con/ert e#cess
sulfuric acid to insolu0le calcium sulfate and thesulfonic acid to calcium sulfonate
Treatment of filtrate +ith sodium car0onate or sulfateyields insolu0le calcium car0onate or sulfate
The filtrate comprises the desired sodium sulfonate
se for the isolation of any sulfonate yielding a solu0lecalcium salt
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INDUSTRIAL EQUIPMENTAND TECHNIQUES
%aterial of construction
Cast iron is resistant to action of sulfuric acid
9ined steel /essels com0ine lo+ cost and high
strength +ith good corrosion resistance
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COMMERCIALSULFONATION METHODS 2atch process
Continuous process
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BATCH PROCESSING Sulfonation is conducted in
autocla/es of standard type
1a?or feature of
consideration are heat
transfer and agitation
;epending upon conditions
e:uipment maay 0e of cast
iron,glass lineed, lead lined
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BATCH PROCESSING
2all*mill sulfonator,opera0le under /acuum +ith
hot air heating, used +ith solid, doughy or
/iscous masses
Plastic coated steal to+ers are used
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HEATING AND COOLING Sometimes direct gas fire is used for heating Steam is most commonly employed Steam under pressure is used in ?ac%ets capa0le of
0earing !4atm pressure .n some cases cooling is re:uired +hich could 0edone 0y using 0rine
2y spraying +ater outside of %ettle
2y circulating through heat e#changer
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CONTINUOUS PROCESS Continuous process in sulfonation is usually
prefera0le in dye intermediates +hich are prepared
in relati/ely small amount from e#pensi/e ra+
materials
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ALIPHATIC SULFONATION Sulfo!et)ylation of aniline
! niline is reacted +ith a:ueous sodiumhydro#ymethanesulfonate
" :ueous sodium 0isulfite is charged to a 0ric% lined
/essel e:uiped +ith a 0lde agitator and copper coilfor heating and cooling
3 7ormaldehyde is then added +ith agitation follo+ed 0y heating for half an hour
$ fter cooling to "&>C aniline is added and
temperature is maintaind to "&>C for 3hoursfollo+ed 0y heating to 3&>C for one hour
& Tests are performed to chec% completionsalting outis done to get sulfonate
' Product is +ashed and filtered off
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ADDITION OF SODIUM BISULFITETO MALEIC ACID ESTER
;i maleate and @&A and ethanol are charged to anenameled ?ac%eted %ettle pro/ided +ith moderateagitation and distillation ta%e off
:ueous sodium hydro#ide is then added to neutralietoluene sulfonic acid catalyst in the crude ester
:ueous 0i sulfite is then added and the mi#ture isheated to !44>C +ith slo+ agitationit is held at thistemp for !" hours
The mi# is cooled to '4>C and the distillation ta%e off isconnected for the remo/al of alcohol sol/ent 0egins atB4>C
;istillation continued for 6 hours aat @!>C to remo/e6&A alcohol
Solution is then cooled and pac%ed
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SULFOETHYLATION OFOLEIC ACID Oleoyl chloride is heated +ith sodium "*
hydro#yethanesulfonate Solid "*hydro#yethanesulfonateis sho/eled into a
homogeneous lead lined condensation %ettle
Heating and stirring 0egin +ith oleoyl chlorideaddition The mi#ture is stirred for !& min after reaching !44>C When the reaction is /igorous and HCl e/ol/ed Temperature rises to !!4>C
7inally po+dered product is attained eutralie +ith sodium car0onate
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MONOSULFONATION OFBENZENE 2enene can 0e monosulfonated 0y partial
pressure distillation method Sulfuric acid is pumped from storage 9i:uid 0enene from storage is pumped to direct
/aporier superheater and then to sulfonator andsulfonation to+er
-eaction time is !& hours Temperature is !B4>C
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SULFONATION OFDODECYLBENZENE The hydrocr0on is pumped into the glass lined
sulfonation %ettle e:uiped +ith tur0o type mi#er ande#ternal heat e#changer
1i#er is turned on and "4A oleum is added as fast as
possi0le, not e#ceeding a temperature of 34>C -eaction time is !&*"4 hours
t the end spentacid has a strength of @B"A and ismi#ed +ith sulfonic acid
Water is added for layer seperation pper laayer of sulfonic acid is neutralied 0y adding
a:ueous soda
ppro#imately @4A of the hydrocar0onis sulfonated
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SULFONATION OF BENZENE
2enene can 0e sulfonated 0y
2atch process
Continuous process
2atch time is more as compared to residence timein continuous reactor
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BATCH PROCESS FOR
MONOSULFONATION OF BENZENE
-eaction timeD!$ hrs
TemperatureD!'4*!B4oC
cid strengthD@4*@"A
Eac%eted cast iron sulfonation %ettle is used gitation done at B4rpm
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MONOSULFONATION OF BENZENE BYCONTINUOUS PROCESS
Sulfuric acid is pumped from storage
9i:uid 0enene from storage is pumped to direct
/aporier super heater and then to sulfonator and
sulfonation to+er -eaction time is !& hours
Temperature is !B4>C
-ATC$ PROCESS FOR %ONOSULFONATION OF
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-ATC$ PROCESS FOR %ONOSULFONATION OF
-EN.ENE
Benzenesupply tank
Benzenefeed line
Perforateddistributor
External oilheatingmechanism
Gauge
CoolingcoilJacket
Recycledbenzene
Condensedliquor tank
MONO ULFON TION OF BENZENEPressure
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MONOSULFONATION OF BENZENE
ulfuric acid tank
Pump
Pressureregulator!eter
ulfon"ator
Benzene #ap$
%irect #aporizer
super heatermeter
ulfonation to&er
Benzene'
&ater#ap$
Condense
r
eparator
&ater
Benzene
(eutralizingdrier
)iq$Benzene
storage tanks
Product
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ANTHRAQUINONE 1-SULFONATE
-a+ materials
:uinone
oleum
Catalyst1ercury sulfate
Sulfonator temp &4*'4oC
-eaction time in sulfonatorD34 min
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ulfonator +iltrate
recei#ersPptator
torage for rotaryfilter
Rotary filter
(eutralmixer
toragemixer for
-./,"saltslurry
+ilter for
reco#eredanthraquinone
!ixer
0ash &aterstorage
*1dryer
torage
Conc$ ,Clsoln$
2.oC
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