Sul Fo Nation

8/16/2019 Sul Fo Nation

1/48

SULFONATION


2/48

Part #1 What is sulfonation

Types f sulfonation

Classification of sulfonates Procedures for preparing sulfonates


3/48

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


4/48

CLASSIFICATION OF

SULFONATES

liphatic and alicyclic

romatic Hetrocyclic

*sulfonates


5/48

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


6/48

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


7/48

CLASSIFICATION OF

SULFATES

Sulfated al%anes

lcohol sulfatesCyclic sulfates

Sulfated car0ohydrates

Sulfated nitrogenous polysachrides


8/48

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


9/48

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


10/48

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


11/48

$&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


12/48

PROCEDURE FOR

CO%PLETING SULFONATION

se of e#cess acid

Physical remo/al of +ater

Chemical remo/al of +ater


13/48

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


14/48

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


15/48

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


16/48

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


17/48

SOL*ENTS

8#cess acid

Chlorinated sol/ents

9i:uid SO"

:ueous sol/ents 1iscellaneous sol/ents

Sol/ent sta0ility


18/48

+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


19/48

%EC$ANIS% OF REACTION

Eelectrophilic substitution


20/48

ARO%ATIC SULFONATION

Without sulfur trio#ide

.ntermediate compound is electrically neutral


21/48

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


22/48

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


23/48

HEAT OF SULFONATION et heat e/ol/ed can 0e calculated from the

follo+ing e:uation


24/48

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


25/48

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


26/48

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


27/48

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


28/48

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


29/48

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


30/48

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


31/48

COMMERCIALSULFONATION METHODS 2atch process

Continuous process


32/48

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


33/48

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


34/48

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


35/48

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


36/48

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


37/48

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


38/48

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


39/48

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


40/48


41/48

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


42/48

SULFONATION OF BENZENE

2enene can 0e sulfonated 0y

2atch process

Continuous process

2atch time is more as compared to residence timein continuous reactor


43/48

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


44/48

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


45/48

-ATC$ PROCESS FOR %ONOSULFONATION OF

-EN.ENE

Benzenesupply tank

Benzenefeed line

Perforateddistributor

External oilheatingmechanism

Gauge

CoolingcoilJacket

Recycledbenzene

Condensedliquor tank

MONO ULFON TION OF BENZENEPressure


46/48

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


47/48

ANTHRAQUINONE 1-SULFONATE

-a+ materials

:uinone

oleum

Catalyst1ercury sulfate

Sulfonator temp &4*'4oC

-eaction time in sulfonatorD34 min


48/48

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

Documents

Sul Fo Nation