PRESENTATION

ON

SULFATION

PRUTHVIRAJ CHAVHAN
(2759)
RAW MATERIALS & ADDITIVES FOR SLES (1M/2M/3M)

RM Name Use

ETLA (1M / 2M / 3M) Sulphate mass Formation

Sulphur SO2,SO3 Formation

Caustic Neutralisation and Product Formation

Soft water Neutralisation

Dry Air For sulphur burning/Quenching/ Dilution

Hydrogen peroxide For bleaching

Citric Acid & Caustic PH Adjustment

Sodium citrate Buffer

 PROCESS FLOW DIAGRAM
Atmospheric Air Exhaust Gases
Section 23
SO3 Absorption

Dry Oleum
Section 11 Air
Air Drying Section 14
SO3
Section Exhaust Gas
Treatment
SO3 + Air
Section 16 Unreacted
Section 12 Gases
Thin Film
SO2-SO3 Section
Sulphonation

Sulphonic
Acid
Section 25
Sulphur Melting Section 33 Product
Section Molten Sulphur Neutralization
Caustic Water
SECTION 11
 SECTION 11 (AIR DRYING SECTION)
Air drying section is used to provide moisture free & dust free air for-
 SO2 Formation in Furnace
 SO3 formation in converter
 For dilution purpose in Film Sulphonation.

Why dry & dust free air?

 Effects of Moisture on Process:
 It leads to Oleum generation
H2O + n SO3 H2S2O7
 It leads to dioxane formation
R(CH2CH2O)n OSO3H + H2O R(CH2CH2O) n-2 OSO3H +
(CH2CH2O)2
 It will affect the quality of product in terms of colour.

 Effect od dust : Dust will enter in production system and chock it. It may
also be carried over into the product.
DESIRED QUALITY OF DRY AIR PRODUCED

 Dust free
 Air Temperature = 4 to 8 0C

 Dew point temperature of dry air = - 60 0C

Sr. No. Dew point of process air gm water/ kg dry air

1 -20 0.634
2 -30 0.234
3 -40 0.079
4 -50 0.024
5 -60 0.0066

6 -70 0.0016
EQUIPMENT LIST OF SECTION 11

 Air filter :11F1 A/B

 Air blower :11K1 A/B
 Air cooler heat exchanger :11E3/E4
 MEG holding vessel :11V3
 MEG chiller :11RG1
 MEG circulation pump :11P1/P2
 Silica gel dryer :11C1 A/B
 Finned tube heat exchanger :11E2
 Regeneration air blower :11K2
 Furnace Dilution Quenching
CW in
CW out

11C1
11K
11E3 A
Moist
1
air
11E4

11C1 1
1
Condensate B E
2
MEG Tank

11RG1 Hot air

11K
2 in
 DIFFERENT TYPES OF DESICCANTS AVAILABLE
Property Molecular Silica Gel CaO CaSO4
sieve

Absorptive capacity Excellent Fair Excellent Good

Regeneration temp. (0C) 250 120-200 1000 235

Absorption capacity(gm H2O/gm 0.18 0.2 0.3 0.066

desiccant)

Absorption capacity at elevated temp. Excellent Poor Good Good

SECTION 25
 SECTION 25 (SULPHUR MELTING SECTION)
 This section is used for melting of solid Sulphur to liquid
form by application of steam.
 Liquid sulphur is then pumped to sulphur burning furnace
12H1

 Why to melt sulphur??

We can’t use solid sulphur because of..
 Ununiform distribution in combustion chamber
 Presence of impurities and ash
 High pumping cost
LIST OF TAGS IN THIS SECTION
Tag no description
25V1 Sulfur melter
25V2 Sulfur melter
25F1 Molten sulfur filter
25F2 Molten sulfur filter
25F3 Molten sulfur filter
25F4 Molten sulfur filter
25P1 Molten sulfur pump
25P2 Molten sulfur pump
PROPERTIES AND QUALITY OF SULPHUR
Sr.no Property
1 Appearance Yellow crystalline solid
2 Crystalline Forms Rhombic and Monoclinic
3 Melting Point 110 to 121 °C
4 Boiling Point 444°C
5 Flash Point 168 to 188°C
6 Auto-Ignition Temperature Liquid: 248 to 261°C
7 Density 1786 kg/m3 @ 140°C

Description Actual Data

Purity(%) 99 min
Ash Content(%) 0.08 max
Moisture content(%) 0.3 max
Arsenic (%) 0.25 max
 IMPURITIES IN SULPHUR & IT’S EFFECTS
Impurity Effect

Moisture 1.Moisture present in sulphur leads to formation of Acids that increases

risk of corrosion
Ash Content 1. Choking problem in Furnace
2. Increase in pressure drop in furnace
3. Increase in back pressure to 11K1
4. Blocking of NRV of sulphur pump leading to flow fluctuations
Hydrogen Sulphide 1. Toxic and can cause risk of explosion hazards

Arsenic 1. It reacts with vanadium pentoxide and decreases its life by

(Less than 0.25%) deactivating it. This is called catalyst poisoning.

Bitumen 1. Bitumen gets deposited on the walls of equipment & increses rate of
(Less than 0.5%) corrosion.
TEMP VS VISCOSITY RELATION FOR LIQUID
SULFUR:-

Temperature c
 SECTION 12
The purpose of section12 is production of SO2 and SO3

S + O2 SO2 + H = -298 KJ/mol S

SO2 + ½ O2 V2O5 SO3 + H = -3043 KJ/mol S

@ 427 OC
1.

2. Steps Involved :
3. 1. Production of SO2
4. 2. Production of SO3
5. 3. SO3 Cooling
EQUIPMENT & THEIR PURPOSE
 sulphur combustion furnace- 12H1
 so2 to so3 converter- 12C1
 air+ so3 cooler before 1st bed of converter-12E2
 air + so3 cooler before 2nd bed of converter-12E3
 quench air distribution in 3rd and 4th bed
 air + so3 cooler after converter - 12E5
 air +so3 cooler after converter- 12E6
 air +so3 cooler after converter- 12E7
 air + so3 cooler blower- 12k1
 combustion air blower -12k2
 combustion air blower -12k3
 startup air preheater - 12H2
 fuel tank- 12V1
 PFD FOR THIS SECTION:
TO WHRB
sulph
ur

12E2
12H1
BED
DRY 1
AIR 12E3
BED 2
TO 16F3

BED 12E6
3 12E5
12
V1 BED
4

12H2
12C1
OLEUM
12K2
12K1
SUMMARY OF STANDARD OPERATING PARAMETERS:

Parameter Standard Observation

Operating Range Frequency
Sulfur Inlet Temperature to 145 to 148 Continuous
12H1 in 'C
Sulfur Flow rate (Kg/hr) 300 continuous
Dry air Dew point in 'C(min) -60 continuous
Dry air temperature in 'C 15 TO 20 continuous
Pressure drop across furnace 0.02 Once in a 8 hrs
12H1 in Barg
12H1 outlet gas temperature 600 to 650 continuous
in 'C
SECTION 16
SECTION 16: FILM SULPHATION REACTOR

Tag no description
16F3/16V5 Oleum filter
16R1 Sulfation reactor
16P1 Cooling water cir. Pump
16P2 Sulphated mass pump
16V4 Gas liquid separator
16S1 Cyclone separator
16F4 A/B Organic filter
16V3 EMERGENCY VESSEL
16V2 ETLA DAY TANK
16E1 ETLA PHE
SECTION PFD:

16S1
 REACTION :

 Features of reaction:
 The reaction between ETLA & so3 is instantaneous
 Reaction is exothermic
 Heat of reaction = -138 kj/g mol of so3 reacted
 The temperature of reaction is controlled by removing heat of
reaction, by circulation of cooling water in shell side
 The sulfonic acid formed is highly unstable and hence it is
immediately pumped for neutralization.
SIDE REACTION:

 Organic feed ETLA contains impurities call PEG.

 This impurity gets converted into 1-4 dioxane in
acidic environment as per reaction below

 HO-CH2CH20)n-H + R-(OCH2CH2)-OSO3H

 R-(OCH2CH2)n-1 -OSO3H + (CH2CH2O)2 + H2O

REACTOR SETUP:.

1.Reactor is plug flow type

with shell and tube
arrangement.

2.Length of reactor is 6 m.

3.Total number of tubes 90.

4. Diameter of each tube 1

inch.
REACTOR EMERGENCY PROTECTION:
 EMERGENCY ENABLE / DISABLED SYSTEM:

 Used to avoid the charring of the reactor.

 This system consists of ETLA solution storage

tank(16V3). Where ETLA is stored under pressure of
about 5-6 kg/cm2.

 It will activate when organic flow falls to or less than

1500 kg/hr. when display shows emergency enabled, so3
inlet valve (kv 16.5) closes automatically and the (kv
16.7) valve opens. So the so3 flow diverted to 23C1
instead of reactor.
 STANDARD OPERATING PARAMETERS:-
 In order to achieve desired quality of sulhonic acid and
SLES 70 following parameters are important:

 So3 +air free from oleum

 Inlet so3 gas concentration = 3.2 and 3.5 %(v/v)
 Inlet so3 gas temp.=43 to 45 c
 ETLA flow through each tube of reactor is equal
 Cooling water temp inlet to reactor = 28 c
 Temp of sulphonic acid outlet from reactor= 38 to 40 c
 REACTOR CALIBRATION:
 Purpose: reactor is calibrated to ensure equal amount of flow to
material.
 Solution used: ETLA
 Procedure:
 1. reactor is washed & dried as per work instruction
 2.bottom cone is removed.
 3. ETLA taken into the reactor by pump 16P3.
 4. start 16P2 & recirculation organic flow amount 2500 kg/hr.
 5. after 10 mins of organic cir. Calibration started.
 6.flow through each tube measured with the help of stop watch and 2 kg
balance.
 7. the % of deviation from average is measured.
 8. if it is more then 3%, nozzles or shims are change.

 Frequency of calibration: every 6 months.

SECTION 33
SECTION-33 : VACUUM NEUTRALIZATION
SECTION

Tag No Description
33D1 Vacuum Neutralizer
33P1 Product transfer pump
33P2 Condensate transfer pump
33P3 Cooling water pump
33P4 Citric acid dosing pump
33P5 Vacuum pump
33P6 Caustic-water feed pump
33MX1 High shear mixture
33V4 Citric acid holding vessel
33V6 Citric acid online vessel
33E1 Vapor condenser
33E2 Caustic water cooler
33V1 Condensate holding tank
PROCESS FLOW DIAGRAM SECTION-33
 IMPORTANT :

1. The sulphonic acid produced in reactor is thermally

unstable, so as soon as it produced it has to be
neutralized using alkali.

2. If sulphonic acid remains un-neutralized for longer period

then it splits into Sulfuric Acid & ETLA.

3.If sulphonic acid is neutralized after time greater than

standard time then

 1,4 Dioxane in SLES70 will increase.

 NDOM content in SLES70 will increase.
 Q-COMPONENT :
 Sulphonic acid ring pressure = -0.1 to 0.05 kg/cm2
 Deviation of Ring pressure :
1.If it is less than -0.1 kg/cm2 :

Result : Improper distribution of sulfonic acid inside

neutralizer
Indication: Pressure indication on ring gauge.
variation in 33D1 current
Acidic Alkaline product cycle
Result : Possible Jelly formation in neutralizer and increase in
Dioxane in SLES70.

2.If it is more than 0.05 kg/cm2 :

Result : Improper distribution of sulfonic acid inside

neutralizer
Indication : Pressure indication on ring gauge.
variation in 33D1 Current
Acidic-Alkaline product cycle
Result : Possible Jelly formation in neutralizer , carryover of
material into 33E1 and increase in Dioxane in SLES70.
 Q-COMPONENT :
 Caustic water ring presure = 0.1 to 0.05 kg/cm2
 Deviation of Ring pressure :
1.If it is less than -0.1 kg/cm2 :

Result : Improper distribution of sulfonic acid inside

neutralizer
Indication: Pressure indication on ring gauge.
variation in 33D1 current
Acidic Alkaline product cycle
Result : Possible Jelly formation in neutralizer and increase in
Dioxane in SLES70.

2.If it is more than 0.05 kg/cm2 :

Result : Improper distribution of sulfonic acid inside

neutralizer
Indication : Pressure indication on ring gauge.
variation in 33D1 Current
Acidic-Alkaline product cycle
Result : Possible Jelly formation in neutralizer , carryover of
material into 33E1 and increase in Dioxane in SLES70.
 FISH BONE DIAGRAM FOR DIOXANE:

neutralizer sulphation
Neu. temp Sm of cyclone Temp. of sm

Residence
time of sm
Sm ring vacuum
Oleum entering in sm
pressure Activity of sm

High
Temp or dioxane
ETLA
Dew point of
Alkalinity of Temp of so3 air
ETLE Dioxane of
Moisture ETLA
in ETLA

PEG in ETLA
R.M SO3
 SECTION-14

1.Section-14,is Exhaust Gas treatment section

2.Exhaust gas from sulfonation reaction section-16,is

treated in section-14
 WHY EXHAUST – GAS TREATMENT…?
1. Exhaust gas from reaction section-16
contains unreacted SO2&SO3.

2. This gas can not be sent directly to atmosphere. If sent

it will cause AIR POLLUTION which is harmful to
nature.

3. To ensure ZERO air pollution, treatment of exhaust

gas from section-16 is must.
HOW EXHAUST-GAS TREATMENT…???

1.Exhaust gas received from reaction section-16 is

treated in 2 steps

2.Step-1:
 1.First organic mist removed to make gas stream
free from organic material using Electrostatic
precipitator (14F1).
3.Step-2
 1.Exhaust gas is then treated to remove SO2 &SO3
in scrubber (14C1).
PFD FOR THIS SEC.
WHY REMOVAL OF ORGANIC MIST….???
What if organic mist is present in Exhaust gas?

1.Organic mist present in exhaust gas has properties of

surfactant

2.If exhaust gas is taken to step-2 i.e.SO2-SO3 absorption

scrubber -14C1 without removal of organic mist then will be
excessive foaming inside scrubber

What if there is foaming inside scrubber?

1.The rate of SO2-SO3 absorption will decrease due to poor

contact area between solvent (water+caustic lye)and solute
SO2- SO3.

2.This will cause SO2-SO3 escape to atmosphere there by

causing AIR POLLUTION.

Hence to have good rate of absorption and to ensure 100%

absorption of SO2-SO3 in 14C1 scrubber organic mist present
in
exhaust gas from sec-16 should br removed as 1st STEP.
HOW REMOVAL OF ORGANIC MIST…..???

 1.Organic mist present in Exhaust Gas is removed by using

ELECTROSTATIC PRECIPITATOR….

 2.What is ELECTROSTATIC PRECIPITATOR?

 AN electrostatic precipitator (ESP), is particulate collection

device that removes particles from a flowing gas using the
force of an ‘’induced electrostatic charge’’
ESP SETUP:
SCRUBBER 14C1 SET UP:
SCRUBBER-14C1 OPERATION:

o The SO2 reacts with caustic to from sodium

sulphite :

SO2 + 2NaOH Na2SO3 +H2O

o The SO3 reacts with caustic to from sodium

sulphate :

SO3 + 2NaOH Na2 SO4 +H2O

 SCRUBBER-14C1 OPERATION :
 Both reactions are Exothermic in nature.

 The operating temperature of caustic water solvent is to

be maintained at 40 C to avoid crystallization of sodium
sulfate.

 The operating temperature caustic water solvent is

maintained at 40 C to by using steam as shown in fig.

 The PH of caustic water solution is maintained at 11 to

get good absorption rate.
SCRUBBER-14C1 OPERATION :

 Concentration of Sodium sulphate inside the column & in

outlet effluent is maintained 8% to 10%.

 If the concentration of Sodium sulphate inside the

column& in outlet effluent increase above 8% to 10% then
there will be crystallization of sodium sulfate inside the
column.

 Sodium sulfate crystals will accumulate in the packing

and will decrease porosity of packing bed.

 This will create back pressure on Gas entering the

column which will cause plant stoppage .
SECTION 23
SECTION 23

1.Section -23, is exhaust gas treatment section.

2.The treatment of exhaust gas containing SO2 (sulphur

dioxide) and SO3 (sulphur tri-oxide) is done in section-
23 during sulphonation plant start-up or shutdown.

3.SO3(Sulphur dioxide) and SO3 (sulhur tri-oxide) are

absorbed in 98.5% sulphuric acid and exhaust gas free
of SO2 & SO3 is sent atmosphere
 SET UP:
Gas free so3 and traces of
so2 to scrubber 14c1

Cooling
water out
Oleum Submersible
from sec 12 Ceramic
pump
saddle
PACKING

23v1

Cooling
water in
Suction 23P1
filter
LIST OF TAGS IN SECTION-23:

Tag NO Description
23C1 Absorption Column
23P1 Sulphuric acid circulation pump
23F2 Sulphuric acid filter
23V1 Sulphuric acid storage tank
23P2 Sulhuric acid transfer pump
23V2 Sulphuric acid storage tank-2
23E1 PHE cooler
 SO2+SO3 SCRUBBER-23C1 OPERATION :

 The gas from the SO3 filter first enters at the bottom of
tower
 The Sulfuric acid at 98.5% concentration is circulating in
the absorption tower
 The gas travels up through the tower ,counter-current to
the acid falling from the top of the tower
 The SO3 gas gets absorbed in 98.5% sulphuric acid
 The acid is continually passed through PHE to remove
heat that is generated by the dilution
 The gas escapes from the top of tower through mist
eliminator which is free from SO3 but contains traces of
SO2
 Then this gas is routed to the Scrubber column to remove
traces of SO2
REACTION INVOLVED IN ABSORPTION COLUMN -
23C1 :
 SO3 is absorbed into H2SO4 to produce oleum (H2S2O7),
which then mixed with water to form sulfuric acid

1.Step 1: SO3 is absorbed in H2SO4:

H2SO4+SO3=H2S2O7

2.Step 2:Oleum is reacted with water to form H2SO4 :

H2S2O7+H2O=2H2SO4 EXOTHERMIC
WHY SULFURIC ACID CONCENTRATION @ 98.5%:
 The 98.5% grade is more stable in storage, called as
concentrated sulfuric acid

 The rate of SO3 absorption is very good with Sulfuric

acid @ 98.5% concentration

 So during absorption process it is necessary to maintain

sulfuric acid concen.98.5%
 PLANT ACTIVITY
 FURNACE(12H1) :
 Refractory balls 60 mm-19300
 Refractory balls 100 mm-325

 MEG SOLUTION MAKING:

 MEG DRUM FILL UP:2150 KG
 WATER ADDITION:8000 KG

 SILICA BED(11C1A/B):
 Alumina-1050
 Blue silica-40
 White silica-5100

 CONVERTER(12C1):
 Cerablanket – 25 mm
 Balls quantity in each bed-837.5 kg
 1st bed catalyst quantity-2500 dm3
 2nd bed catalyst quantity-2710 dm3
 3rd bed catalyst quantity-2810 dm3
 4th bed catalyst quantity-3220 dm3

o REACTOR CALIBRATION
THANK YOU !!