Continuous SO3 Film Sulphonation & Sulphation

Sulphurex F

#136
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Introduction
Since its foundation in - lower operating increasing challenges of
1960, Desmet Ballestra pressure the today’s surfactant
SpA is the world leader in industry.
the design and supply of - no extra cooler
Chemical plants for requirements and no To this aim Desmet
Surfactants and need of chilling water Ballestra is in the position
Detergents production. equipment to offer to its customers:

Desmet Ballestra is the - extra low energy • Availability of modern

technology supplier of all consumption and efficient pilot
major surfactants and plant facilities where
detergents manufacturers Desmet Ballestra has they can test new
worldwide and in its 47 implemented the world’s raw materials, verify
years activity has largest sulphonation performances and
implemented more than plants (24000 Kg/h as easily apply the
1600 plants in over 120 100% active surfactant) findings to industrial
countries. and is constantly scale plants with
optimizing its process minimum costs
Desmet Ballestra’s film through the continuous
sulphonation work of its R&D Centre. • A very efficient Spare
technology presents Particularly has Parts department
outstanding advantages developed proprietary structured to answer
over the competing Know How and processes in real time to the
processes, namely: for surfactant upgrading customer needs
downstream the minimizing
- outstanding sulphonation process, maintenance cost
performances in i.e.: Dioxane stripping and and production
terms of product Drying process for pure losses
quality specially dry surfactant production.
when sensible raw • A dedicated
materials are Desmet Ballestra can Technical Assistance
processed offer standard plant department
design for capacities structured to assist
- exceptionally good ranging from 1 to 8 ton/hr customers in
conversion rate and and customized design troubleshooting
colour with maximum for larger capacities. evaluation of plant
achievable performances,
absorption of SO3 The mission of Desmet preparation of plant
gas Ballestra is to establish maintenance plans,
consistent and long term personnel training
- simpler construction relationships with its and studies for plant
which entails easier customers offering a full revamping and
maintenance range of services and technological
technical support so to updating
enable them to face the
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The recent integration of Resources and • 3-D computer design

Ballestra in the Desmet capabilities • Capability to supply all
Ballestra Group has the range of services
substantially enhanced • 150 employees and full from feasibility studies
the Ballestra presence in time consultants to turn-key projects
the world markets and its • R&D Centre with • Global sourcing of
capability to offer cost laboratories and full equipment and
competitive plants with a scale pilot plants materials
strong local back-up • ISO 9000 Certification • Project financing
management. • Up to 250,000
engineering hours per
year

Sulphonation Plant Panoramic View

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Process Air Drying

The atmostheric air is The compressed air is subsequent absorption on
compressed up to 0,6 dried by refrigeration a dessicant bed.
Kg/cm2 as requested by condensation of the water
the downstream contained in the
sulphonation process. atmospheric air and

Main features of the unit:

¾ Low operating pressure (0,7 Kg/cm2 max.)

¾ Process Air Dew Point lower than -70°C

¾ Fully automatic regeneration of absorbent medium (silicagel/Al2O3)

¾ Low energy consumption due to the recovery of the hot air from SO3
production unit for absorbent medium regeneration

¾ High reliability and efficiency

Air Drying
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SO3 Production
Liquid sulphur is burned
with the process air in a
special furnace to
produce a gas containing
7% by volume of SO2.
The SO2 is then
converted to SO3 in a
special conversion tower
equipped with 4 catalyst
beds and intercoolers to
optimize cynetically and
thermodynamically the
reaction yield. The SO3
gas is finally cooled to 50-
60°C as requested by the
sulphonation process.

Main features of the unit:

¾ Very high reaction yield : 98,5% guaranteed and possibility to achieve 99,5%
with the use of special Cesium catalyst

¾ High reliability, safety and long plant lifetime due to the use of air as cooling
medium instead of water to minimize corrosion risks

¾ Special design of sulphur furnace (no preheating burner nor sulphur spraying
system) ensuring high operating reliability and easiness

¾ High energetic efficiency thanks to the use of hot cooling air for silicagel
regeneration in the Air Drying Unit

¾ Very compact design of the conversion tower with internal intercooler

¾ Reduced plant start-up time due to a special sulphur furnace which does not
require preheating

Conversion
Tower
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Sulphonation Unit
The SO3 gas outcoming
the SO3 production unit is
filtered by a special high
efficiency brink filter to
eliminate any trace of
carried-over oleum. Then
is fed to the top of the
Multitube Falling Film
sulphonation reactor
where also the organic
raw material is fed under
mass flow control. The
reaction of SO3 gas with
the organic raw material
take place in the MTFR.
At the outlet of the reactor
the gas/liquid mixture is
separated in a special
gas/liquid separator and
in a downstream gas
cyclone. The sulphonic
acid is sent to a special
ageing/stabilizing unit
when Linear
Alkylbenzene is
processed, or straight to
the neutralization unit
when Fatty Alcohol or
Ethoxylated Fatty Alcohol
are processed.

Main features of the unit:

¾ Product quality meeting the highest international standards

¾ High operating flexibility thanks to the capability to process any raw material
used in detergent and surfactant industry

¾ High reliability and operation easiness

¾ Automatic in-line control of sulphonation degree

¾ Low energy demand thanks to the low pressure drop of the MTFR

¾ Optimized design achieved through over 300 industrial Film Sulphonation

plants implemented and operative worldwide

Sulphonation Plant
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Main features of the Desmet Ballestra’s Multitube Film Sulphonation reactor

¾ Outstanding performances in terms of product quality

¾ Very high heat transfer efficiency that enables an accurate control of the
temperature profile in the reactor

¾ Low pressure drop (0,3 Kg/cm2 average) resulting in a reduced energy

consumption of the whole sulphonation plant

¾ Once through design. The sulphonation reaction is accomplished within the

residence time of the reactants in the reactor (less than 1 minute) without
need of external recycling loop. This enables the automatic in-line control of
the sulphonation degree through the reactor

¾ no extra cooler requirements and no need of chilling water equipment

¾ High flexibility with possibility of product flying change-over with minimum

product contamination

¾ Operation easiness

¾ Easy scale-up of the reactor as all distribution heads and reaction tubes are
identical. Scale-up is achieved simply increasing the number of reaction
tubes with practically no limitations on reactor size and capacity

¾ High reliability and longer lifetime thanks to the use of sophisticated

corrosion resistant alloys in critical parts

PRODUCTS CHARACTERISTICS

A.M. % Free % SO4 °Klett

RAW MATERIALS
Conc. % Oil (*) (*) (**)

Linear Dodecylbenzene 60 - 75 0.8 - 1.2 0.5 - 1.2 10 - 25

Natural Lauryl Alcohol 30 - 75 0.8 - 1.5 0.5 - 1.0 2-5

C12-C14 or C12-C18

Synthetic Alcohol 30 - 75 0.8 - 1.5 0.5 - 1.0 5 - 10

C13-C15

Natural or Synthetic Alcohol 30 - 75 1.0 - 1.5 0.5 - 1.0 10 - 15

Ethoxylated with 2 or 3 EO

Natural and Synthetic Fatty 30 - 65 1.5 - 2.5 0.7 - 1.2 20 - 40

Alcohol C16-C18

Alpha-Olefins 30 - 75 1.2 - 2.0 0.7 - 1.2 30 - 50

Methylesters 30 - 65 1.8 - 2.5 2 - 2.5 50

(bleached)

(*) On 100% Active Matter

(**) 5% A.M. solution, 40 mm cell n. 42 filter, unbleached, unless otherwise specified
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Neutralization Unit
The sulphonic acid specifically for Ether guarantee the necessary
outcoming the Sulphates processing, in chemical stability to the
sulphonation unit is a Vacuum Neutralization reaction mass. Final
neutralized with caustic Unit to yield high active product pH value is
soda or an alternative neutral paste (70-75% adjusted in-line by
alkaline agent (i.e.: concentration). In both addition of a buffering
Ammonia) in a special cases the neutralization agent in a final mixer.
Double Step process is carried out at
Neutralization Unit or, high pH values to

The main features of the proposed unit are:

A. Double Step Neutralization Units

- High shear mixers of Desmet Ballestra proprietary design, ensuring

intimate mixing of reactants even at high concentration conditions

- Accurate control of the temperature profile in the loop thanks to the high
recycling rate and the low pressure drop cooler so to prevent any risk of
product degradation

- Easy in-line transition from low concentration (27-30%) to high

concentration (70-75%) paste production

- Accurate control of free alkalinity

B. Vacuum Neutralization Unit

- Efficient Dioxane removal from finished product by evaporation of the

azeotropic mixture water/dioxane

- Possibility to achieve dioxane content in finished product (SLES) below 10

ppm when coupled with the Desmet Ballestra MTFR

- Product deaeration to increase density and improve appearance

(transparency)

- Mild operating conditions with accurate control of temperature profile and

minimum residence time of the product at high temperature so to prevent
any risk of hydrolysis

- High flexibility: capability to process any kind of raw material/product with

possibility to easily switch from one raw material to a different one with
minimum product contamination
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SULPHUREX F
New Exhaust Gas
SO 3 Gas Treatment

Organic Exhaust Gas to

Material SO 2 Scrubber

FILM
SULPHON ATION
REACTOR

2ND Cyclone

WET FILTER

1ST Cyclone

SULPHONIC ACID
TO
AGEING / NEU TRALIZATION
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Exhaust Gas Treatment Unit

The exhaust gas exiting
the sulphonation reactors
is processed to reduce
the level of pollutant to
values widely accepted
by the most stringent
international standards on
emissions to atmosphere.
The maximum content of
the polluting agents
guaranteed at plant stack
are the following:
- Organic mist : 25 mg/m2
- SO3 : 15 ppm (vol.)
- SO2 : 5 ppm (vol.)
The exhaust gas
undergoes 2 subsequent
steps of treatment before
being released to the
atmosphere: reduction of
organic mist content and
final washing with a
caustic soda solution to
reduce the amount of free
SO2 discharged. This
latter step is carried out in
a suitable SO2 scrubber,
while for the elimination of
the organic mist Desmet
Ballestra can offer 2
alternative technological
solutions having the same
efficiency:

¾ Electrostatic Precipitator :

The updated design of the Desmet Ballestra ESP includes honeycomb shaped
tube bundle for optimized fluodinamic inside the ESP and more compact design
and hastelloy electrodes for higher reliability and lower maintenance cost.

¾ N.E.G.T :

The new unit is based on a special brink filter constantly washed with fresh organic
raw material.

This new system, while guaranteeing the same performances (in terms of
cleanness of the gas at the stack outlet), allows the complete recovery of the
sulphonic acid carried over by the exhaust gas. The cost related to the disposal of
the ESP drippings, which constitute a problem of increasing importance for the
surfactant manufacturers due to the worldwide concerns on pollution control, is
therefore totally eliminated.

An additional advantage of the proposed gas treatment system is that it enables

the recovery, as finished product, of the organic otherwise normally wasted.
This factor constitutes a non-marginal improvement of the whole process
economics.

Finally the new system is characterized by a minimum maintenance cost.

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Special Plant Configurations

The previous pages Nevertheless specific configurations are briefly
illustrate the standard plant configurations are illustrated.
Sulphonation Plant necessary/available for For each case, more
configuration as required the production of few detailed and dedicated
by the most common surfactants specialties. documentation is
applications for the available on demand.
surfactants and Hereinafter the most
detergents industry. common specific plant

TYPICAL

DRY METHYLESTER SULPHONATES

Plant Configuration

AIR DRYING SO3 PRODUCTION SULPHUR MELTING

ME FILM SULPHONATION EXHAUST GAS TREAT.

MES AGEING

MES COOLING &

RE-ESTERIFICATION

DOUBLE STEP
NEUTRALIZATION

MES BLEACHING /
AGEING

MES FLASH
MES-DRYING
PRECONCENTRATION

MES COOLING / FLAKING

MES MILLING DRY-MES powder

Standard Units

Additional Units
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TYPICAL

DRY ALPHAOLEFINS SULPHONATES

Plant Configuration

AIR DR YING SO3 PR OD UC TION SU LPH UR MELT IN G

AO FILM SU LPH ONATION EXHAUST GAS T REAT.

NEU TRALIZATION

AOS HYDR OLYSIS

AOS FLASH
AOS-DR YING
PRECON CENT RATION

AOS COOLING / FLAKING

AOS MILLING DRY-AO S powder

Standar d U nits

Addi tional Units

DRY LAURYL ALCOHOL SULPHATES

N EU TR A L P AS TE

W IP ED
FI LM E VA PO RA TO R C O N D E NS ER
C O ND E N SA TE

VE N T

FL A KE R

EX TR U DE R
C O N D ITI O N ED A IR
S L S N EE DL E S
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2008-04-09