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Primarily of ferric oxide with oxide of potassium like promoter.

Other oxides of they


have been used like supplementary promoters of metal, the chrome once the cerium
was included, tin, calcium, platinum, and Titanio. By and large, the market of the supply
of catalyst is dominated by two companies, CRIY Süd Chemie. For low to's application
softwares steam-driven EB, the catalyst Hypercat of CRI is the greater part of
The stable and selective catalyst on the market. The catalyst Hypercat is also known
for his height.
The I prorate of mechanical and wear force bass Sobre last decade, the majority of
plants Badger have the catalyst used suppliedly by CRI.
The space velocity primarily affects the needy fever to achieve a given conversion.
The inlet of the reactor that fevers should be enlarged like the space velocity is
enlarged, and vice versa.
Because the catalyst loses activity gradually, principally as a result of loss of the
promoter of potassium, practice is common to increase the temperatures of entrance of
the reactor to compensate the lost activity and to hold the constant conversion. When
the fevers of the inlet of the reactor
The finaIly's reach the limit of the mechanical design of the team, the plant can extend
catalyst
The life for the reducing specific yield and that way the space velocity through the
reactors. In order to minimize
They correlated the costs with frequent tumarounds for replacement of catalyst, the
space velocity typically
He is willing to achieve between one 24 and the 36-month mn's length.
As good previous mark, like a mn of catalyst progresses and the section of reaction
has been enough it
The mechanical limits ( fevers ) of the design, the producers either should suspend
operation to replace
The catalyst or reduce specific yield, cost-reducing intense griefs have both of whom.
In order to offset
The aging process of catalyst, developed Badger a technique of the novel to become
stabilized or to reactivate
The technology of stabilization of catalyst of the caIled of catalyst of dehydrogenation (
CST ). Now proven
In two commercial facilities, CST's basic concept is replenishing for the volatile activity
Promoters, potassium compounds usuaIly, while you plant it they are in operation. In
that way making, catalyst
The loss of activity is in great decelerated measure, that way I replace of catalyst of the
aIlowing to be deferred. Data
Derivative of the commercial plant and the operations of the pilot plant indicate that
CST can
Extend life of catalyst of over there as much as 50 percent.
The main by-products of the reaction of dehydrogenation are toluene and benzene.
Although a loss of performance, both are technically valuable products at great height.
The benzene is many times
The recycIed for the unit EB, while toluene is either you returned to aromatics's unit or
he sold for
Refiners. Toluene is produced by means of both EB and styrene, with the bigger
portion coming
Of the way of the styrene.
C6H5 CH2CH3 →℠C6H5 CH3 +H2 +C
Ethylbenzene
C6H5 CH2CH3’C6H5 CH3 + C
Similarly, benzene is also formed road EB and styrene by the following:
C6H5 CH2CH3 C6H6 + CH3 + C
Erhylbenzenc Benzene Merhane Coal
The impurities that affect purity of the product include rnethylstyrene and
curnene. This heav ier C9 combines and produced in the dehydro's reactors,
Cumene is shaped principally in the areas of mental gap of the reactor ( i.e.,
Noncatalytically ), with EB being the primary forerunner.

C6H5 C3H7 of 2C6H5 CH2CH3 + C6H5 CH3


Elhylbcnzene Cu mene Tolucne

A big portion of the cumene formed by this reaction, as well as any cumene that enters
the plant of the styrene with cool EB, is dehydrogenated catalytically forming
methylstyrene.

C6H5 C3H7 →℠C6H5 C3H5 + H2


I hydrogenate Cumene To Methylslyrene
In general, however, methylstyrene is made for the most part in the catalyst,
Being the primary forerunner.
2C6Hs CH CH2 + CH4 - 7 C6H5 C3Hs + C6Hs CH3
To Methylstyrene Styrene Methane Toluene
The vapor plays a role of utmost importance and one adds for three reasons. First, it
serves as a heat
The source for reaction. Secondly, the effect of dilution of the vapor decreases the
partial pressures
Of styrene and hydrogen to deviate the thermodynamic equilibrium favoring the
conversion stops
EB. At last, the vapor reacts with carbon coke deposited on the surface of catalyst
through the watergas
Deviate reaction and that way you hold activity of catalyst. Coal deposits in the catalyst
like one
The benzene byproduct and the formation of toluene are eliminated easily like coal xide
gave over there
The reaction with vapor. Die the high temperatures of the reactors of dehydrogenation,
the production
Xi gave of coal of it is a magnitude of major order than that business about carbon
monoxide.

Coal water closet Carbon Hydrogen's monoxide

Coal Water Carbon H ydrogen

The DESCRIPTION of PROCESS


The process Badger ATOFINA styrene consists in two main sections: Reaction and
distil lation. The section of reaction includes a steam-driven boiler, two reactors of
radial flow, an inter-reactor reheat money-changer, a money-changer of heat of the
fodder outflow, an effluent condenser, It
The system of reaction of dehydrogenation Badger ATOFINA uses the fixed specific
gravity's two reactors of radial flow of scales of measurement
In the series ( the Fig. 11,2,1 ).
Before the reactors, cool airs and recycle that EB ( recovered in the section of
distillation ) is mixed
With low-pressure vapor river above the money-changer of the fodder outflow. The
vapor is added in this step
In order to impede formation of carbon coke and subsequent carburation of metal in
high temperatures. Inside it
The money-changer of the fodder outflow, the two-phase fodder is first vaporized and
then overheated. After,
This EB's current STEAM is combined with additional superheated steam, bringing
entire
Feed mixture to requisite fever reaction. Before entering the primary reactor,
The boiler's vapor is with the fodder completely mixed of EB STEAM in a series of
The proprietary devices of mixture to insure a homogeneous rnixture of the fodder and
that way an uniform steamto
Distribution EB. The eloquent high velocities and the brief time of the residence are
pleasing to minimize
The little catalytic thermal reactions I laugh above the catalyst bed. The Badger
ATOFINA
Process uses the proprietary intemals in the reactor's heart you reduce time of the
residence for both and
Uniformly distribute the fodder through the length of the catalyst bed. The fever of the
inlet of
The primary reactor is something similar determinedly than the conversion EB is
approximately 35 for 40 percent.
The outflow of the primary reactor is reheated by the change with superheated steam
I laugh above the secondary reactor in a money-changer located at once. In order to
minimize thermal
The little catalytic reactions, the boiler belong to couples of married close with the secondary reactor. Once

Reheated, the outflow flows for the secondary reactor, where the additional conversion takes

The place. At the mercy of raw materials and the prices of energy, the global optimal conversion EB

It is 60 typically for 70 percent for step. For a specific catalyst, the higher conversion requires

The taller reactor managing fevers, which one logically reduce selectivity and catalyst
Life. As sketchy in the debate of chemistry, in addition to styrene, the small part has importance of the

Benzene and toluene ( the SMALL PIECE ) and footprint's other impurities are produced in the reactors. Recuperation

Of SMALL PIECE and the removal of the greater part of the components of the footprint they are impressively consummated

In the section of distillation SM.

Of the secondary reactor, the outflow is first cooled against fodder of the reactor in a piled up one

The money-changer of the feedleffluent. The outflow cooled of the reactor of the money-changer of the feedleffluent is then

Halfway extract in the styrene's raw condenser. At the mercy of the specific economy at place,

This condenser is either a shell and money-changer of the tube using water of refrigeration or an air fin types the blood of

Money-changer. Furthennore, in some plants where the maximum environmental fever of air is high

( i.e., 40 for 50 C ), the money-changer of the air fin is followed by a condenser of the water adornment of refrigeration.

Badger ATOFINA also offer an optative plan of recuperation of heat that recovers energy

Of the condensing current of the outflow of the reactor. After the recuperation of relatively the lofty Ievel

The energy of the outflow in the money-changer of the fodder outflow, the eft1uent is further on cooled and

To condensed stockings vaporizing EB's azeotrope WATER CLOSET. In a prescribed proportion, EB and

The water form an azeotrope of minimal boiling point in which the boiling point of the mixture

It is significant lower than those of the two pure components. When vaporizing the azeotrope,

Because each EB's mole vaporized, between 2,5 and 3,2 steam-driven mole is vaporized like wel!.

Once he vaporized and buy thirst, this current is then used like fodder of the reactor, that way slimming down it

The net steam-driven consumption for the system of the reactor. Of the vaporizer of the azeotropic, the reactor

The outflow is halfway den of opposing view thirst, and that way the refreshing requirements of water are it also significantly

Reduced. With the natural prices that grow upon occasionally of the gas the United States and it relatively

The steam-driven and combustible high cost in the Far East, this plan of recuperation of heat you have one reasonably

The payout's attractive time. At present, this plan is in five plants usedly Badger.

Of the condenser, the effluent flows for a drum of installation of guy of pitcher. The liquid

The organic and watery phases are separated, and the steam-driven current ( the vent's gas ) is disengaged.

The watery phase ( process extract ), containing you dissolved footprint's hydrocarbons, it is

Inclined for a column of denudation where hydrocarbons and the light gases, principally the coal dioxide,

You are removed by the direct steam-driven denudation. Of the striptease artist, the extract of process is filtered

And reused like feedwater of the boiler either to process vapor generators or for the offsite's boilers.

The gas of the vent of the drum of installation, consisting of noncondensables ( primarily hydrogen,

Carbon dioxide, and methane ), aromatics, and water, flows for the suction of the gas of the vent

Buy sister. Of the compressor, the vent's gas is cooled in money-changers' series, consequently
Condensing a lot of water and aromatics. The liquids of the come from the den of opposing view they are then recycled

The raw drum of installation. After the refreshing step, to the vent's gas one goes

The system of the absorberlstripper for residual aromatics's recuperation. In the absorber column, it

The current of the gas of the vent is contactee with a current of thin oil cooled, usually I join more aromatic snob

The current like residue of the unit EB. In the absorber, all aromatics are approximately stirred of it

The vent's gas. The substantial oil of the funds of the absorber is then directed a column of denudation,

Where the thin oil is regenerated by the steam-driven denudation. Of the expenses of the column of denudation,

The recovered aromatics and the vapor of denudation are recycled for the drum of installation by it

The styrene's raw condenser. The substantial gas in hydrogen of the vent of the unit of the styrene is frequently

Burning like fuel either in the steam-driven boiler of process or in the offsite's boiler. A little number

PSA chooses to recover hydrogen of high purity of the gas of the vent using technology of plants.

Being compared with using it like fuel, the recuperation of hydrogen ( PSA ) requires than it

The vent's gas be buy thirst stops significantly the higher pressures.

The phase decanted it is ( raw styrene ) of hydrocarbon of the drum of installation instilled

The section of distillation for purification. The styrene's section of purification consists in three

The completely operating systems of the column of distillation of low temperatures of under they vacuum. The show of

These columns should produce a product of purity styrene monomer tall, recovering what's valuable

The benzene byproduct toluene, and recycle EB not converted back to the section of the reactor.

As talked-over, the styrene's rate of polymerization is significant even in low fevers.

They are styrene in order to minimize fonnation of polymer ( produce loss ), the distillations taken be in relatively

Decrease temperature, usually 100 C or less, in the presence of chemical products of the suppressor of the retardant material.

At the mercy of the requirements of separation and the system's liquid volume of hold-up, expenses

The styrene's pressure of the columns of distillation is typically in between 30 and 200 mmHg tyrannical.

You are like good mark, in order to reduce formation of polymer to long whole of the section of
distillation, standard
The habit to add the styrene's raw fodder chemical products of the suppressor of the andlor from
the retardant material I laugh arrive of
The columns of distillation. The majority of diligent suppressors today are cured aromatic with
Hydroxyl, niter, or functional groups amine, like dinitrophenol, dinitrocresol, and
Phenylenediamine. The various suppressors are provided to the industry by companies so
Crompton, GE Betz, Ondeo Nalco, and AH Marks. Die the highly competitive nature of
The suppressor's supply, many of the additive chemical products are proprietary and or under
the cover of patent
Protection.
These chemical additives act as radical exterminators that either entered ( expand ) or inhibits
The reaction of polymerization. In addition to the efficiency of inhibition, a number of other
factors
You should be considerate in suppressors' selection: Toxicity, thermal stability, volatility,
The reduction of viscosity, and the requirement for the presence of molecular oxygen. In like
manner,
The majority of chemical products of the suppressor are fixed no volatile snobs that egress the
process with it
The residue's current, which one is in the long run burned-out as you went!. As a result,
contained nitrogen
Form NOx in the course of combustion in the suppressor. As a result, one quite
The content nitrogen relative to it is the important factors to select a suppressor today
The effectiveness of inhibition of the chemical product. As the regulating laws get more
rigorous with appreciation
For the NOx's emissions, in particular in the United States and Europe, the industry is gradually
Moving over to additives that they contain less or not much nitrogen.
The basic configuration of the section of distillation is shown in Higo. 11,2,2. In the first part
Column, the BITTEN column, benzene and the toluene produced in the reactors of
dehydrogenation
He is of ethylbenzene and styrene separatedly. The aerial distilled liquid of the BITTEN column
The envoy is often a splitter of benzene toluene recovering benzene for recycle for the unit EB.
The toluene byproduct is returned to aromatics's unit, sold like a byproduct, or convert
The benzene in a reactor of dealkylation. With the high selectivity of the styrene of the majority
of modern plants,
The installation of an unit dedicated of dealkylation of toluene is difficult to justify.
Funds flow of the toluene column of benzene it is sent to the EB recycle column,
Where Cs, principally ethylbenzene, he is of styrene and retraining separatedly of return to
Reactors. This separation is of account particular because any of Cs ( ethylbenzene
And xylenes ) that egresses the fact that the column arrives at the bottom becomes an impurity
of the product of the styrene. Because
Points, EB's separation and styrene are difficult of their relatively close boiling. In
100 mmHg, the boiling point of EB are 74 C as compared with 82 C for styrene. Come in
The average for a base design, the specification EB ( of Cs ) for the product SM is
Between 100 and 1000 ppm wt. Nevertheless, in order to tell your product apart of that of
Other producers SM, relatively they produce a big number of plants less than 100 ppm, and
Some product them s than 10 ppm. In spite of the fact that more energy is significantly
Required for to manufacture the too many producers of quality tall the product, SM rarely can
grab one
The higher price.
The combination of close point of boiling and contents under EB in the funds proves to be one
The big number of theoretic distillation adapts for the stage to achieve requisite separation EB
STYRENE.
Besides, the operating pressure of the column should be constant fall to reduce
The temperatures of work and that way the formation of polymer. To the mid 1980s, you
specialized strainer
They used the trays to achieve this separation. Even with your fall of low pressure
In comparison to the strainer's standard trays, the use of trays gave fevers of funds as a result
inside
The excess of 120 C that The other main inconvenience for design of the column of the trayed
was it relatively
The liquid overwhelming volume of hold-up in the trays. Inevitably, both the higher fever of
funds
And the volume of hold-up gave as a result high rates of formation of polymer.
The standard habit today is using packings of structure of fall of low pressure of high efficiency
As those decided for Koch Glitsch and Sulzer Chemtech. In comparison to it
Trays, packing structures have two important advantages; First, the fall of pressure for
theoretician
The stage is very lowermost, and secondly, the liquid hold-up becomes shorter significantly.
You used at the mercy of the density of packing one's bags ( the surface area for the volume of
the unit ), the HETP
( the height for theoretic dish ) you are in the mood for on the order of 250 500 mm with a fall
of pressure for
Less 1 mmHg's stage.
Reciduo
Flash

11,2,2 of the figure configuration antacid of the section of distillation


Having these beneficial characteristics, the use of delivering optimization of permissions of it
The column manages pressure with respect to the uppercase investment and managing costs (
the vapor,
The watermark of refrigeration, of polymer, and the suppressor's consumption ). By and large,
what's optimal
Design results in a fever of funds of less than 100 C and in the extreme cases around
85 the Monkey C, the lowermost combination of fall ( the fevers lowermost of funds ) of
pressure and
The liquid hold-up reduced has significantly reduced than the quantity of formed compared
polymer
With the I designate of the column of the trayed Correspondingly, the suppressor's consumption
is to the so reduced
A great extension with the use of structured packing.
Funds flow of the EB recycle column she is nourished for the styrene finishing off column.
The fodder for the column contains styrene, small amounts of ethylbenzene, C9 Aromatics,
The poly-cyclic heavy compounds, polymer, and the suppressor. The crucial separation of the
finishing
The column should remove aromatic compounds C9, primarily a methylstyrene, of the tinished
The styrene's product. The styrene purified and recovered up above as a distilled liquid product
is first
Discouraged before being sent to the offsite's stockpile. The heaviest materials of the funds of
the column
It is pumped for a system of the drum of the twinkle for styrene's recuperation of the residue.
Fever
The system is something similar that the residue contains between 5 determinedly of this
twinkle of the pumparound
And 10 the % wt styrene. As well, that way I plants control the total quantity of volatile
components
In this current of the residue to take responsibility either a viscosity or target of flash point. I eat
mentioned
Earlier, styrene that the residue is burnt like fuel neither in heaters to the ones that fire in
process or in boilers of the offsite glued itself.
The product Styrene is normally red sto in tanks refrigerated or cooled. If the styrene is it not
Consumed immediately, in order to impede formation of polymer, you should be inhibited for
storage and
The transportation with 4 tert butyl catechol ( TBC ). The standard rate of addition of the
industry of
TBC is 10 for 15 ppm by weight. This suppressor's level allows you his use by many
polymerization
The processes without your removal, to the still supplying adequate shelf life. For TBC stops
Be effective, the fever of storage carefully controlled oxygen, and dissolved you should owe
Be present. For example, in a level 10 ppm and a fever of 24-c storage, the maximum
The commendable time of storage is approximately 4 to 5 weeks, considering in 15 C that can
be so tall
I eat 2 to 3 months.
The SPECIFICATION of the PRODUCT
Both the market and the specific application software of polymer largely dictate specifications
SM.
By and large, however, the industry gravitates toward the higher and higher purities.
In the meantime 10 years back the typical purity of the design 99,80 % were wt, today plants are
designed
For at least 99,90 % wt, with some producers asking for wt so at great height like 99,95 %.
Generally,
Purity of 99,9 percent makes smaller all the impurities stops sufficiently to moo levels for
virtually every polymer
Application softwares. Reason with consumers why they can be wanting more high purity
include avoiding
Savor detection in thrown food foam packaging, reducing treatment of water of expanded
polystyrene
The plants, and the reducing emissions of products finished like latex carpet to be in backward
movement.
The specifications of typical product of degree of polymer are SM shown in 11,2,2 of the table.
MANAGING ECONOMY
As a general rule, plants are styrene highly integrated of one point of sight of steam-driven
balance
With laugh to it lead unit EB. As a whole, the unit EB is a net steam-driven exporter,
considering it
The styrene's unit is a big steam-driven consumer. More treat the consumers in the styrene's unit
swiftly they require
Fume with anger in low levels of pressure, typically in the reach of,0 for 5,0 kg/cm2. g. On 80
percent
The unit is attributable for raw materials of the operating variable cost of a styrene, benzene
And the ethylene for ethylbenzene. As a result of the effect that you counterbalance of
To's proportion steam-driven EB versus the styrene's selectivity, prepare them of operation of
every plant of the styrene
The specifications of the 11,2,2 one belonging to the table for Polymer Grade Típico
SM Producto
Styrene
C8 's ( EB + xylenes )
Or Methylsryrene
Phenylacetylene
Polymer
Aldehydes ( benzaldehyde )
Peroxides ( hydrogen peroxide ) Inhibitor ( TBC )
Chlorides
Sulfur
Color, APHA

99.8-99.95 wt or or
100-1000 ppm wt
150-500 ppm wt
100 ppm wt
5-10 ppm wt
30-50 ppm wt
30 ppm wt
10-15 ppm wt
2-5 ppm Wl
2-5 ppm wt
10-15

TABLE 11,2,3 The Typical Raw Material


And the Consumptions of Energy

Item, units
Ethylbenzene, kg 1,057
Brr by product, kg 0,029
Steam, kg 2,550
Fuel oil, 1000 kcal 0,090
Cooling water closet, m3 0,215

It is optimized for her premises price fixing of raw materials and energy ( primarily fuel and the vapor ). It
The consumptions of the unit indicated in 11,2,3 of the table are typical for a plant SM autonomous located inside
The area of the Coast of the USA Gulf.
I realize that the figures of consumption presented at the table include only the styrene's unit on-site
The team's goods. The fuel figure of consumption supposes than both the vent they asphyxiate carbonated and
The residue of the unit of the styrene is burned-out as you went!.

CHAPTER 11,3
POLY-MERI EUROPE
STVRENE GO IN PROCESSION
TECHNOLOGY

Leonardo Trentini and Herman Galeotti


" c. Buonerba " Investigate Center Mantova, Italy

INTRODUCTlON
Styrene is one of the antacid more important chemical products. Your ex ten the sive's production pulled out inside
United States during the World War N, when the supply of natural rubber of South Asia
It is cut-out of access by allied countries. After the war, styrene's increasing use stops
Synthetic rubber and because polystyrene obtained forcefully a worldwide expansion of plants. Meanwhile,
Technology and the improvement of catalyst increased capacity of the plant, efficiency enormously,
And the certainty environmental. In 2003, the styrene's worldwide capacity is close to 25 million
Metric tons a year ( MTA ).
In the early 1960s, Polimeri Europe ( in that time Montedison and back then EniChem ) began
Styrene's production in Mantova, Italy. Once your research center in Mantova was driven along, inside
The second half of the 1970s that the company began the development of a proprietary technology
Improving the process and tune equipment of existent units. The result of the tinal of this
The effort was the design of a new unit of production of the styrene that went by current in the beginnings of
The 1990s in Mantova. He has allowed Polimeri the opportunity to run the styrene's proprietary plants to
Europe to acquire great expertise in all respects different of the technology of the styrene and any
The event that can happen during industrialist spreads.
Commercialize in the competitive present styrene, small differences in raw materials and public services
The specific consumption cans the intluence's profit heavily. For this reason, it is very important
In order to have in account whatever you can affect the choice of parameters of process for new one
Unit. The goal is finding the greater part of design optimized, specifically made to order for the conditions of the place
And the customer's needs. Taking advantage of your long experience in the job in both design and manufacture
Of units of the styrene, Polimeri Europe is now in position from offering a competitive styrene
Technology.

THE CHEMICAL PROCESS:

Approximately 90 percent of the worldwide styrene that production is in carbonated asphyxia


etilbenceno of phase
Dehydrogenation. Dehydrogenation Etilbenceno can be executed by a simple therma!
Reaction. The use of catalysts, however, enables a higher selectivity for styrene. It
React to them highly endothermic ( HO6100C 29,80 kcal mole ) and they occur with
enlarged one
Moles' number, as shown from below:

C6H5CH2CH3”C6H5CHCH2 + H2

It is a reaction of equilibrium and because this reason is delimited thermodynamically. Equilibrium


The unchanging Kp is calculated as follows:

Where P; The pressure of the component is component I, and can be written also like

Where n; Moles' number of the component is I and the P is system's total pressure of the reactor.
K,, you stick hard to the constant fever. According to second equation, it is possible
In order to enlarge products ( n, .Y and nH ) over there to decrease the total managing pressure, the other term of numerator, in the
systern of reaction. In such a way, not only ethylbenzene conver that sion will enlarge, but the selectivity for styrene will also
be improved.
Before introducing reaction, the vapor adds up the ethylbenzene itself. You have the essential paper stops
Supply the heat needed by reaction, over ali in the adiabatic's condition. Arrive considering second equation, it is pertinent to
increase the ethylbenzene's conversion also for increas ing moles' total number in the system ( Inside ), making the ethylbenzene
smaller pre-s partial sure for the dilution. That way it is of course the vapor also have a thermodynamic direct effect on the
equilibrium of reaction: The ethylbenzene's conversion increases if to's proportion steam-driven ethylbenzene I the ncreases.
The vapor has others two positive effects in the catalyst:

The decreases of the lt that they formed forerunners' quantity of carbon coke or of carbon coke for for ethylbenzene's parallel
crunchy reactions smoke reforming reactions.
Avoid over-reduction of catalyst and deactivation controlling the status of oxidation of iron; The vapor that has good manners of
the oxidant balances hydro's high capacity of reduction gene in fever and high concentration.

The main by-products of reaction are toluene and benzene. He is believed for them to come from the following reactions:

C6HSCH2CH3 + H2 C6HSCH3 + CH4


( AH " 6IO C 24,26 kcal mole )

C6H5CH2CH3 + H2 C6H6 + C2H4


( AH 6 IO C - 15,56 kcal mole )
Carbon dioxide is also an important byproduct. You come from the vapor reforming reaction with the carbon coke populated
in the catalyst. Then, because of the tall tempera painting that works

POLY-MERI EUROPE STYRENE PROCESS TECHNOLOGY

Nire, a little of heavy components takes shape. Nevertheless, your quantity is impor tant because they cause material
consumption, and as a result, they affect the global selectivity of process.
The rate of reaction for the main reaction can be
written like

Where the k, it is the b and constant kinetics!.


The pressures of the he departed from ethylbenzene ( peb ), styrene ( psty ), and hydrogen ( pH2 ) they have an effect

The rate of reaction. Partial styrene's pressures and hydrogen inhibit the rate of reaction because they appear in the numerator of
the subtractive factor to subtract. The result will be that the ethylbenzene's more conversion increases and the styrene's
concentration comes closer for the thermodynamic equilibrium, what's more the will of rate of reaction
Decrease.

The following equations of rate are developed for


the main by-products:

Where the k, it is the b and constant kinetics!.


The pressures of the he departed from ethylbenzene ( peb ),
styrene ( psty ), and hydrogen ( pH2 ) they have an effect
The rate of reaction. Partial styrene's pressures and
hydrogen inhibit the rate of reaction because they appear in
the numerator of the subtractive factor to subtract. The
result will be that the ethylbenzene's more conversion
increases and the styrene's concentration comes closer for
the thermodynamic equilibrium, what's more the will of rate of
reaction
Decrease.

The following equations of rate are developed for the main


by-products:

Against the styrene's preceding equation, in this case styrene's inhibiting factor and
Hydrogen is not present. The result is that in the high conversion ( discussing equilibrium )
The styrene's rate of reaction becomes slower and slower than toluene and benzene
Reaction evaluates, that way decreasing selectivity for styrene.

The DESCRIPTlON of the FLOW of PROCESS:

The Reaction of Dehydrogenation


I believe that a typical unit of dehydrogenation evidence 11,3,1. The cool and recycled ethylbenzene is
Mixed with superheated steam just before the first reactor's inlet. Back then reaction
The mixture flows through the catalyst bed between two concentric screens, spreading out radially
Of the center toward the external shell. The radial design provides some nimizes of flow with big area and of the my
The fall of pressure through the catalyst.
And general, styrene walks in procession they have the adiabatic's reactors. From dehydrogenation
Reaction is endothermic, the fever of the bed of reaction of the mixture and of catalyst
The decreases of inlet to expel et of the reactor. The top the conversion in the reactor,
What's more fever decreases. A typical fever of the inlet of an industrial adiabatic
The reactor is over 600 C, and the decrease of fever in the reactor makes it usually
More than 50 C. They are the rate of reaction in the fever of the outlet of the reactor very slow. Stops
This reason, we have to reheat the mixture of reaction before you enter in another one
The stage to have conversions closer for the thermodynamic equilibrium of reaction. Two
Or three reactors are used serially with a boiler of inter-stage. Heat is supplied over there.

Reactor 1
Reactor 2
Estireno
Raw

ETIL BENZENE

RECUPERATOR OF HEAT

CONDENSER

VAPOR

SUPER HEATER
STEAM-DRIVEN

Water
'

''

The superheated steam that, at the end of the cycle, he will enter the first reactor jointly with
The ethy's benzene.
The fine dehydrogenated mixture, after heats up recuperation, is sent to the following section,
Where the organics and the vapor are condensed and once offgases were separated from ( hydrogen, coal
Dioxide, methane, ethy letter n, etcetera.). This section is generally known like the cold zone, postulate
The section of reaction, the inclusive heat overheating and the effluent recuperation of heat, she is appointed it
The hot zone.
Offgas is removed by a compressor that assures atmospheric pressure for the reactorso
Water and the organic phase are separated in the drum of installation. The water is then purified and
Reused normally, while the organic phase is sent to the section of distillation.
He rethinks a basic simple plan of process in Higo. ] 1,3,1. With reference to this
The plan, Po Imeri Europe can offer the different process the utions that way stops better satisfying the customer's some 's
Need.
It is the case, for example, of the hot zone where the following water main is some ternatives
Avai ab and:
1. Reaction. At the mercy of the global balance of the cost-reducing different aspects ( the ated of the re
For energy, matter s rough, taste yst, and capacity ), join of the following two options
You can be provided:
to. Two stages of reaction
b. Three stages of reaction
2. Heat up recuperation in outflow of reaction. After the fashion of vapor the electrical engineer's proportion of cost,
one of it
Availab is after two options and:
to. In a first step, preheat the ethy's benzene and primary steam-driven vapor mixture, and then, inside
I join second, it louses up boíl and overheating they smoke before being envoy to the oven.
b. Generate only superheated steam of medium pressure to be fed for a turbine like driver
Of offgas's compressor of vacuum; The ethy's benzene and the primary steam-driven vapor mixture
It will be preheated at the zone of the convective of the steam-driven boiler.
Distillation
I believe than 11,3,2 show a train of distillation of the typica in an unit Po Imeri Europe Styrene. Crude oil
Styrene, containing styrene ( about 70 percent ), benzene ethy, benzene, for uene, and a certain amount
The heavy components, they are nourished for the first co umn, where benzene and it is recovered inside for uene
Expenses. The mixture back then comes from the passage for another co umn, generally atmospheric operation
Pressure, where benzene and aside is put for uene.
Benzene Ethy, styrene, and tar they are envoys to the following co umn of the train, where ethy -
Benzene is separated from the styrene. This is I join very separation difficu t because the standard
Points boi ethylbenzene's ing and styrene differ for only 9 C. The co umn, equipped
With structured packing, you are driven below vacuum; In order to have requisite purity the styrene ( usually
No the ess back then 99,9 percent ), the residual lowermost contents of benzene of the ethy in the current
Too much should be on the skids 100 ppm ). In order to achieve this white, a lot of theoretica
Stages are required, usually in this 80. ] Benzene Ethy, with some residual styrene ( normally
No more than 2 percent ), it is recovered up above and retraining for dehydrogenation
Section.
Funds are instilled for the following column, where the pure styrene is recovered it
I hit the top of bottoms he is further on tried in last equipment recover additional styrene
Of the residue. In styrene's aerial vapor co umn p tert buty - catechol ( TBC ) is
Addition to impede the ymerization styrene's po during storage.
Although the work of distillation co umns in vacuum, the hothead arrives at the bottom he can stand out of 85
For 110 C. For this reason, we have to add up a suppressor to avoid the styrene's oss of deserved thing
For polymerization. This is a very critical characteristic of the design because po's formation ymer
The train cannot have a negative impact within the distillation in and on the crude opposing view matter s

BENZENE
SEPARATOR OF
BENZENE TOLUENE

ESTIRENO's COLUMN
SEPARATOR OF

ETILBENCENO/

ESTIRENO
COLUMN OF
BENZENE TOLUENE

TAR
RAW ESTIRENO

RECYCLE
ETILBENCENO
BENZENE
TOLUENE
ESTIRENO

TOLUENE

The clear cut train of distillation represents 11,3,2

The sumption but also on the cost maintenance and, more than this, on the reliability of the plant.
The different substances can be fm once this purpose was used. The majority of common families are
nitroderivatives,
The free fanatics, etcetera.; They can be used alone or in combination with each one else to have
A synergetic possible effect. In order to impede that formation of polymer, all the systems would be used general
The so-called suppressors are Iy, but these compounds can be divided really in two guys: Right
Suppressors and retardant materials. A true suppressor reduces the rate of polymerization to come closer zero even
He wears down, al'ter than the increments of rate so that they would be if no suppressor was present if no suppressor
was present.
A retardant material reduces the rate of polymerization to a very level bass, which one gradually
It increases in the course of time. Each has advantages and disadvantages. Suppressors generally sound out
themselves
Less formation of polymer during the normal processing but he wears down relatively rapidly.
On the other hand, in the meantime not quite I eat retardant materials efficient in impeding polymerization,
Retain any effectiveness for an extended period This has a lot of importance in case of a system
Close, where the retardant material will supply the protection during time you were necessary him
Reset normal operation or for the fevers of the column to quit to fall for one point stops her where polymerization
It is insignificant. For this reason, it is not been advisable to use a true suppressor as the sole
Polymerization foresee ter. A 01'inhibitor of the combination and a retardant material can result in one excellent
grade
Show ( the case D, Higo. 11,3,3 ).
A careful contents of the suppressor of the 01'the of monitoring in the section of distillation is in particular
Important to impede styrene's formation of polymer divinylbenzene, as well as polystyrene
( Divinylbenzene is a present of byproduct in raw styrene below 100 ppm ). Styrene divinylbenzene
Polymer is a polymer designated materially interrelated and insoluble of popcorn
Because the appearance of 01'its. The popcorn polymer contains radical stuck s and they can start it
The 01'styrene of polymerization. When styrene monomer spreads out in popcorn polymer, add
For the stuck fanatics and the swellings of popcorn irreversibly. The swelling also fragments it
Popcorn, bonds of rupture and fanatical new generators.
An extensive section of distillation of the 01'the of study has been carried out by Polimeri Europe
That gives a modern purpose as a result, including especial adequate dispositions to achieve low point
The material losses and the consumption of energy with consumption of the suppressor low. I join width

Suppressors' reach and retardant materials have been proven and they can be proposed. Polimeri Europe also
You have developed a program of simulation made suitable to optimize dose of the retardant material of the suppressor against
The prediction of formation of polymer.

PROCESS ANUS MECHANlCAL OESIGN


CHARACTERISTICS AOVANCEO

When a styrene's new unit is designed, many the different targets should be successful. These
Include:
I decrease the consumption of energy of
Low point of conversion performance of
The ethylbenzene's height of consumption
For a long time the life of catalyst
The low-cost maintenance
Low point of reliability of the plant
Because some of these whites are in conflict with each other at least in part, a compromise
He has to be found, case for the case, in the relation with conditions of the place and customer needs. With
This goal, Polimeri Europe can supply appropriate solutions, correctly making the greater part of
The different characteristics of the design.

Investigation and the Operation:

Track record of Polimeri Europe and the expertise in the styrene's technology come of
Dictate to manufacture experience, like the start and the closing, maintenance and certainty,
And the environmental Laboratory of subjects and the pilot plant to experiment in catalysts of dehydrogenation and polymerization
Inhi tors/retardarders.
The continuous monitoring of facilities of production and the results of proofs of the laboratory feed themselves
The improvement continues of technology.

The PROCESS'S design:


Technology Poly-Meri Europe is flexible; As once the previous, different solutions were mentioned they can be
The moving balance embraced of energy, the shows of process, and the life of catalyst. Important one
The additional tool is analysis ( for CFD ) thermal fluodynamic and applied to the reactors hot of the area
Money-changers and interconnecting playing the pipes. The targets of the water main that succeeded with one so
The system is enlarged recuperation heat, minimal fall of pressure, and reduced deficiency of homogeneity
In distribution.
Case studies have been carried be obeying cases:
EB's mixer STEAM to reduce time of the residence of the ethylbenzene in tall form ( the interior cone, the vessel outside ) of the Reactor of
fever to trigger in a low fall of pressure outside

Badl and affecting the flow in profile through catalyst you put to bed the money-changers .Heat to balance the internal
fall of pressure and to equal the flow.

The intentness for rninimizing the void hot volume, where the low reactions of selectivity take place, and the
exact designee to run the reaction in the low pressure has driven a design of the irnproved that maximizes show of
catalyst and global selectivity of process.

The Mechanical Design

Aspects Ali of mechanical design they are of great worry for Polimeri Europe. The exactness at this field is
irnportant because directly you affect reliability of the unit in reality. Thermal and mechanical analyze ( including
to UGLY ) she is the most correct tools. The main white men should minimize temperature gradients, softening
discontinuity in the thickness of the wall, and improving stress distribution.
Case studies have been accomplished in obeying cases:

The reactor's baskets


The inlet's big mouthpieces outlet
The attachrnent of the sheet the tube's vessel
The guides and the supports for piping and team
The effects of earthquake

Because of the extreme care in the details and the choice of the best materials and generally of the technical
solutions more safe, even if they are lightly more expensive in terms of beginning the cost investment, the plant ali
cornponents, like hot vessels of the zone and interconnected pipes, it will attain a light height of mechanical
reliability.
The preceding realizations should not be conceived as separated. Ali have often to be able to make good use of
thern side by side in order that a good comprornise can be caught up with.
It is the case, for exarnple, of hot layout of the zone, where the pertinent mutual positions of reactors and the
money-changers are selected to minimize time of the residence in tall perature of the tern in interconnecting pipes,
having in account the fall of pressure and interpreting with the shepherd's pipe elasticity.
With ali the quoted anteriormentes you mentioned guidelines in mind, the new unit will be optimized according
to the concessionary requirements, symmetric of every process points of view, and mechanically reliable.

THE FAVORABLE SHOW OF LUCK

For the styrene's unit working with three stages of the reactor, a typical set of parameters of process is reported in
Mesa I J,3,1. The consumption of public services ( electric power, the vapor, and you went they asphyxiate
carbonated ) typically is related to the adopted plan and depends on the customer's needs.
TABLE 11,3,1 Specific Consumption
For to Typical Styrene Unit
EB 1055 KG T ESTERENO
Steam/oil 1,4
Run length 3 Yr
SM purity 99,9 %
Conversion 72 %

The COMMERCIAL EXPERIENCE


The styrene's two plants based on the proprietary technology he is in current in Italy: ·1972, 430 KTA, two reaction stage, with
recuperation of heat of the fodder outflow 1992, 190 KTA, three stages of reaction, with steam-driven generation reheated of
medium pressure,
In order to drive offgas's compressor
A third unit ( 60 KTA ) is in current at the United Kingdom. A styrene's unit ( 600 KTA )
Authorized be in 2005 in lran putly in progress for Polimeri Europe WiII.