PHENOL ACETONE PLANT

• 40,000 metric tons Phenol• 23,000 metric tons Acetone• 2,500 metric tons Alpha Methyl Styrene (AMS)

Production

Phenol Acetone

Production

Phenol/Acetone Plant

neeb sah noitces noitcaereht,ynapmoC muelortePhsitirBybdesnecilyllanigirO noitarepo eht sevorpmi osla hcihw ,9991 ni ssecorp tra eht fo etats a ot dedargpu .)SMA( enerytS lytheM aflA fo noitacifirup eht sedulcni dna noitcesnoitadixOehtfo

Facilities are formed of 8 sections:

1.OXIDATION/CONCENTRATION.2.REACTION.3.WASHING OF CLEAVAGE.

5.DISTILLATION OF PHENOL.6.PURIFICATION OF AMS / RECOVERY OF CUMENE.7.RECOVERY OF PHENOL.8.DEFENOLATION.

4.DISTILLATION OF ACETONE.

Production

1. OXIDATION / CONCENTRATION

The raw material for this section is Cumene which is oxidized using compressed air. Cumeneis previously washed with a caustic solution to remove impurities that can affect the oxidation.Air may be eventually washed to mainly neutralize SO2 traces coming out of the Sulfuric AcidPlant stack. S02 free dry air is fed through the bottom to each one of three reactors(Oxidizers) interconnected in series under pressure and temperature conditions. Cumene isfed to the first of said reactors to form Cumene hydroperoxide (CHP) in concentrations of up to12% the mixture of Cumene and CHP overflows to the 2nd and then to 3rd oxidizer to reach 1712%, the mixture of Cumene and CHP overflows to the 2 and then to 3 oxidizer to reach 17and 21% as CHP respectively. This reaction is exothermic so that vapors with traces ofcumene are carried in the spent gasses stream. The Cumene is recovered in acondensation/separation system (Off Gas Section) and after washing (to remove organic acids

d f h l) i d h id i C f h dand traces of phenol) reintegrated to the oxidation process. Cumene free exhausted gases aresent to the atmosphere.The so oxidized process stream is sent into a pressure relief vessel and thereafter to a coupleof columns where cumene in excess evaporates under conditions of vacuum and temperatureof columns where cumene in excess evaporates under conditions of vacuum and temperatureto concentrate the CHP up to 80%; vapor of cumene is then condensed and sent to thecaustic washing system to later be reincorporated to the oxidation process.

Production

Production

high boiling point by products and the highest output of one market demand by product: Alpha Methyl Styrene (AMS).The system is formed of 2 reactors and uses Sulfuric Acid to catalyze the reaction.

In the 1st reactor take place the following reactions:Partial Cleavage of CHP.Dehydration of Carbinol to deliver AMS.

The reaction system is to cleavage the CHP to produce Phenol and Acetone with the lowest delivering of

REACTION

Reaction of Carbinol with CHP to produce Di Cumyl Peroxide (DCP)Reaction of Carbinol with CHP to produce Di Cumyl Peroxide (DCP).

Such reactions develop under conditions of:1.Temperatures between 50 a 53 Celsius degrees2 Low concentration of catalyzer2. Low concentration of catalyzer3.Concentration of Cumene in CHP ranging between 10 to15%.4.Recycling flux of Acetone in excess with respect to CHP.5.Less than 1.0% of Water content in produce of reaction

In the 2nd reactor following reactions are carried into effect:•Total cleavage of CHP to Phenol and Acetone•Conversion of DCP to AMS, Phenol and Acetone•Conversion of Carbinol to AMS•Conversion of Carbinol to AMS.

Production

REACTION

Above reactions take place under below conditions:1.High temperature (125 - 140ºC).2.Low acidity on account of addition of a co-catalyzer (Aqueous Ammonia solution) which reacts with theSulfuric Acid stream to form up to 70 85% of Ammonia BisulphateSulfuric Acid stream to form up to 70 - 85% of Ammonia Bisulphate3.Smooth Sulfuric Acid activity due to water being injected at 2º reactor inlet4.Minimal residence time in the system.5.Addition of Acetone in excess to reach higher selectivity by lowing Phenol And Sulfuric Acidconcentrationsconcentrations.Mentioned conditions support the lowest output of by products and the highest production ofAMS.The 1st reactor system consist of one 3 heat exchangers/two recycling pumps loop. CHPis pumped to the recycling loop through one static mixer where is mixed with other products of reactionis pumped to the recycling loop through one static mixer where is mixed with other products of reactionbefore going into heat exchangers. Sulfuric Acid is pumped to the recycling pumps inlet where Acetone andwater are added too. Thereafter goes to an intermediate vessel where more Acetone, Water and AqueousAmmonia Solution is added to promote high selectivity of conversion to DCP. Produce of reaction ispumped to the 2nd reactor system which consist of one heat exchanger one heater and accessories forpumped to the 2nd reactor system which consist of one heat exchanger, one heater and accessories forconversion to DCP.

Production

REACTION

To prevent vaporization of Acetone the 2nd reactor operates pressurized at 7.5 – 8kg/cm2. From there products of reaction are sent to an internal flashing stage to obtain ina separator tank under vacuum conditions Acetone which is cooled and condensedin 3 Condensers and then stored to feed both 1st and 2nd reactorin 3 Condensers and then stored to feed both 1st and 2nd reactorConcentrated CHP in the bottom of the evaporator is cooled and stored before pass to thestage of washing produce of Cleavage.

SAFETY IN SECTION OF REACTION

The high recirculation rate of added product of reaction through the heat exchange reactors

.

to CHP ratio is a key feature for safety operation of the sectionto CHP ratio is a key feature for safety operation of the section.Low concentration of Sulfuric Acid in the first reactor system contributes to smooth thereaction.Operation of one calorimeter on line behind reactor 1C based on proportionality of rise intemperature among the calorimeter inlet/outlet and the volume of CHP cleavage in it toassure the formation of DCP.

Production

Production

WASHING OF CLEAVAGE

f f (S f )Before distillate the produce of cleavage, the catalyzer (Sulfuric Acid) and organic acidsshould be neutralized to avoid by products and to prevent corrosion to equipment. Suchneutralization is made by means of aqueous sodium sulfate solution and adding alkaline pHsodium phenate solution to neutralize the extracted acid and to free Phenol from the phenatesodium phenate solution to neutralize the extracted acid and to free Phenol from the phenateto obtain more sodium sulfate. The aqueous phase is drained to the defenolation section.

Washing of cleavage is made in two vessels; the first one is used as a mixer and the secondas decanter. Washed produce of cleavage overflows to the first storage vessel from where isas decanter. Washed produce of cleavage overflows to the first storage vessel from where isfed to one coalescer for sodium salts to be removed up to a highest concentration of 30ppm.

The product so treated is stored in the 2nd vessel to be fed to distillation section.

Production

Production

DISTILLATION OF ACETONE

The Distillation section counts on 2 main Distillation trains for purifying Phenol AndAcetone in separate starting with one column from which feeding streams are sent toeach one.

A) In the Crude Acetone column, product of Cleavage is pre heated and then fed as amixture of liquid and vapor. The quality of finished products depend on the correctoperation of this column On the top crude Acetone is obtained and part of thisoperation of this column. On the top crude Acetone is obtained and part of thisstream is sent back as reflux. The balance is fed to the Lights Column.

B) In the Lights Column low boiling point impurities are taken out on the top and phenol) g g p p p pcarried from the Crude Acetone column is neutralized. Lights free Acetone in thebottom of the column is fed to the Acetone Stripping column. Temperature ofoperation to this column is supplied by hot vapors coming on from the hydroextractive column in the Phenol Train that is used as heating fluid in the Lightsextractive column in the Phenol Train that is used as heating fluid in the LightsColumn re boiler.

Production

DISTILLATION OF ACETONE

The Distillation section counts on 2 main Distillation trains for purifying Phenol AndAcetone in separate starting with one column from which feeding streams are sent toeach one.

A) In the Crude Acetone column, product of Cleavage is pre heated and then fed as amixture of liquid and vapor. The quality of finished products depend on the correctoperation of this column On the top crude Acetone is obtained and part of thisoperation of this column. On the top crude Acetone is obtained and part of thisstream is sent back as reflux. The balance is fed to the Lights Column.

B) In the Lights Column low boiling point impurities are taken out on the top and phenol) g g p p p pcarried from the Crude Acetone column is neutralized. Lights free Acetone in thebottom of the column is fed to the Acetone Stripping column. Temperature ofoperation to this column is supplied by hot vapors coming on from the hydroextractive column in the Phenol Train that is used as heating fluid in the Lightsextractive column in the Phenol Train that is used as heating fluid in the LightsColumn re boiler.

Production

DISTILLATION OF ACETONEDISTILLATION OF ACETONE

C) Bottoms of lights column are received in the Stripping Column where Acetone is removedfrom the feeding stream composed of Acetone, Cumene, AMS, and other componentsheavier than Acetone. Product in the bottom is sent to a decanter where the organic phaseoverflows to the feeding tank of AMS distillation/Cumene recovery section and the remainingaqueous phase is sent to washing of Cleavage system.

D) The Pure Acetone Column operates as a Rectifier Tower, it process the distillated productcoming out from the top of the Stripping Column. Acetone of 99.65% Purity is obtained on thetop, part of this Acetone is recycled as reflux to the column for the rectification and thebalance is sent to the Pure Acetone Storage Tank.

In the Pure Acetone Column bottom, heavy products with traces of Acetone are obtained.This stream is used as reflux in the Stripping Column to distillate all of the AcetoneThis stream is used as reflux in the Stripping Column to distillate all of the Acetone.

Production

Production

DISTILLATION OF PHENOLDISTILLATION OF PHENOL

This section counts on 4 columns:

A) To the Column of Heavies are fed the bottoms of the Crude Acetone Column whichare Phenol and heavy impurities. There under conditions of vacuum and temperaturephenol and lights are obtained on the top while heavy impurities plus small volumesf di till t d h l i i th b tt Thi d t i t t th Ph lof non distillated phenol remain in the bottom. This product is sent to the Phenol

Recovery Section.Product on top of the Column of Heavies goes through a heat exchanger to becondensed and to heat the stream coming out from the bottom of the Hydrocondensed and to heat the stream coming out from the bottom of the HydroExtractive/Dehydrator Column. The so condensed product is then cooled and storedin the Column of Heavies Reflux Tank. From this tank, part of the produce is sentback to the top of same column for rectifying phenol and the balance is sent to theH d E t ti /D h d t l f li ht t b t dHydro Extractive/Dehydrator column for lights to be separated.

Production

DISTILLATION OF PHENOLDISTILLATION OF PHENOL

B) In the Hydro Extractive/Dehydrator column products lighter than phenol (Cumene,Toluene, water, etc,) are eliminated. In the hydro extractive section (top of the column), , ,) y ( p )light hydrocarbons and water being injected as reflux to form with them low boilingpoint azeotropes are separated while in the Dehydrator section (bottom of the column)traces of water in phenol overflowing through heat exchangers located in the top of itare fully eliminated Heating of this section is made with High Pressure Steam fromare fully eliminated. Heating of this section is made with High Pressure Steam fromSteam Generators located in the Utilities Plant.

C) Phenol from the bottom of the Dehydrator Section is fed to the Pure Phenol Columnpreviously passing trough the Purification Resins Columns where content of impuritiesp y p g g plike Ketones, Mesitile Oxide and hydroxiacetone are reduced to meet salesspecifications. Before being fed to the Pure Phenol Column, phenol coming out of thePurification Resins Columns is filtered, pre heated and passed through a heatexchangerexchanger.

Production

DISTILLATION OF PHENOL

D) In the Pure Phenol Column traces of heavies are separated in the bottom and traces oflights are eliminated in the top. Purity of phenol being obtained in the middle of the column ist l t 99 97% P t f thi d t i t b k t l fl th ti iat least 99.97%. Part of this product is sent back to same column as reflux, other portion is

sent to the first distillation column to eliminate lights and the balance is sent to be cooled to49-50°C and then stored in the day tanks. From these vessels, Pure Phenol is sent tostorage in the finished product tank farm where Citric acid is added to prevent discolorationstorage in the finished product tank farm where Citric acid is added to prevent discolorationof the product.

Production

Resins of Purification

CWR

CWS

Phenol Purification

To PhenolResins

Production

PURIFICATION OF AMS/ RECOVERY OF CUMENE

This section is made of 3 columns which operates under vacuum conditions to purify AMS

A) In the Column of Lights the portion of Cumene/AMS is separated from mixed lighthydrocarbons coming from the Storage tank: Before being fed, this stream is preheated in a heat exchanger with Medium Pressure Steam. On the top of the columnlow boiling point components are obtained and condensed to be stored in theColumn of Lights Reflux Tank. Part of stored material is sent back to the column andthe balance is purged in batch as small fractions of light products to the stage ofrecovering of phenolrecovering of phenol.The portion with higher boiling point composed of Cumene/AMS is taken out of thebottom of the column to be condensed in 2 condensers and then stored in a Tankfrom which is fed to the Cumene Column

Production

PURIFICATION OF AMS/ RECOVERY OF CUMENE

B) The column of Cumene separates a stream of AMS free Cumene/light impurities onB) The column of Cumene separates a stream of AMS free Cumene/light impurities onthe top. This product is condensed and stored in a tank to partially being recycled to thecolumn and the balance sent to the stage of washing of cumene as recovered product tobe oxidized. In the bottom of the column lights free AMS/Heavies remain to be fed to thegcolumn of Purification of AMS.A good control of content of Cumene in the bottom of this column is key for thecompliance of required finished product quality. To keep it one Chromatograph operateson line analyzing samples received from the column bottom line of recirculation each 13on line analyzing samples received from the column bottom line of recirculation each 13minutes and reporting contents of impurities like Sec and Tert Butyl benzene as well asn- Propyl Benzene.

Production

PURIFICATION OF AMS/RECOVERY OF CUMENE

C) The Column for Purification of AMS functions as a Rectifier Tower It receivesC) The Column for Purification of AMS functions as a Rectifier Tower. It receivesthe stream coming on from the bottom of the Column of Cumene. On the topAMS is obtained and condensed to be stored in a vessel. Part of the storedmaterial is sent back to the column for the rectification and the balance is sent tothe storage Day tank with a purity of at least 99.51%. To avoid polymerization anstabilizer is added.From the bottom of the column a stream of heavy impurities mixed with smallquantities of AMS is extracted and cooled to be placed together with productquantities of AMS is extracted and cooled to be placed together with productdrained from the bottom of the column of Cumene and be sent as purge ofheavies to the section for recovery of phenol

Production

Production

RECOVERY OF PHENOLRECOVERY OF PHENOL

In this stage Phenol, Cumene and AMS contained in the stream coming on from trainsof distillation is recovered.In one Cracking Drum the free phenol is distilled and heavy phenols are thermallyfractioned. Heaviest products are drained in batch to be stored and disposed asalternative fuel oil.Products distilled in the Cracking Drum leave as vapors on the top directly to theProducts distilled in the Cracking Drum leave as vapors on the top directly to theAcetophenone Column where Phenol, Cumene and AMS are evaporated and thereaftercooled and condensed in a tank from which one portion is recycled back to the columnfor rectification and the balance is sent to the section of washing of cleavage.g gIn the bottom, Acetophenone with traces of phenol is extracted, cooled and stored forbeing used as solvent to dilute heavy residues in the Cracking Drum.The energy for heating these 2 phases is provided to heaters by hot vapors of a thermicoil in turn evaporated in a direct flame heater that operates with natural gasoil in turn evaporated in a direct flame heater that operates with natural gas.

Production

Production

DEFENOLATION

This section is to recover the phenol contained in all of different aqueous streamsThis section is to recover the phenol contained in all of different aqueous streamsdrained from process: Washing of Cleavage, Distillation of Acetone, vacuum ejectors hotwells and washing of equipment when carried out. Operation is made in 3 stages:Primary Decanter. Water stored in a ditch is fed to the 1rst stage where content of phenoly g pin the aqueous phase is extracted using Cumene recycled from the Secondary decanterby mixing both streams. The turbulence generated makes the phenol pass to theCumene before going into the decanter. The mixture is decanted and the separatedaqueous phase with traces of phenol is sent to the Plant Waste water System Theaqueous phase with traces of phenol is sent to the Plant Waste water System. Thecumene with phenol overflows to the mixer.Mixer. In this equipment is installed an internal diffuser to improve efficiency in extractionof phenol. Before entering to the mixer streams with fresh caustic soda and sodiumphenate with caustic soda in excess are injected. It is in this stage when defenolationoccurs.Secondary Decanter. In this stage phenol free cumene is decanted and then overflowsto the tank of feeding to purification of AMS Part of the aqueous phase is recycled to theto the tank of feeding to purification of AMS. Part of the aqueous phase is recycled to thePrimary Decanter and the balance is sent to section of Washing of Cleavage as sodiumphenate.

Production

ProductionPHENOL ACETONE

NAMEPLATE CAPACITY, TPY: •• • ACETONE 23,000• AMS 2,500

INSTANT VELOCITY; TPD:INSTANT VELOCITY; TPD:• PHENOL 120• ACETONE 72• AMS 7

PHENOL 40,000

OST, % : 96.8

YIELDS OF RAW MATERIALS TO PHENOL, TON/TONCUMENE: 1 396CUMENE: 1.396CUMENE 1.3339 (WITH CUMENE CONVERTED TO AMS CREDITED)H2SO4: 0.0139CAUSTIC SODA: 0.0126AMMONIA: 0 0010AMMONIA: 0.0010

YIELDS OF BY PRODUCTS TO PHENOL, TON/TONACETONE 0.605AMS 0 064AMS 0.064TAR 0.0516

Production

PHENOL ACETONE

CONSUMPTION OF UTILITIES VS PHENOLCONSUMPTION OF UTILITIES VS PHENOLSTEAM, TON/TON: 6.32ELECTRICITY, KWH/TON: 326.00REFRIGERANT, M3/TON: 11.00COOLING WATER, M3/TON: 428.00COMPRESSED AIR, M3/TON: 104.00NATURAL GAS, M3/TON*: 10.00

*Consumption on Thermal Oil Heating System.

Photos

Photos

Photos