EB PlantEQUATE Petrochemical Company

AgendaAgenda

EB Unit DescriptionEB Unit Description

EB Plant OverviewEB Plant Overview --Basic chemistryBasic chemistry

-Design of EB plant-Design of EB plant - Catalyst- Catalyst

-Operating conditions-Operating conditions

EB Unit DescriptionEB Unit Description

The Ethylbenzene Unit consists of The Ethylbenzene Unit consists of three main sections: three main sections:

1.1. Alkylation Reactor SectionAlkylation Reactor Section

2.2. Transalkylation Reactor SectionTransalkylation Reactor Section

3.3. Distillation Section.Distillation Section.

EB Unit OverviewEB Unit Overview

EB Block Flow DiagramEB Block Flow Diagram

EB simple flowEB simple flow

C1201

C1211

G1213/4G1203/4

E1210

F1205

G1230/1

G1313/4

C1311

E1310

C1301

E1320

C1710

C1120

Y1118

Y1117

Y1116

Y1115

C1110

E1305

C1307

E1405

G1402/3

G1413/4

E1420

C1411

E1409E1410

H1415

C1401

G1502/3

C1810/11

C1501

G1513/4

C1511

E1509E1510

Fresh BZ

ET

E1111

E1711

C8520

F1205

C2501

ResidueTank

PC

MPCC

LP

E1311

E1112

E1211

EB TankD2001

N2

Flr

BZ

EB Plant OverviewEB Plant Overview

-Basic chemistry-Basic chemistryThe chemistry of EB reactions is centered on Benzene molecules and Ethylene molecules. The chemistry is fundamentally based on carbon and hydrogen atoms arranged in various combinations.

Benzene feed to the process is a six carbon ring compound with three double bonds alternating between the carbons, C6H6

Ethylene feed to the process is a two carbon molecule with double bonds between the carbons, C2H2 C = C

In the EB Process there are two types of reactions:

1- Alkylation Reaction. 2-Transalkylation Reaction.

The reaction will produce Ethyl Benzene (EB) in the presence of Zeolite catalyst

Alkylation ReactionAlkylation Reaction

Alkylation reaction is the main reaction in EB process where one ethyl group is supplied by Ethylene molecules is being attached to one Benzene ring to produce Ethyl Benzene (EB)

C6H6 + C2H4 C6H6 + C2H4 C8H10 C8H10

BZ Ethylene EB

The Alkylation reaction is an exothermic reaction, it’s an irreversible reaction and essentially all the ethylene is reacted

Poly Ethyl Benzene (PEB’s) are also produced while producing EB

PEB reactions as shown below:

C6H5-C2H5 + C2H4 C6H4-(C2H5)2

Ethyl Benzene Ethylene Diethyl Benzene

C6H4-(C2H5)2 + C2H4 C6H3-(C2H5)3

Diethyl Benzene Ethylene Triethyl Benzene

C6H3-(C2H5)3 + C2H4 C6H2-(C2H5)4Triethyl Benzene Ethylene Tetraethyl Benzene

Other minor by product are caused by :

1-Ethylene attached at the end of an ethyl group of EB

C6H5-C2H5 + C2H4 C6H5-C4H9Ethyl Benzene Ethylene Butyl Benzene (BB)

2-Benzene reacts with PropyleneC6H6 + C3H6 C6H5-C3H7Benzene Propylene normalpropylbenzene (NPB)

 

 

  

3-Benzene reacts with PropyleneC6H6 + C3H6 C6H5-C3H7 Benzene Cumene (CUM)

4-Ethylene reacts with Toluene C6H5-CH3 + C2H4 C6H5-C3H7Toluene Ethylene Ethyl Toluene

Propylene

At the design ratio of Benzene to Ethylene feeds is 2.5 molar basis and seven catalyst beds, the alkylation reaction creates:

a.Diethyl Benzene 9.7%b.Triethyl Benzene 0.6%c.Tetraethyl Benzene 0.03%d.Butyl Benzene 0.02%

Transalkylation (TA) ReactionTransalkylation (TA) Reaction

The purpose of TA Reactor is to reacts recycle PEB with Benzene to produce The purpose of TA Reactor is to reacts recycle PEB with Benzene to produce EB. EB.

C6H4-(C2H5)2 C6H4-(C2H5)2 + + C6H6C6H6 2C6H5-C2H5 2C6H5-C2H5

Diethyl Benzene Benzene Diethyl Benzene Benzene Ethyl BenzeneEthyl Benzene

C6H3-(C2H5)3C6H3-(C2H5)3 + + C6H6 C6H6 C6H4-(C2H5)2 + C6H5-C2H5 C6H4-(C2H5)2 + C6H5-C2H5

Triethyl Benzene Benzene DiethyBenzene EthylBenzeneTriethyl Benzene Benzene DiethyBenzene EthylBenzene

C6H5-C4H9C6H5-C4H9 + C6H6 C6H6 2 C6H5-C2H5 2 C6H5-C2H5

Butyl Benzene (BB) Benzene Butyl Benzene (BB) Benzene Ethyl Benzene Ethyl Benzene

Design of EB PlantDesign of EB Plant

Ethylene specificationEthylene specification

Page 17

ComponentComponent RequirementRequirement

EthyleneEthylene 99.96 vol. %, minimum99.96 vol. %, minimum

Methane + EthaneMethane + Ethane 0.02 vol. %, maximum0.02 vol. %, maximum

AcetyleneAcetylene 1 vol. ppm, maximum1 vol. ppm, maximum

C3 and HeavierC3 and Heavier 10 vol. ppm, maximum10 vol. ppm, maximum

Free OxygenFree Oxygen 2 vol. ppm, maximum2 vol. ppm, maximum

Carbon MonoxideCarbon Monoxide 1 vol. ppm, maximum1 vol. ppm, maximum

Carbon DioxideCarbon Dioxide 5 vol. ppm, maximum5 vol. ppm, maximum

HydrogenHydrogen 2 vol. ppm, maximum2 vol. ppm, maximum

Nitrogen (as N2)Nitrogen (as N2) 100 ppm, maximum100 ppm, maximum

Sulfur (as S)Sulfur (as S) 0.1 wt. ppm, maximum0.1 wt. ppm, maximum

WaterWater 5 vol. ppm, maximum5 vol. ppm, maximum

Alcohol (as Methanol)Alcohol (as Methanol) 1 vol. ppm, maximum1 vol. ppm, maximum

DienesDienes 5 wt. ppm, maximum5 wt. ppm, maximum

Carbonyls (as MEK)Carbonyls (as MEK) 1 vol. ppm, maximum1 vol. ppm, maximum

Total Nitrogen CompoundsTotal Nitrogen Compounds 0.1 wt. ppm, maximum0.1 wt. ppm, maximum

Benzene specificationBenzene specificationComponentComponent RequirementRequirement

BenzeneBenzene 99.85 wt. %, minimum99.85 wt. %, minimum

Solidification Point (Anhydrous Basis)Solidification Point (Anhydrous Basis) 5.40°C, minimum5.40°C, minimum

HH22S and SOS and SO22 0.1 wt. ppm, maximum0.1 wt. ppm, maximum

Total SulfurTotal Sulfur 1 mg/l, maximum1 mg/l, maximum

ThiopheneThiophene 1 wt. ppm, maximum1 wt. ppm, maximum

Acidity Acidity No free acidNo free acid

Acid Wash Color (Anhydrous Basis)Acid Wash Color (Anhydrous Basis) No. 2, maximumNo. 2, maximum

Total Chlorides (as Chlorine)Total Chlorides (as Chlorine) 3 wt. ppm, maximum3 wt. ppm, maximum

WaterWater 200 wt. ppm, maximum200 wt. ppm, maximum

Nitrogen CompoundsNitrogen Compounds 1 wt. ppm, maximum1 wt. ppm, maximum

Non-AromaticsNon-Aromatics 1000 wt. ppm, maximum1000 wt. ppm, maximum

TolueneToluene 500 wt. ppm, maximum500 wt. ppm, maximum

Copper CorrosionCopper Corrosion Shall pass testShall pass test

Bromine IndexBromine Index 10, maximum10, maximum

EB SpecificationEB Specification

ComponentComponent RequirementRequirement

EthylbenzeneEthylbenzene 99.85 wt. % Min.99.85 wt. % Min.

NonaromaticsNonaromatics 500 ppm wt. Max.500 ppm wt. Max.

BenzeneBenzene 1000 ppm wt. Max.1000 ppm wt. Max.

TolueneToluene 1000 ppm wt. Max.1000 ppm wt. Max.

Benzene + TolueneBenzene + Toluene 1000 ppm wt. Max.1000 ppm wt. Max.

StyreneStyrene 500 ppm wt. Max.500 ppm wt. Max.

XylenesXylenes 50 ppm wt. Max.50 ppm wt. Max.

CumeneCumene 100 ppm wt. Max.100 ppm wt. Max.

DiethylbenzeneDiethylbenzene 2 ppm wt. Max.2 ppm wt. Max.

SulfurSulfur 2 ppm wt. Max.2 ppm wt. Max.Total Chlorides (as Chlorine)Total Chlorides (as Chlorine)

2 ppm wt. Max.2 ppm wt. Max.

Color, Pt-CoColor, Pt-Co 5 Max.5 Max.

Ethylene feed systemEthylene feed systemControl Ethylene feed rate to the Alkylation Control Ethylene feed rate to the Alkylation reactorreactor

Control Plant EB CapacityControl Plant EB Capacity

Ensure B/E ratio is acceptableEnsure B/E ratio is acceptable

Benzene feed systemBenzene feed systemRemove catalyst poisons from benzeneRemove catalyst poisons from benzene

Take regular samples to track guard bed Take regular samples to track guard bed performanceperformance

Replace BZ treater4 mol-sieve as neededReplace BZ treater4 mol-sieve as needed

Use freshest mol-sieve in “downstream” Use freshest mol-sieve in “downstream” treatertreater

Alkylation systemAlkylation systemReact ethylene with benzene to make React ethylene with benzene to make EthylbenzeneEthylbenzene

Control reaction parameters for optimum Control reaction parameters for optimum selectivity and catalyst lifeselectivity and catalyst life B/E ratio at 2.5 (molar) or 7.04 (weight)B/E ratio at 2.5 (molar) or 7.04 (weight) Inlet temperatureInlet temperature Water concentrationWater concentration

Alkylator ReactorAlkylator Reactor

Reactive Guard Reactive Guard BedBed

AlkylatorAlkylator

IntercoolerIntercooler

Ethylene mixersEthylene mixers

Reactive Guard BedReactive Guard BedSeparate vessel containing catalystSeparate vessel containing catalyst

Allows replacement while keeping unit in Allows replacement while keeping unit in operationoperation

Catalyst aging typically only in first bedCatalyst aging typically only in first bed

TransalkylatorTransalkylatorReact PEB with benzene to make EBReact PEB with benzene to make EB

No Temperature increaseNo Temperature increase

Preheater to control reactor temperaturePreheater to control reactor temperature

Benzene columnBenzene columnRecover benzene from Recover benzene from

reactor productreactor product

Furnace reboilerFurnace reboiler

Condenser generates Condenser generates

MP steamMP steam

0.5% EB in overhead0.5% EB in overhead

700 ppm Bz in bottom 700 ppm Bz in bottom

productproduct

EB columnEB columnSeparate EB product from Separate EB product from

PEB and heaviesPEB and heavies

Steam reboilerSteam reboiler

Condenser generatesCondenser generates

LP steamLP steam

1 ppm DEB in1 ppm DEB in

EB productEB product

1 wt% EB in bottom product1 wt% EB in bottom product

PEB columnPEB columnSeparate PEB product Separate PEB product

from heaviesfrom heavies

Steam reboilerSteam reboiler

Condenser preheatsCondenser preheats

condensate (BFW)condensate (BFW)

50 ppm dicyclics 50 ppm dicyclics

in PEB productin PEB product

5 wt% TEB in 5 wt% TEB in

bottom productbottom product

Lights ColumnLights ColumnDry fresh benzene Dry fresh benzene

(<25 ppm in bottoms)(<25 ppm in bottoms)

Remove non-aromatics Remove non-aromatics

and lights componentsand lights components

Heat input by vapourHeat input by vapour

stream from Bz columnstream from Bz column

Condenser preheats Condenser preheats

fresh benzenefresh benzene

Portion condensed by Cooling WaterPortion condensed by Cooling Water

Benzene treatersBenzene treatersRemove organic N-components Remove organic N-components

from benzenefrom benzene

Mol-sieve operating atMol-sieve operating at

elevated temperature (115°C)elevated temperature (115°C)

Benzene Treaters containsBenzene Treaters contains

two types of molecular sieve, two types of molecular sieve,

which has function:which has function:1. As water adsorber 1. As water adsorber 4A molecular sieve 4A molecular sieve 2. As benzene impurities adsorber 2. As benzene impurities adsorber 13X molecular 13X molecular sievesieveVolume ratio between water adsorber and benzene Volume ratio between water adsorber and benzene impurities adsorber impurities adsorber 1 : 3 1 : 3

Benzene Treater contains of two types of molecular Benzene Treater contains of two types of molecular sieve, which has function:sieve, which has function:

1. As water adsorber 1. As water adsorber 4A molecular sieve 4A molecular sieve 2. As benzene impurities adsorber2. As benzene impurities adsorber 13X molecular 13X molecular sievesieve

Volume ratio between water adsorber and benzene Volume ratio between water adsorber and benzene impurities adsorber impurities adsorber 1 : 3 1 : 3

Basic chemistry in the Benzene Treater:Basic chemistry in the Benzene Treater:

C C66HH66 + B + A + B + A C C66HH6 6 + BA + BA Benzene Benzene Basic compound Active site on Benzene without Basic compoundBasic compound Active site on Benzene without Basic compound

attached attached dissolved in Benzene Molecular sieve Basic compound to molecularsieve dissolved in Benzene Molecular sieve Basic compound to molecularsieve

EB PlantEB Plant

Catalyst:Catalyst:

Zeolite catalyst.Zeolite catalyst.

Type :Type :

1- EM – 3300 (Alkylation Reactor)1- EM – 3300 (Alkylation Reactor)

2- EM – 3700 (TA Reactor)2- EM – 3700 (TA Reactor)

Catalyst poisons:Catalyst poisons:Nitrogen compounds will deactivate the catalyst Nitrogen compounds will deactivate the catalyst by neutralizing acid sites. Maximum 1 ppm in by neutralizing acid sites. Maximum 1 ppm in Benzene feed and 0.025 ppm out of the RGB.Benzene feed and 0.025 ppm out of the RGB.

Chloride will interact and weaken the catalyst Chloride will interact and weaken the catalyst binder. Maximum 1 ppm in Benzene.binder. Maximum 1 ppm in Benzene.

Water, will deactivate the catalyst.Water, will deactivate the catalyst.

Metals, will permanently deactivate the catalyst.Metals, will permanently deactivate the catalyst.

Operating ConditionOperating Condition

1.1. BZ to C2 ratio : 7.04 wt/wt or 2.5mol/mol BZ to C2 ratio : 7.04 wt/wt or 2.5mol/mol

2.2. C2 conversion is nearly 100% C2 conversion is nearly 100%

3.3. Effluent Pressure : 34.1 kg/cm2 Effluent Pressure : 34.1 kg/cm2

4.4. Inlet bed temperature : 195 °C Inlet bed temperature : 195 °C

5.5. Outlet bed temperature : 257 °C Outlet bed temperature : 257 °C

6.6. Catalyst : EM-3300 Catalyst : EM-3300

Alkylation ReactorAlkylation Reactor

1.1. BZ to PEB ratio BZ to PEB ratio : 2.0 wt/wt: 2.0 wt/wt

2.2. DEB Conversion DEB Conversion : 62%: 62%

3.3. Effluent pressure Effluent pressure : 31.1 kg/cm2: 31.1 kg/cm2

4.4. Operating temperature Operating temperature : 200°C : 200°C

5.5. Catalyst Catalyst : EM-3700: EM-3700

TA Reactor TA Reactor ::

1.1. Operating pressure Operating pressure : 1.5 kg/cm2: 1.5 kg/cm2

2.2. Overhead temperature Overhead temperature : 111 °C: 111 °C

3.3. Bottom temperature Bottom temperature : 115 °C: 115 °C

4.4. Number of tray Number of tray : 20 trays: 20 trays

5.5. Water content at bottom Water content at bottom : 25 ppm (design): 25 ppm (design)

Light Column Light Column

BENZENE TREATERBENZENE TREATER

1.1. Operating pressure Operating pressure : 18.2 kg/cm2: 18.2 kg/cm2

2.2. Inlet bed temperature Inlet bed temperature : 110 °C: 110 °C

3.3. Delta pressure Delta pressure : 0.35: 0.35

4.4. N2 compound at outlet: 30 ppb (0.03 ppm)N2 compound at outlet: 30 ppb (0.03 ppm)

5.5. Adsorbing media Adsorbing media : Molecular sieve (4A and 13X) : Molecular sieve (4A and 13X)

BENZENE COLUMNBENZENE COLUMN

1.1. Operating pressure Operating pressure : 13.2 kg.cm2: 13.2 kg.cm2

2.2. Key component temperature Key component temperature : 269 °C (tray 11): 269 °C (tray 11)

3.3. Reflux ratio Reflux ratio : 1.62: 1.62

4.4. Overhead temperature Overhead temperature : 200 °C: 200 °C

5.5. Bottom temperature Bottom temperature : 280 °C: 280 °C

6.6. Number of tray Number of tray : 40 trays: 40 trays

7.7. BZ content at bottom BZ content at bottom : less than 700 ppm: less than 700 ppm

8.8. EB content at overhead EB content at overhead : 0.5 % wt: 0.5 % wt

EB COLUMNEB COLUMN

1.1. Operating pressureOperating pressure : 1.1 kg/cm2: 1.1 kg/cm2

2.2. Key component temperature Key component temperature : 221 °C (tray 5): 221 °C (tray 5)

3.3. Overhead temperature Overhead temperature : 169 °C: 169 °C

4.4. Bottom temperature Bottom temperature : 231 °C: 231 °C

5.5. Reflux ratio Reflux ratio : 1.3: 1.3

6.6. Number of tray Number of tray : 54 trays: 54 trays

7.7. EB content in the bottom EB content in the bottom : < 1% wt: < 1% wt

8.8. DEB content in the overhead : < 1 ppmDEB content in the overhead : < 1 ppm

PEB COLUMN PEB COLUMN

1.1. Operating pressure Operating pressure : -0.8 kg/cm2: -0.8 kg/cm2

2.2. Key component temperature Key component temperature : 176 °C (tray 4): 176 °C (tray 4)

3.3. Overhead temperature Overhead temperature : 141 °C: 141 °C

4.4. Bottom temperature Bottom temperature : 229 °C: 229 °C

5.5. Reflux ratio Reflux ratio : 0.2: 0.2

6.6. Number of tray Number of tray : 20 trays: 20 trays

7.7. TEB content in bottom TEB content in bottom : < 5 %wt: < 5 %wt

8.8. Heavies content in overhead : < 50 ppmHeavies content in overhead : < 50 ppm