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EB Plant EQUATE Petrochemical Company. Agenda. EB Unit Description EB Plant Overview - Basic chemistry -Design of EB plant - Catalyst -Operating conditions. EB Unit Description. The Ethylbenzene Unit consists of three main sections: Alkylation Reactor Section - PowerPoint PPT Presentation
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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