Hydrocracking Fundamentals & Features

Mukesh Mohan

What is Hydroprocessing ?
It is used to upgrade naphtha,distillates,heavy oils and residul stocks by Removal of sulfur and nitrogen Metals and other contaminants Saturation of olefins and aromatics

Rise in Hydroprocessing capacity in Refinery

Increase in demand of Middle Distillate fuels has increased the hydroprocessing capacities. Stringent environmental legislation. Cetane increase, Density reduction
200 180 160 140 120 100 80 60 40 20 0 2000 2005 200

IndianOil

12 10 8 6

12

7.5 6

53

4 2 0

2.4

2000
HYDROGEN, KNm3/hr

2005

REFINERY CAPACITY, MMTPA 3 HYDROPROCESSING CAP, MMTPA

BENEFITS OF HYDROCRACKING
Produces Low Sulphur Products Improves Combustion Quality
High Cetane Low Aromatics/Olefins High H2 Content Excellent Color Stability - Lowering N2 content

Improves Downstream Processing

FCC or RFCC Olefins or Aromatics Plant Lube Oil Production

COMPARISON OF ALTERNATE CRACKING PROCESS

Hydrocracking Op. Press. Naphtha Middle Distillates ATF Product Quality Post treatment of products Capital, Maint Cost High Low High Yes High No High

FCC Low High Moderate No Low Yes Low

Thermal cracking Low Low Moderate No Low Yes Low

Process Chemistry
Crude Oil Properties Hydrotreating

Crude Oil Composition

Various colors Various contaminant levels Various flowing properties

Crude Oil Composition wt%

Carbon Hydrogen Sulfur Nitrogen Metals 84-87 11-14 0.1-2.0 0.01-0.2 0.0-0.1

Crude Oil Composition

Paraffins Naphthenes Aromatics

H H

H c

c H H Ethane C2H8

Paraffins (Alkanes)

H H

H c H

H c H

H c H H H

Single bonded hydrocarbons Name ending in ane Chemical Symbols CnH2n+2 Ranging from C1 to C50+ Saturated Each molecule contains its full amount of hydrogen No double bonds or impurities Stable

Paraffinic / Waxy

Naphthenes
Cyclo-paraffins Symbol - CnH2n Ringed saturated hydrocarbons May have one ring or several combined May contain impurities such as nitrogen and sulfur
H H H c H c H c c H H H c H H

c H H

H H H H c H c H c

H c H H c c H H H

cyclo-hexane

H c H Butene C4H8

H c c H H

H c

H H

Olefins (Alkenes)

H H c c H

H c c H

H c

H H

Pentadiene C5H8

Double bonded hydrocarbons. Chemical symbols CnH2n for 1 double bond Diolefins 2 double bonds Unsaturated Lacking some hydrogen due to double bonds Formed in refinery processes that crack without the presence of hydrogen Break down readily in treating reactors

H c H c c H H c H Toluene c c

H
H H c c c H c H c H

c H

Aromatics

H c

Cyclo-alkene Benzene (aromatic) Base is benzene ring Can have sub groups Methyl, Ethyl H H c c Unsaturated H c c H Lacking hydrogen due to 3 double c c H H bonds per ring c c c c PNAs H H polynucleararomatic PNA Polynuclear aromatics Two or more benzene rings

Nitrogen Compounds in Petroleum

Basic Nitrogen NH H C 3 Amine N 2 N Pyridine N Quinoline Phenanthridine

Non-Basic NH Indole NH Carbazole

Sulfur Distribution
Sulfur exists throughout the boiling range of petroleum, except the lightest fractions Sulfur concentration increases with increased boiling range
7 6

Sulfur, Wt%

5 4 3 2 1 0 <350C 350-450C 450-550C >550C CatCanyon Arabian Hvy. SJV Hvy

Distillation Range

Sulfur Compounds in Petroleum

H3C Mercaptan SH S H3C Disulfide H3C S CH3

S Thiophene

S Benzothiophene

S CH3

CH3 S Dibenzothiophene

Substituted Benzothiophene

Nitrogen DistributionHondo Crude (California Offshore)

Nitrogen rises as boiling range increases

1.5 1.2

Nitrogen, Wt%

0.9 0.6 0.3 0 <315C 315-370C 370-425C 425-480C 480-535C >535C

Distillation Range

Nitrogen Compounds in Petroleum

Basic Nitrogen NH H C 3 Amine N 2 N Pyridine N Quinoline Phenanthridine

Non-Basic NH Indole NH Carbazole

Hydrocracking Unit Reactions

Desired reactions
Treating to remove contaminants Adding hydrogen to unsaturated hydrocarbons Cracking to obtain desired boiling range products

Undesired reactions - Coking - Contaminant poisoning

Reactions
Treating Sulfur Nitrogen Olefins Oxygen Metals
Cracking To desired endpoint To desired product slate

Hydrotreating Chemistry
Desulfurization Denitrification Olefin Saturation Aromatic Saturation Metals Removal Oxygenates Removal Halides Removal

Why Pretreat Feedstock

Improve cracking catalyst effectiveness
By reducing organic nitrogen in cracking reactor feed

Reduce temperature rise in cracking beds

Treating reactions can be very exothermic

Treating Reactions
Metals removal Olefins saturation Sulfur removal Nitrogen removal

Easiest

Hardest

Oxygen removal

Hydrotreating
Approximate relative heats of reaction
(per kg or lb) Olefin Saturation 100 Desulfurization Denitrogenation 20 2

Treating By-Products
Organic Sulfur H2 S Organic Nitrogen NH3 Oxygen compounds H2 O

Features of HDS and HDN Reactions

Hydrodesulfurization (HDS)
Sulfur removed first then the olefin is saturated

Hydrodenitrogenation (HDN)
Aromatic saturated first then nitrogen is removed

Postulated HDS Mechanism

(A) Desulfurization HC - CH +2H2 HC - CH S (B) Olefin Saturation H2C=CH-CH=CH2 + 2H2

H2C=CH-CH=CH2 + H2S

H3C -CH2 -CH2-CH3

HDS Reactions
S Heptanethiol +2H2 Butadiene +2H2 Butane H +H2 Heptane + H2S + H2S

S Thiophene S Butylpropyl Sulfide

+ H2S Propane

S CH3+2H2 Methylphenyl Sulfide

+ CH4 + H2S Benzene Methane

Reaction Rate Equation for Desulfurization

At high conversion levels, desulfurization reactions follow first-order kinetics The rate constant for easy sulfurcontaining molecules may vary greatly from hard Gas oils contains a variety of sulfur compounds that vary greatly in their ease of sulfur removal (different rate constant)

Thiophene Sulfur is Most Difficult Approx. Factor of Difficulty

CH3CH2SCH3CH2+ 2H2 Diethylsulfide (B.P. 92C) S Thiophene (B.P. 84C) + 2H2 S Benzthiophene (B.P. 221C) + 2H2 + 2H2 2C2H6 + H2S Base = 1 + H2S 5

+ H2S

15

+ H2S

14

Dibenzthiophene (B.P. 315C(est.))

Nitrogen Removal
Amine C-C-C-C-N C Pyrrole C N C N C N C C + 4H2 C-C-C-C (and C-C-C) + NH3 C C-C-C-C-C (and C-C-C-C-) + NH3 C C C C C H H + H2 C-C-C-C + NH3

Pyridine

C C C C

C + 5H2 C

Quinoline

C C

C C

C + 4H2 C

C-C-C-C + NH3 C

2000 1500 1000 500 0

Arabian Hvy

Nitrogen Distribution in Middle-Eastern Crudes

Nitrogen concentrates in the heavier portions of a crude
1500 1200 900 600 300 0

Kuwait Crude

50 55 60 65 70 Mid. wt-% on Crude

Dubai Crude
6000 5000 4000 3000 2000 1000 0 50

60 70 80 90 Mid. wt-% on Crude

As boiling range increases, the complexity of the organic nitrogen molecules also increase, making the nitrogen more difficult to hydrotreat Nitrogen: Dubai > Arabian Heavy > Kuwait > Murban

50

55 60 65 70 Mid. wt-% on Crude

1200 1000 800 600 400 200 0

Murban Crude

65

70 75 80 85 90 Mid. wt-% on Crude

Postulated HDN Mechanism

(A) Aromatic Hydrogenation CH HC HC N (B) Hydrogenolysis H2C H2C N CH2 CH2 CH2 + H2 CH3-CH2-CH2-CH2-CH2-NH2 CH CH + 3H2 H2C H2C N CH2 CH2 CH2

(C) Denitrogenation CH3-CH2-CH2-CH2-CH2-NH2 + H2

CH3-CH2-CH2-CH2-CH3+NH3

Thermodynamic Effects on HDN Reactions

HDN proceeds through aromatic saturation H2 + NH3

N
A

The overall reaction is rate (not equilibrium) limited in all ordinary conditions Aromatic saturation equilibrium decreases with increasing temperature Rate of NH3 production depends on concentration of intermediates such as A, which decrease with increasing temperature Raising temperature is less effective at EOR

Implications of HDN Chemistry

Complexity makes HDN more difficult than HDS Saturation of aromatic rings requires more H2 for HDN than HDS (On a molar basis) Higher H2 consumption releases more heat Aromatic saturation is equilibrium controlled at high temperature (> 400 C or > 750 F) Desired aromatic saturation requires a narrow range of temperature applicability

Typical Olefin Saturation Reactions

+H2 1-Heptene +H2 Cyclohexene +H2 3-Ethyl-2-Pentene 3-Ethylpentane Cyclohexane n-Heptane

Typical Aromatics Saturation Reactions CH CH

3 3

+ 3H2 Methylcyclohexane + 2H2

Toluene

Naphthalene

Tetralin (Tetrahydronaphthalene) + 3H2

Tetralin

Decalin (Decahydronaphthalene)

Thermodynamic Equilibrium for Aromatics Saturation

+ 3H2 H2 C H2 C Keq Keq 2 x 106 2200 7.1 0.14 0.063 H2 C CH2 CH2 C H2 Cyclohexane

Benzene Temperature, C 150 205 260 315 370

At 1 ATM H2, equilibrium favors benzene at temperatures >315C (600 oF) This is why naphtha catalytic reforming works For most aromatic compounds at 70-140 Kg/cm2 (1,000-2,000) H2 PP, aromatics are favored above 400C (750 oF)

Aromatic Saturation Temperature Effect

Aromatic Saturation

Temperature

Metals Removal
Organo-Metallic Adsorption (Metal + Catalyst) + Hydrocarbon Compounds Reaction

Catalyst Pill

Pore

Halides Removal
C C C C C-C-C-C-Cl C + H2 HCl + C C HCl + NH3 NH4Cl C C C C-C-C-C

HYDROCRACKING
The process of converting higher molecular weight hydrocarbons into more valuable lower molecular weight hydrocarbons C22 H46 + H2 C16H34 + C6H14

In presence of Hydrogen at high temperatures(290 455 deg C) & high pressures (105-190 Kg/cm2g) in presence of a catalyst The products are clean, saturated & high in value

Hydrocracking Reactions
Addition of hydrogen to aromatic centers Addition of hydrogen to olefinic double bonds Acid-catalyzed cracking of paraffins and side chains on aromatics Acid-catalyzed isomerization of paraffins Formation of coke on the surface of catalyst Removal of coke by addition of hydrogen

Hydrocracking Reactions
Feed Hydrogen
Treating Reactions
S N

+ 6H 2 + 7H 2

H 2S + NH 3 +

Polyaromatics Hydrogenation + 2H 2 + 3H 2

Monoaromatics Hydrogenation R R + 3H 2 Hydrodealkyalation R R + H2 + RH + H2 Hydrodecyclization R +H R H+R H

2 1 2

+ RH

+ H2 Hydrocracking C nH 2n+2 + H 2 Hydroisomerization R 1 - CH 2 - CH 2 - R 2

+ C 2H 6 C aH 2a+2 + C bH 2b+2 R R CH 2 - CH 2 - R 2

Products

Hydrogen

Sequence of reactions taking place down the height of a trickle bed hydrocracker employing amorphous catalyst

Hydrocracking Reactions
Bi-functional mechanism Requires two distinct types of catalytic sites to catalyze separate steps in the reaction sequence

Bi-Functional Mechanism
Metal Function:
Generates olefin or cyclo-olefin

Acid Function:
Generates carbenium ion from olefin by proton transfer Carbenium ion cracks Converts carbenium ion to olefin by proton transfer

Metal Function:
Saturates olefins

Postulated Hydrocracking Mechanism of a Paraffin

(A) Formation of Olefin R-CH2-CH2-CH-CH3 CH3 (B) Formation of Tertiary Carbenium Ion R-CH=CH-CH-CH3 CH3 (C) Isomerization and Cracking + R-CH2-CH2-C-CH3 CH3 (D) Olefin Hydrogenation CH3 CH3 CH3-CH-CH3 Acid + R-CH 2+ CH2= C-CH3 CH3 Acid CH3 R-CH2-CH2-CH-CH3 + Metal CH3 R-CH =CH-CH-CH3

CH2=C-CH3

Metal H2

N-Paraffins Hydrocracking
Adsorption on metal sites Dehydrogenation (olefin forms) Desorption from metal sites and diffusion to acid sites Skeletal isomerization and/or cracking of olefins on acid sites through carbenium ion intermediates Desorption of olefins from acid sites and diffusion to metal sites Hydrogenation of these olefins on metal sites Desorption of resulting olefins

Hydrocracking Reaction Mechanism

H c c H + + c H R 3. Diffusion to acid sites H c c H H c H 2. Olefin formation
H H c R c H

H R c H

H c H

H H

H c R

4. Crack R

H H 5. Hydrogenation H H

R
R

c H

ACID SITE

METAL SITE
1. Dehydrogenation

H R

H c

H c R

c H H

Hydrocracking Science and Technology; Julius Scherzer, A.J. Gruia. \ Organic Chemistry 5th addition TW Graham Solomons.

Effect of Chain Length on Hydrocracking Conversion

100 Degree of Conversion,% 80 60 40 20 0 240 n-Decane n-Nonane n-Octane n-Heptane n-Hexane

280 300 320 340 Temperature, C Influence of reaction temperature on hydrocracking conversion of n-alkanes with different chain length
Figure From: J. Weitkamp, ACS. SYMP.SER. 20,6, (1975)

260

Postulated Hydrocracking Mechanisms

Naphthene cracking Multiring aromatic cracking Dealkylation Isomerization

All proceed through bi-functional mechanism

Heavy PNA Formation & Coking

Raw Feedstocks Contain Precursors Condensation Reactions Large PNAs Formed on Catalyst Surface

HPNAs in Reactor Effluent

Coke Formation

Possible Pathways for Multiring Aromatics

Metal

Acid

Acid R Acid

HYDROCRACKING
TYPICAL HYDROCRACKER FEEDSTOCKS
Naphtha Heavy Vacuum gas oil Thermally or catalytically cracked gas oil

TYPICAL HYDROCRACKER PRODUCTS

Middle distillates(HSD, KERO/ATF) Naphtha LPG

HYDROCRACKING
UNIT CONFIGURATIONS

Once Through Type Single Stage with Recycle Two stage

BENEFITS OF HYDROCRACKING
Middle Distillate yield is 80% as compared to 45% in FCCU Entire feed stock can be converted to the product range i.e. no coke or by products Low Sulphur, Nitrogen and Aromatic content in Products

HYDROCRACKING
HISTORY OF HYDROCRACKING
Initial units came up during World War II for supplying gasoline to Europe & America Initial catalysts used were natural clays & operating pressures were about 250 kg/cm2g Continuous developments in catalyst has resulted in lower pressure operation to produce desired quality products At present more than 150 units are operating in the world.

HYDROCRACKER UNITS OPERATING IN INDIA

SR.NO. 1 2 3 4 5 6 7 8 REFINERY COMPANY IOCL MRPL IOCL MRPL IOCL NRL COMMISSIONING YEAR DECEMBER 1993 JULY 1996 APRIL 1999 NOVEMBER 1999 JULY 2000 NOVEMBER 2000 2004 IOCL DEC 2005

GUJARAT REFINERY MANGLORE REFINERY PANIPAT REFINRY MANGLORE REFINERY MATHURA REFINREY NUMALIGARH REFINERY CPCL PANIPAT REFINERY

PROCESS CHEMISTRY
HYDROTREATING REACTIONS
(Relative) Heat Liberation Olefin Saturation Easiest & Rapid 2 Desulfurisation 1 DeNitrification 1 Aromatic Satrn Most Difficult 1 OTHER Reactions are Demetalisation , Oxygen & Halides Removal Rate of Reaction

PROCESS CHEMISTRY
HYDROCRACKING REACTIONS
Rate of Reaction Easiest

Heteroaromatic Multiring aromatic Monoaromatic Multiring Naphthene Mononaphthene Paraffin

Most Difficult

All the Hydrocracking Reactions are highly exothermic in nature

CATALYST
HYDROTREATING
Metal based catalyst Ni-Mo for higher severity Co-Mo for lower severity

HYDROCRACKING
Bifunctional Silica - Alumina catalyst Acidic sites for cracking reactions Metal sites for hydrogenation, dehydrogenation Two types of hydrocracking catalysts
Amorphous for producing middle distillates Zeolites for producing naphtha, LPG

CATALYST
Catalyst poisons
Temporary
Ammonia Coke

Permanent
Metals

CATALYST IN OHCU & HCU

SL.NO. CATALYST FUNCTION 1 For even disrtibution of catalyst & FeS removal Catalyst TK-10 TK-711 2 3 Metal removal from feed Hydrotreating HC-DM HC-K PR-OHCU Bed Type of loading Qty(MT) R1B1 R1B1 R1B1 Sock Sock Sock 1.5 3.64 3.3 94.051 Catalyst TK-10 TK-711 HC-DM HC-T PREP-HCU Bed Type of loading R1B1 R1B1 R1B1 R1B1,B2,B3 Sock Sock Sock Dense

R1B1,B2, B3 Sock/Dense* R2 B1,B2, R3B1,B2 R3B2

4 5

Hydrocracking Post treatment

HC-22 HC-K

Sock Sock

229.632 6.846

DHC-32 HC-K**

R2B1, B2 V-003

Dense Sock

* One bed is sock loaded & the other two beds are dense loaded. ** Future requirement

REACTOR INTERNALS

IMPORTANT PROCESS VERIABLES

REACTOR TEMPERATURE FEED QUALITY RECYCLE GAS RATE HYDROGEN PARTIAL PRESSURE HYDROGEN PURITY WASH WATER RATE

PREP HCU - FEED QUALITY

HYDROCRACKER BLEND FEED PROPERTIES COMPONENT FLOW RATE FLOW RATE vol % wt % API SPECIFIC GRAVITY TOTAL SULPHUR NITROGEN HYDROGEN estimated CONRADSON CARBON C7 INSOLUBLES C7 asphaltene content BROMINE NUMBER METALS Ni+V Si OTHERS ANILINE POINT POUR POINT UOP K calculated UNIT MT/YEAR m3/hr BLEND calculated 1,700,000 229 100 100 21.2 0.9625 3.29 1800 11.86 0.59 0.05 < 500 2.40 1.0 0.6 0.8 80.2 11.81 C IBP 5% est. 10% 30% est. 50% 70% est. 90% 95% est. EP
O

@15 OC wt % wppm wt % wt % wt % wppm wppm

VGO 1,360,000 184 80.41 80 22 0.9218 3.00 1400 12.02 0.50 < 0.05 0.00 1.0 1.0 82 32 11.88 320 364 390 430 460 485 525 537 570

CGO 340,000 45 19.59 20 18.1 0.9459 4.44 3400 11.22 0.97 < 0.12 12.00 1.0 3.0 73 11.56 317 362 388 425 452 482 528 541 574

O O

C C

ASTM DISTILLATION (D-1160)

315 370 390 429 458 485 525 545 574

PRE HCU
PRODUCT SPECIFICATIONS
PRODUCT LPG PROPERTY Vapour Pres.@ 65 OC Max Vaporisation @2 OC & 760 mmHg Copper Strip Corrosion Reid Vapour Pressure Max Sulphur Content Max Sulphur Content Max Nitrogen Content Max ASTM D86 VOL% 10 / FBP Max Sulphur Content Max Freezing Pt/Flash Pt /Smoke Pt Cetane Number Sulphur Content Max SPEC 16.87 kg/cm2 95% min Not worse than 1 0.4 kg/cm2 (a) 5 ppmw 5 ppmw 1 ppmw 205OC / 300 OC 30 ppmw -51OC/40OC/21mm 56 min 50 ppmw

Light Naphtha Heavy Naphtha Kerosene

HSD

COMPARISON OF OHCU & HCU

NO 1 2 3 4 5 6 7 8 9 10 11 AREA PROCESS CONVERSION FEED QUALITY UNIT CAPACITY (MMTPA) NO.OF REACTORS CATALYST OPERATING CYCLE HYDROTREATING CATALYST HYDROCRACKING CATALYST HIGH PRESSURE SEPARATORS RECYCLE GAS AMINE TREATMENT STRIPPER COLUMN HEAT SOURCE EXISTING HYDROCRACKER ONCE THROUGH 60% VGO 1.5 1.7 3 ON HS VGO ON LS VGO PREP HYDROCRACKER RECYCLE MODE FULL CONVERSION (97%) VGO+Hy COKER GAS OIL 1.7 ON VGO+HCGO 2 24 MONTHS HC-T DHC-32 TWO YES MP STEAM DIRECT INJECTION

18 MONTHS HC-K HC-22 SINGLE NO REBOILER FURNACE

COMPARISON OF OHCU & HCU

NO 12 AREA VACUUM COLUMN AND VACUUM FURNACE POWER RECOVERY TURBINE MUG COMPRESSOR SPILLBACK CONTROL EXISTING HYDROCRACKER YES PREP HYDROCRACKER NO TWO : ONE EACH FOR CHARGE PUMP AND LEAN AMINE PUMP. COMMON ONLY FOR FIRST STAGE AND COMMON FOR ALL COMPRESSORS BACK PRESSURE TYPE ( HP to LP ) DRY GAS SEAL

13

ONE : ON CHARGE PUMP

14

INDIVIDUAL STAGE

15

16

MUG COMPRESSOR FOR EACH STAGE & FOR SUCTION KNOCK OUT EACH COMPRESSOR DRUMS RECYCLE GASCOMPRESSOR (RGC) FULLY CONDENSING (HP STEAM TURBINE STEAM SUPPLY) SEAL OIL SEAL MAKE UP GAS JOINING AT

SUCTION OF RECYCLE GAS DISCHARGE OF RECYCLE COMPRESSOR GAS COMPRESSOR NO

17

BUFFER GAS COMPRESSOR YES

COMPARISON OF OHCU & HCU

YIELD PATTERN (Wt%)
PRODUCT GAS LPG L IG H T N A P H T H A HEAVY NAPHTHA KEROSENE D IE S E L U N C O N V E R T E D O IL / BOTTOM S E X IS T . OHCU 1 .3 7 1 .2 1 2 .1 6 4 .3 1 2 5 .1 1 2 5 .6 4 3 9 .2 PREP HCU 1 .6 1 2 .4 1 1 3 .2 4 3 .3 4 2 3 .9 4 4 8 .7 6 2 .9 5

REACTOR CATALYST LOADING DETAILS

Reactor - 1
Inlet Diffuser

Reactor - 2
Inlet Diffuser

Liquid Distributor Bed 1A Bed 1B Bed 1C Bed 1D Bed 1E 3mm Dia 6mm Dia TK-10, 1.75 m , Sock, 115mm TK-711, 10.58 m , Sock, 680mm HC-DM, 10.58 m , Sock, 680mm HC-DM, 10.58 m , Sock, 680mm HC-T, 13.26 m , Dense, 1140mm Ceramic, Sock, 75 / 75mm
3 3 3 3 3

Liquid Distributor 6mm Dia Ceramic, Sock, 75mm

Bed 1

DHC-32, 96.27 m , Dense, 6415mm

Liquid Distributor 6mm Dia Ceramic, Sock, 75mm

3mm Dia 6mm Dia Ceramic, Sock, 75 / 75mm

Bed 2 3mm Dia 6mm Dia

HC-T, 29.58 m , Dense, 2545mm

Liquid Distributor
Ceramic, Sock, 75 / 75mm

6mm Dia

Ceramic, Sock, 75mm

Liquid Distributor 6mm Dia Ceramic, Sock, 75mm

Bed 3

HC-T, 59.16 m , Dense, 5140mm

Bed 2

DHC-32, 96.27 m , Dense, 6465mm

3mm Dia 6mm Dia Ceramic, Sock, 75 / 75mm Ceramic, Sock, 19mm Dia Outlet Collector

3mm Dia 6mm Dia Ceramic, Sock, 75 / 75mm Ceramic, Sock, 19mm Dia Outlet Collector

REACTOR FACTS & FIGURE

THICKNES S EQ. NO. SERVICE Shell/ head Dia (ID) mm SIZE Leng th (TT) mm OPERATING Press Kg/c m2 g DESIGN Press Kg/cm 2g Wt(Ton) Erec/Ope rating MOC VEND OR

Temp (deg C)

Tem p (deg C) 454

R001

REACTOR 1 HYDROTREATIN G

261/133

445 0

1300 0

431 (max)

174.1

189.5/F V

SA 336 GR F22V + SS 347 WO(Shell) SA 832 GR22V +SS 347 WO(Head)

KOBE Steel, JAPA N

584/920.9

R002

REACTOR 2 HYDROCRACKI NG

256/130

445 0

1340 0

429 (max)

171

454

186/FV

SA 336 GR F22V + SS 347 WO (Shell) SA 832 GR22V +SS 347 WO (Head)

KOBE Steel, JAPA N

588/942.2

V003

HOT SEPARATOR/ REACTOR(Futur e)

204/105

410 0

8200 271( max)

164.5

400

169/FV

SA 336 GR F22V (Shell) SA 832 GR22V (Head)

KOBE Steel, JAPA N

282/341.7

REACTOR CATALYST LOADING DETAILS

Reactor - 1
Inlet Diffuser

Reactor - 2
Inlet Diffuser

Liquid Distributor Bed 1A Bed 1B Bed 1C Bed 1D Bed 1E 3mm Dia 6mm Dia TK-10, 1.75 m , Sock, 115mm TK-711, 10.58 m , Sock, 680mm HC-DM, 10.58 m , Sock, 680mm HC-DM, 10.58 m , Sock, 680mm HC-T, 13.26 m , Dense, 1140mm Ceramic, Sock, 75 / 75mm
3 3 3 3 3

Liquid Distributor 6mm Dia Ceramic, Sock, 75mm

Bed 1

DHC-32, 96.27 m , Dense, 6415mm

Liquid Distributor 6mm Dia Ceramic, Sock, 75mm

3mm Dia 6mm Dia Ceramic, Sock, 75 / 75mm

Bed 2 3mm Dia 6mm Dia

HC-T, 29.58 m , Dense, 2545mm

Liquid Distributor
Ceramic, Sock, 75 / 75mm

6mm Dia

Ceramic, Sock, 75mm

Liquid Distributor 6mm Dia Ceramic, Sock, 75mm

Bed 3

HC-T, 59.16 m , Dense, 5140mm

Bed 2

DHC-32, 96.27 m , Dense, 6465mm

3mm Dia 6mm Dia Ceramic, Sock, 75 / 75mm Ceramic, Sock, 19mm Dia Outlet Collector

3mm Dia 6mm Dia Ceramic, Sock, 75 / 75mm Ceramic, Sock, 19mm Dia Outlet Collector

Units Reaction Philosophy

A. B. HydroTreating HydroCracking Metal-Catalysed Acid-Catalysed-cumMetal-Catalysed Co-Mo / Ni-Mo Catalyst Low Zeolite with Metals

HT Reactions: Rate of Reacn (Rel) Heat Librn/ H2 consu Olefin Saturation Easiest & Rapid 2 Desulfurisation 1 DeNitrification 1 Aromatic Satrn Most Difficult 1 OTHER Reactions are Demetalisation , Oxygen & Halides Removal HC Reactions: Rate of Reacn Heteroaromatic Easiest Multiring aromatic Monoaromatic Multiring Naphthene Mononaphthene Paraffin Most Difficult Net Exothermic in nature followed by Hydrogenation reactions for Saturation of cracked unsaturated molecules

Introduction: PREP UOPs HCU

Unit Design Capacity 1.7 MMTPA [212.5 TPH Fresh Feed] UOP , USA EIL , INDIA DICL , KOREA Toyo , Japan Punj Lloyd , Petron , others

Licensor PMC LSTK Contractor Main Sub-contractor Construction Agencies involved

DCS Implementation (on Conventional Mode) PMC DCS PLC Vibrn Monitoring EIL , INDIA YIL , INDIA Triconex , USA Bently Nevada , USA

Major Equipments & Vendors

R 001, R 002, V 003 KOBE STEEL, Japan Heaters (F 001 & F 101) Petron [designed by EIL] HP B-L HE (20 nos) IMB, Italy [designed by ABB HT] Feed Filter ( 6 x12 cartridges) Ronnigen Peter , USA All AFCs GEI HAMON Industries Ltd, Bhopal MUG Compressor (K2A/B/C) THOMASSEN C S,
(each @ 50% of Normal Process Load, with single common Spillback)

Motor (each 4.7 MW) RGC with HP LP Turbine

(DG Seal by Burgman)

ASI Robicon, BHEL(4448 kW, 11670 max cont rpm) EBARA, Japan Toshiba, Japan PERONI POMPE SpA, Italy KSB

Feed & Amine Pumps & PRTs Feed / Amine Motors (3.7/1.55 MW) Wash Water Pump PF Bottom Pump

Salient Features of the Unit

Single Stage Distillate Unicracker [HSD mode, along with LPG maxn] Liquid Recycle with Full Conversion [Design Conversion = 97 wt% on FF] Designed for High S & High N content feedstocks Designed to process 20 wt% HCGO in combined FRESH FEED MPT of REACTOR 38 oC Low & High Rate Depressurization levels of 7 & 21 Kg/cm2 Employs Hot HP Separator & RG H2S Absorber (using DEA or MDEA), and deletion of Vacuum Tower [features differing from existing OHCU] Liquid phase Catalyst Sulfiding procedure 2 yrs min operating cycle between Cat Regen Unit Turndown ratio being 50% of Design Capacity Unit tripping based on high reactor skin/ bed temp. (454 C)

Design Feed Characteristic

Design based on following Feedstocks A. 100% KEC B. 50:50 :: AL:AH AMC 80:20 :: VGO:HCGO 42:30:20:8 :: LVGO:HVGO:HCGO:HGO

Both Feedstocks bearing similar characteristics S content Total N Broad TBP cut Metals [Ni+V / Total] CCR C7 insolubles wt% ppmw oC ppmw wt% wt% 3.3 1800 370 550 1.0 / 2.0 (max) 0.5 (VGO) / 1.0 (HCGO) 0.05 (VGO) / 0.12 (HCGO)

Product Characteristics
LPG Vap Pr @ 67oC Vaprsn @ 2oC, 760 mmHG Cu Strip Cor (1 hr @38oC) LN HN Kero / ATF S RVP S S kV @ -20oC Color (Saybolt) Freez / Flash / Smoke pt HCU Blended HSD Pool [Total HSD + Total HN + part Kero] Cetane no (SOR & EOR) S Flash (min) // Pour (max) kV @ 40oC D86 85/95 LV% UCO Bleed S 16.87 kg/cm2g 95 LV% (min) Not worse than No. 1 5 ppmw (max) 0.4 kg/cm2A (max) 5 ppmw (max) 30 ppmw (max) 8 cSt (max) 20 (min) -51oC / 40oC / 21mm(min) 56 (min) EURO IV 50 ppmw (max) 36oC // 15/0 oC S/W 2-5 cSt 350 / 370 oC (max) 50 ppmw (max)

* UOP to provide Pdt Yield for meeting envisaged 340 oC (max) @ 95 LV% as per EURO IV

Product Yield Pattern , WT% on ( Fresh Feed + MU H2 )

Streams SOR EOR

FF+MU H2 rate, T/h S Ab + DeE offgas CFD offgas OFFGASES LPG DeB Naph PF LN NAPHTHA PF HN Kero/ATF KERO/ATF HSD HCU DIESEL POOL * UCO Bleed
Balance (H2S + others)
* Total HSD + Total HN + Part KERO

212.5 + 6.4 0.63 1.40 2.03 2.41 5.66 7.58 13.24 3.34 23.94 19.15 48.76 56.89 2.94 3.34

212.5 + 6.4 0.67 1.52 2.19 3.05 6.97 8.26 15. 23 3.49 23.74 18.99 46.00 54.24 2.94 3.35

MU H2 @ 6,366 kg/h (or 68,406 NM3/h)

Catalyst Specifications
Reactors
Rx- 1 (75-R-001) BED-1 TK-10, TK-711 TK-10, TK-711 HC-DM (1/10) HC-DM (1/16) HC-T BED-2 BED-3 Total Catalyst Rx- 2 (75-R-002) BED-1 BED-2 Total Catalyst Rx- 3 (75-V-003) Future BED HC-K Sock 15.25 DHC-32 DHC-32 Dense Dense 96.27 96.27 192.54 185020 DHC-32 HC-T HC-T Sock Sock Sock Sock Dense Dense Dense 1.75 10.58 10.58 10.58 13.26 29.58 59.16 135.49 91815 HC-T TK-10 HC-DM 11215 1410 TK-711 5250

Catalyst Type

Loading Method

Catalyst Volume, M3 Weight, Kg

Rx Secn PFD
127.5

VGO CGO
[Ratio Control]

42.5

FG B/W Surge drum

N2 [Split range]
3.5 kg

155.3 @ 177 C

Hot ex Units
42.5

Cold ex Strg
80 C

Liq Recycle 150 C

Feed Surge drum

Feed Filter
162 C 5 kg

SM 150 C Coalescer Slop FCC

P 001 A/B

HS HFD
367.8 T/h 197 kg F 001 38 T/h R 001/002 Design Temp = 454 oC R 001/002 Design Pr = 189.5 / 186 kg/cm2g 413 C, 173.3 KG 387 C 172.1 kg R 001 419 C, 170.2 KG 399 C 169.1 kg R 002

DCU

PRT P 002

RG ex E 001
235 C 319 C

177.5 kg 337 C

RG Heater

452 C

9.3 T/h

5.8 T/h RG-Q

E 004
TC C/V E 005 A/B/C 264 C E 003 A/B/C

E 002
366 C

RG-Q 9.7 T/h

434 T/h @ 271 C

Total Rx RG-Q 28.2 T/h @ 64 C 325 C 341 C 400 C 409 C

3.4 T/h RG-Q

RG-Q
405 C 169.3 kg 409 C 162.2 kg

To HS
31.35 DUTY 24.37 DUTY 10.52 DUTY

430 C, 170.4 KG

428 C, 162.8 KG

RG Loop PFD
RG to F 001, E 005 A/B/C 73 T/h To Stripper 177 C 74 C Rx eff ex E 005 A/B/C 157.3 kg E 001 A/B HS E 009 MUG 105 C 6.4 T/h 28.2 T/h Rx Quench 64 C, 179 kg RGC 60 T/h Bleed

Spillback
16 T/h @ 66 C EA 001 A-H 172 C 146 C 23.82 DUTY 235 C RG to E 004 E 002 F 001 55 C 154.7 kg CW E 006 CS 42 C LC LC RG Scrub KOD P 113 A/B Wash water injn

DV

RGC KOD

201 C

45 C * 153.7 kg

19 T/h

RG Scrub

226.5 T/h

PRT

LC 32 kg

EA 002

53 C

*
51 C 31.6 kg To DHDT LC CFD PRT P 004 RA to ARU 52 C LC HSS S/R LSS To SWS 17.4 T/h LA ex ARU MUG Spillback C/V LC N2 [Split range] 2 kg BFW 40 C 45 C LA Surge drum P 003 A/B

269 C

HFD Bleed FRC LC

CS PRC MUG 1st Suc PRC

To Stripper 291 T/h

Bleed C/V

LER PFD
2.7 T/h 126 C, 9.5 kg CorInh CW 174 C Ex CFD 20 T/h ExHFD 268 C 17 T/h SM @ 3.6 T/h 346 T/h To PF 16.9 kg 0.17 T/h Sweet FG 29.2 kg 194 C 246 C Naphtha r/d @ 29 T/h CW 64 C 29.9 kg CW 16.6 T/h PF LN 161 C 5.43 T/h 41 C 113 C 185 C 0.66 T/h 40 C 110 C Sand Filter LPG Caustic wash 49 C CW LPG 5.27 T/h 40 C, 20 kg r/d 10 Beo Caustic To & Fro RA to ARU LPG W/w 2 T/h Unstab Naph Stab Naph 12.4 T/h Mixer LPG 5.94T/h 33.3 kg STR 41 C 8.5 kg SAb SW CW 55 C, 31 T/h HSD r/d 160 C DeB 198 C UCO 28 T/h SW 8.8 kg 41 C 48 C Sour FG 1.2 T/h toDHDT 46 C, 29 T/h 0.45 T/h 17.6 kg 81 C 18.3 kg CW 41 C

98 C DeE SW

ex LA Surge drum 45 C 20 T/h

LPG Amine Abs

RA

DMW

PF Circuits
285 C To F 101 PF BOT PUMP 359 C, 14 kg E 104 P 105 A/B B 213 C KERO STR RBLR 278 C 258 C B 198 C DeB RBLR 225 C B SL CW 80 C 80 C 6.4 T/h UCO Bleed

246 C PF FEED SM 9.4 T/h

208 C

194 C

BFW 177 C

155.3 T/h Liq Recycle Oil

148 T/h IR 270 C, 4.6 kg

SL 8 T/h

BFW

EA 111 7.3 T/h HN R/D

228 C

191 C

178 C

HSD PA 170 T/h

HN R/D 164 C, 9 kg

CW

169 C HSD PA P 106 A/B 243 C, 11 kg B HSD R/D P 111 A/B STR = SL @ 3.3 t/h VAP RTN 261 C 165 C 214 C 160 C 189 C B P 110 A/B DMW 65 C CW 45 C Coalescer 107 T/h

HN to HSD @ 7.3 T/h HSD RD 124.5 T/h

HN STR RBLR 164 C

DeB FEED 81 C @ 48 T/h 206 C, 8 kg 65 C CW 52.4 T/h

KERO to HSD @ 10.5 T/h KERO RD 42 T/h

KERO RD F 101 33.82 DUTY PF TOP 120 C, 1.055 kg/cm2G TOP REFLUX @ 192 T/h @ 83 C REFLUX PR @ 0.35 kg/cm2G by FG Split range Controller PF Bottom STR SL @ 7.2 T/h P 108 A/B IR 234 T/h P 107 A/B VAP RTN 195 C

181 C, 6 kg

121 C

HN REFLUX @ 214 T/h @ 145 C KERO PA 256 T/h To HGU VAP RTN 157 C

KERO PA

Major Optg Parameters to Monitor

HCGO ratio in Combined Fresh Feed Combined Fresh Feed C7 Insolubles , Total Metals , Total N Each Rx Temperature values , Bed Ts , Rx Ps , Beds Radial Temp gradient [WABT for monitoring Cat Deactivation rate] Gas-to-Oil ratio of each Rx R 001 effluent N2 content H2 Partial Pressure at Cold Separator Wash water injection rate Monitoring Ammonium Bisulfide content in HP secn Sour water Recycle Gas H2 Purity Combined Feed Ratio & Conversion & Yield Pattern LP section Typical optg & QC aspects

Important Data of the Unit:

RG before H2S Absorber RGC normal Process Load RG MW / H2S Wash water injection rate Lean Amine to RG Scrubr Lean Amine to LPG Wash LA / RA H2S load CFR - FF - LR Combined Feed UCO Bleed CPP = = = = = = = 8.32 wt% = 59,900 kg/h (or 3,70,841 NM3/h) = 3.62 / Nil = 18 T/h , and HP Sour Water NH3 / H2S load = 2.61 / 5.38 wt% = 226.5 T/h (DEA) = 19.7 T/h (DEA) = 0.24 / 2.60 wt%

1.8 [This helps towards LOW TEMP OPRN & Higher HSD Selectivity] 212.5 T/h 155.3 T/h 367.8 T/h 3 wt% on FF rate 56 wt%

H2 Ppr at oulet of CS (as per PPkg data) = 144.2 kg/cm2G [CS Pr = 154.7 kg/cm2G] H2 Ppr at inlet of E001 A/B (ie. the H2 online analyser location) = 170.9 kg/cm2g Gas-to-Oil ratio at the Inlets of R 001 & R 002 = 640 & 976 NM3/M3 , resp R 002 each BED avg Temp rise (ie. T) should not exceed 28 oC R 002 each BED max Temp rise (ie. T) should not exceed 33 oC R 001 each BED max Temp rise (ie. T) should not exceed 42 oC In R 001 or R 002 , IF any Temp pt exceeds its normal level by 28 oC OR, exceeds Rxs Design Temp level, THEN Depressuring of the system is to be done @ 21 kg/cm2/min

Energy saving features like Power generation to the tune of nearly 1630 kW in two numbers of Power Recovery Turbines. Pre heating DM water by using some of the hot streams, thus avoiding extra cooling by air and water. Collection and Recovery System for Steam Traps Condensate . Using MP steam as the reboiling medium for the Stripper column instead of a dedicated furnace. Designed to utilize stripped sour water and fractionator o/h boot water as wash water. Common stack and APH for two numbers of furnaces viz.,. Recycle Gas Furnace and Product Fractionator Feed Heater. Designed to handle DEA (Di Ethanol Amine) but in place of DEA presently MDEA(Methyl Di Ethanol Amine )is being used for scrubbing of LPG, Offgases and the Recycle Gas. Use of dedicated Pump gland Cooling Water System for cooling of glands, bearings and bridle for Pumps and Compressors, in place of cooling water. The return water from these Pumps and Compressors are routed back to cooling water return header.

Thank You