HydrocrackingFundamentals & 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

3

IndianOil

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

6

2.4

12

7.5

0

2

4

6

8

10

12

2000 2005

REFINERY CAPACITY, MMTPA

HYDROPROCESSING CAP, MMTPA

53

200

0

20

40

60

80

100

120

140

160

180

200

2000 2005

HYDROGEN, KNm3/hr

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

LowLowHighProduct Quality

LowHighLowNaphtha

YesYesNoPost treatment of

products

LowLowHighCapital, Maint Cost

NoNoYesATF

ModerateModerateHighMiddle Distillates

LowLowHighOp. Press.

Thermal crackingFCCHydrocracking

Process Chemistry

• Crude Oil Properties

• Hydrotreating

Crude Oil Composition

• Various colors

• Various

contaminant

levels

• Various

flowing

properties

Crude Oil Composition

wt%• Carbon 84-87

• Hydrogen 11-14

• Sulfur 0.1-2.0

• Nitrogen 0.01-0.2

• Metals 0.0-0.1

Crude Oil Composition

• Paraffins

• Naphthenes

• Aromatics

Paraffins

(Alkanes)• 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

H

H

H

H

Hc

c

c

H

H

cHH

HH

Hc

c

H

HH

H

Ethane C2H8

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

H

H

cc

c c

HccH

H

H

cyclo-hexane

H

H

H

H

H

H

H

Hc

cc

c c

HH

H

H

H

cH

H

Olefins

(Alkenes)• 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

H

Hcc

c

c

H

H

H

HH

Butene

C4H8

H

H

HH

c

c

c

H

c

c

H

H

H

Pentadiene C5H8

Aromatics• Cyclo-alkene

– Base is benzene ring

• Can have sub groups

– Methyl, Ethyl

• Unsaturated

– Lacking hydrogen due to 3 double

bonds per ring

• PNA’s

– Polynuclear aromatics

– Two or more benzene rings

H

H

H

cc

c c

Hcc

H

H

H

cc

c cH

polynucleararomaticPNA

H

H

cc

c c

Hcc

H

H

H

Benzene (aromatic)

H

H

cc

c c

Hcc

H

H

H

cH

H

Toluene

Basic Nitrogen

Pyridine Quinoline Phenanthridine

N N

N

Indole Carbazole

Non-Basic

N H N H

Amine

N H2CH

3

Nitrogen Compounds in

Petroleum

Sulfur Distribution

0

1

2

3

4

5

6

7

Su

lfu

r, W

t%

<350°C 350-450°C 450-550°C >550°C

Distillation Range

CatCanyon

Arabian Hvy.

SJV Hvy

• Sulfur exists throughout the boiling range of petroleum, except the lightest

fractions

• Sulfur concentration increases with increased boiling range

SCH

3

CH3

S

SS

CH3

SHCH3

S

CH3

CH3

S

Thiophene Benzothiophene

Substituted Benzothiophene Dibenzothiophene

Mercaptan Disulfide

Sulfur Compounds in Petroleum

Nitrogen Distribution-Hondo Crude (California Offshore)

� Nitrogen rises as boiling range increases

0

0.3

0.6

0.9

1.2

1.5

Nit

rog

en, W

t%

<315°C 315-370°C 370-425°C 425-480°C 480-535°C >535°C

Distillation Range

Basic Nitrogen

Pyridine Quinoline Phenanthridine

N N

N

Indole Carbazole

Non-Basic

N H N H

Amine

N H2CH

3

Nitrogen Compounds in

Petroleum

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 ChemistryDesulfurization

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

• Oxygen removal

Easiest

Hardest

Hydrotreating

• Approximate relative heats of reaction

(per kg or lb)

– Olefin Saturation 100

– Desulfurization 20

– Denitrogenation 2

Treating By-Products

• Organic Sulfur

H2S

• Organic Nitrogen

NH3

• Oxygen compounds

H2O

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

S

HC-CH+2H

2H

2C=CH-CH=CH

2 + H

2S

(B) Olefin Saturation

H2C=CH-CH=CH

2 + 2H

2H

3C -CH

2 -CH

2-CH

3

HDS Reactions

S

Heptanethiol Heptane

+2H2

Butadiene

S

Thiophene

H + H2S

Butylpropyl Sulfide Butane Propane

+2H2

+ H2S

+ CH4

+ H2S

CH3+2H

2

Methylphenyl Sulfide Benzene Methane

+H2

+

S

S

+ H2S

Reaction Rate Equation

for Desulfurization• At high conversion levels, desulfurization

reactions follow first-order kinetics

• The rate constant for “easy” sulfur-

containing

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

CH3CH

2SCH

3CH

2+ 2H

2

Diethylsulfide (B.P. 92°C)

Thiophene (B.P. 84°C)

Benzthiophene (B.P. 221°C)

Dibenzthiophene (B.P. 315°C(est.))

2C2H

6 + H

2S

+ H2S 5

15

14

Approx. Factor of Difficulty

Base = 1

+ H2S

+ H2S

+ 2H2

S

+ 2H2S

+ 2H2S

Nitrogen Removal

Amine C-C-C-C-NH

H+ H

2C-C-C-C + NH

3

PyridineC

N

+ 5H2

C

C

C

C C-C-C-C-C (and C-C-C-C-) + NH3

C

Pyrrole

C C

NCC + 4H

2C-C-C-C (and C-C-C) + NH

3

C

QuinolineC

C

+ 4H2

C

C

C

CC

N

C

C

CC

C-C-C-C + NH3

CC

C

C

Nitrogen Distribution

in Middle-Eastern Crudes� Nitrogen concentrates in the

heavier portions of a 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

Arabian Hvy

50 55 60 65 70

2000

1500

1000

500

0

Mid. wt-% on Crude

Dubai Crude

Mid. wt-% on Crude50 60 70 80 90

6000

5000

4000

3000

2000

1000

0

Kuwait Crude

Mid. wt-% on Crude

1500

1200

900

600

300

050 55 60 65 70

Murban Crude

Mid. wt-% on Crude

1200

1000

800

600

400

200

065 70 75 80 85 90

Postulated HDN Mechanism

(A) Aromatic Hydrogenation

(B) Hydrogenolysis

(C) Denitrogenation

+ H2

CH3-CH

2-CH

2-CH

2-CH

2-NH

2

CH3-CH

2-CH

2-CH

2-CH

2-NH

2 + H

2CH

3-CH

2-CH

2-CH

2-CH

3+NH

3

+ 3H2

CH

N

CHHC

HC CH

CH2

N

CH2H2C

H2C CH2

CH2

N

CH2H2C

H2C CH2

Thermodynamic Effects on HDN Reactions

H2

+ NH3

“A”

� HDN proceeds through aromatic saturation

� 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

N N

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 n-Heptane

+H2

Cyclohexene Cyclohexane

+H2

3-Ethyl-2-Pentene 3-Ethylpentane

Typical Aromatics Saturation Reactions

+ 3H2

+ 2H2

+ 3H2

Tetralin

(Tetrahydronaphthalene)

Decalin

(Decahydronaphthalene)

CH3

Methylcyclohexane

Naphthalene

Tetralin

CH3

Toluene

Thermodynamic Equilibrium forAromatics Saturation

Keq Cyclohexane

C

C

C

C CH2

CH2

H2

H2

H2

H2

+ 3H2

Benzene

Keq

150

205

260

315

370

2 x 106

• At 1 ATM H2, equilibrium favors benzene at temperatures >315°C (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 400°C (750 oF)

2200

7.1

0.14

0.063

Temperature, °C

Aromatic Saturation

Temperature Effect

TemperatureTemperature

Aro

ma

tic

Aro

ma

tic

Sa

tura

tio

nS

atu

ratio

n

Metals Removal

Organo-Metallic

CompoundsAdsorption

Reaction(Metal + Catalyst) + Hydrocarbon

Catalyst

Pill

Pore

Halides Removal

+ H2

C

C

C

C

C-C-C-C-Cl

C

C

C

C

C

C-C-C-C

CHCl +

HCl + NH3

NH4Cl

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

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

employing amorphous catalyst

Feed Hydrogen

Products Hydrogen

+ 6H2

H2S +

+ 7H2

NH3

+

+ H2

+ RH

R

R

+ 2H2

+ 3H2

+ 3H2

R R

R+ H

2+ RH

R

R + H2

R1H + R

2H

+ H2

+ C2H

6

CnH

2n+2+ H

2C

aH

2a+2+ C

bH

2b+2

S

N

Treating Reactions

Polyaromatics Hydrogenation

Monoaromatics Hydrogenation

Hydrodealkyalation

Hydrodecyclization

Hydrocracking

Hydroisomerization

CH2

- CH2

- R2

R1

- CH2

- CH2

- R2

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

(D) Olefin Hydrogenation

CH2=C-CH3

CH3

H2

MetalCH

3-CH-CH

3

CH3

(C) Isomerization and Cracking

R-CH2-CH

2-C-CH

3

CH3

CH3

R-CH 2+ CH

2= C-CH

3

Acid ++

(B) Formation of Tertiary Carbenium Ion

R-CH=CH-CH-CH3

CH3

CH3

AcidR-CH

2-CH

2-CH-CH

3+

(A) Formation of Olefin

R-CH2-CH

2-CH-CH

3

CH3

CH3

MetalR-CH =CH-CH-CH

3

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

ACID SITE METAL SITE

1.Dehydrogenation

2. Olefin

HH

formation

Hc

c

c

H

R

R H

H

acid sites3. Diffusion to

R

c

c

H

H

c

H

R

H

H

H

Hc

c

cH

R

R H

H

4. Crack

H

R

c

H

c+

H

c

RH

+

5. Hydrogenation

H

HR

cH

c

H

H

H

H

c

R

H

HH

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

0

340320300280260240

100

80

60

40

20

n-Decanen-Nonane

n-Heptanen-Octane

n-Hexane

Influence of reaction temperature on hydrocrackingconversion of n-alkanes with different chain length

Figure From: J. Weitkamp, ACS. SYMP.SER. 20,6, (1975)

Temperature, °C

Effect of Chain Length on Hydrocracking Conversion

Deg

ree

of

Co

nv

ersi

on

,%

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

AcidMetal

Acid

RAcid

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. REFINERY COMPANY COMMISSIONING

YEAR

1 GUJARAT REFINERY IOCL DECEMBER 1993

2 MANGLORE REFINERY MRPL JULY 1996

3 PANIPAT REFINRY IOCL APRIL 1999

4 MANGLORE REFINERY MRPL NOVEMBER 1999

5 MATHURA REFINREY IOCL JULY 2000

6 NUMALIGARH REFINERY NRL NOVEMBER 2000

7 CPCL 2004

8 PANIPAT REFINERY IOCL DEC 2005

PROCESS CHEMISTRY

HYDROTREATING REACTIONS

Rate of Reaction (Relative) Heat Liberation

Olefin Saturation Easiest & Rapid 2

Desulfurisation 1

DeNitrification 1

Aromatic Satrn Most Difficult 1

OTHER Reactions are Demetalisation , Oxygen & Halides Removal

PROCESS CHEMISTRY

HYDROCRACKING REACTIONS

Rate of Reaction

Heteroaromatic Easiest

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

Catalyst Bed Type of loading Qty(MT) Catalyst Bed Type of loading

1For even disrtibution of

catalyst & FeS removalTK-10 R1B1 Sock 1.5 TK-10 R1B1 Sock

TK-711 R1B1 Sock 3.64 TK-711 R1B1 Sock

2 Metal removal from feed HC-DM R1B1 Sock 3.3 HC-DM R1B1 Sock

3 Hydrotreating HC-K R1B1,B2, B3 Sock/Dense* 94.051 HC-T R1B1,B2,B3 Dense

4 Hydrocracking HC-22

R2 B1,B2,

R3B1,B2 Sock 229.632 DHC-32 R2B1, B2 Dense

5 Post treatment HC-K R3B2 Sock 6.846 HC-K** V-003 Sock

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

** Future requirement

PR-OHCU PREP-HCU CATALYST FUNCTIONSL.NO.

REACTOR INTERNALS

IMPORTANT PROCESS VERIABLES

� REACTOR TEMPERATURE

� FEED QUALITY

� RECYCLE GAS RATE

� HYDROGEN PARTIAL PRESSURE

� HYDROGEN PURITY

� WASH WATER RATE

PREP HCU - FEED QUALITYCOMPONENT UNIT BLEND calculated VGO CGO

FLOW RATE MT/YEAR 1,700,000 1,360,000 340,000

FLOW RATE m3/hr 229 184 45

vol % 100 80.41 19.59

wt % 100 80 20

API 21.2 22 18.1

SPECIFIC GRAVITY @15 OC 0.9625 0.9218 0.9459

TOTAL SULPHUR wt % 3.29 3.00 4.44

NITROGEN wppm 1800 1400 3400

HYDROGEN estimated wt % 11.86 12.02 11.22

CONRADSON CARBON wt % 0.59 0.50 0.97

C7 INSOLUBLES wt % 0.05 < 0.05 < 0.12

C7 asphaltene content wppm < 500

BROMINE NUMBER 2.40 0.00 12.00

METALS wppm

Ni+V 1.0 1.0 1.0

Si 0.6 3.0

OTHERS 0.8 1.0

ANILINE POINT OC 80.2 82 73

POUR POINT OC 32

UOP K calculated 11.81 11.88 11.56OC

IBP 315 320 317

5% est. 370 364 362

10% 390 390 388

30% est. 429 430 425

50% 458 460 452

70% est. 485 485 482

90% 525 525 528

95% est. 545 537 541

EP 574 570 574

HYDROCRACKER BLEND FEED PROPERTIES

ASTM DISTILLATION (D-1160)

PRE HCU

PRODUCT SPECIFICATIONS

PRODUCT PROPERTY SPEC

Vapour Pres.@ 65 OC Max 16.87 kg/cm2

Vaporisation @2 OC & 760 mmHg 95% min

Copper Strip Corrosion Not worse than 1

Reid Vapour Pressure Max 0.4 kg/cm2 (a)

Sulphur Content Max 5 ppmw

Sulphur Content Max 5 ppmw

Nitrogen Content Max 1 ppmw

ASTM D86 VOL% 10 / FBP Max 205OC / 300 OC

Sulphur Content Max 30 ppmw

Freezing Pt/Flash Pt /Smoke Pt -51OC/40OC/21mm

Cetane Number 56 min

Sulphur Content Max 50 ppmwHSD

LPG

Light Naphtha

Heavy Naphtha

Kerosene

COMPARISON OF OHCU & HCU

NOEXISTING

HYDROCRACKER

PREP

HYDROCRACKER

1 ONCE THROUGH RECYCLE MODE

2 60%FULL CONVERSION

(97%)

3 VGO VGO+Hy COKER GAS OIL

1.5 ON HS VGO

1.7 ON LS VGO

5 3 2

6 18 MONTHS 24 MONTHS

7 HC-K HC-T

8 HC-22 DHC-32

9 SINGLE TWO

10 NO YES

11 REBOILER FURNACEMP STEAM DIRECT

INJECTION

AREA

PROCESS

CONVERSION

FEED QUALITY

4UNIT CAPACITY

(MMTPA) 1.7 ON VGO+HCGO

NO.OF REACTORS

CATALYST OPERATING

CYCLE

HYDROTREATING

CATALYST HYDROCRACKING

CATALYST

HIGH PRESSURE

SEPARATORS

RECYCLE GAS AMINE

TREATMENT

STRIPPER COLUMN HEAT

SOURCE

COMPARISON OF OHCU & HCU

NOEXISTING

HYDROCRACKERPREP HYDROCRACKER

12 YES NO

13 ONE : ON CHARGE PUMP

TWO : ONE EACH FOR

CHARGE PUMP AND LEAN

AMINE PUMP.

14 INDIVIDUAL STAGE COMMON

15FOR EACH STAGE & FOR

EACH COMPRESSOR

ONLY FOR FIRST STAGE

AND COMMON FOR ALL

COMPRESSORS

FULLY CONDENSING (HP

STEAM SUPPLY)

BACK PRESSURE TYPE ( HP

to LP )

OIL SEAL DRY GAS SEAL

SUCTION OF RECYCLE GAS

COMPRESSOR

DISCHARGE OF RECYCLE

GAS COMPRESSOR

17 YES NOBUFFER GAS COMPRESSOR

RECYCLE GASCOMPRESSOR (RGC)

SEAL

MAKE UP GAS JOINING AT

POWER RECOVERY

TURBINE

MUG COMPRESSOR

SPILLBACK CONTROL

MUG COMPRESSOR

SUCTION KNOCK OUT

DRUMS

STEAM TURBINE

VACUUM COLUMN AND

VACUUM FURNACE

16

AREA

COMPARISON OF OHCU & HCU

YIELD PATTERN (Wt%)

P R O D U C T E X I S T . O H C U

P R E P H C U

G A S 1 .3 7 1 .6 1

L P G 1 .2 1 2 .4 1

L IG H T N A P H T H A 2 .1 6 1 3 .2 4

H E A V Y N A P H T H A 4 .3 1 3 .3 4

K E R O S E N E 2 5 .1 1 2 3 .9 4

D IE S E L 2 5 .6 4 4 8 .7 6

U N C O N V E R T E D O IL / B O T T O M S

3 9 .2 2 .9 5

REACTOR CATALYST LOADING

DETAILS

Reactor - 1

TK-10, 1.75 m3, Sock, 115mm

TK-711, 10.58 m3, Sock, 680mm

HC-DM, 10.58 m3, Sock, 680mm

HC-DM, 10.58 m3, Sock, 680mm

HC-T, 13.26 m3, Dense, 1140mm

Ceramic, Sock, 75 / 75mm

Bed 1A

Bed 1B

Bed 1C

Bed 1D

Bed 1E

3mm Dia

6mm Dia

HC-T, 59.16 m3, Dense, 5140mm

Ceramic, Sock, 75mm

Ceramic, Sock, 75 / 75mm

6mm Dia

3mm Dia

6mm Dia

Ceramic, Sock, 75 / 75mm

3mm Dia

6mm Dia

6mm Dia

HC-T, 29.58 m3, Dense, 2545mm

Ceramic, Sock, 75mm

Ceramic, Sock, 19mm Dia

Inlet Diffuser

Liquid Distributor

Bed 2

Bed 3

Outlet Collector

Liquid Distributor

Liquid Distributor

Reactor - 2

DHC-32, 96.27 m3, Dense, 6415mm

Ceramic, Sock, 75 / 75mm

Bed 1

3mm Dia

6mm Dia

Ceramic, Sock, 75 / 75mm

3mm Dia

6mm Dia

Ceramic, Sock, 75mm6mm Dia

Ceramic, Sock, 19mm Dia

Inlet Diffuser

Liquid Distributor

Bed 2

Outlet Collector

DHC-32, 96.27 m3, Dense, 6465mm

6mm Dia Ceramic, Sock, 75mm

Liquid Distributor

REACTOR FACTS & FIGURE

282/341.7KOBE Steel, JAPA

N

SA 336 GR F22V (Shell)

SA 832 GR22V

(Head)

169/FV400164.5271(max)

82004100

204/105HOT SEPARATOR/ REACTOR(Future)

V-003

588/942.2KOBE Steel, JAPA

N

SA 336 GR F22V + SS 347

WO (Shell)

SA 832 GR22V +SS 347 WO

(Head)

186/FV454171429 (max)

13400

4450

256/130REACTOR 2 HYDROCRACKING

R-002

584/920.9KOBE Steel,

JAPAN

SA 336 GR F22V + SS 347

WO(Shell)

SA 832 GR22V +SS 347

WO(Head)

189.5/FV

454174.1431 (max)

13000

4450

261/133REACTOR 1 HYDROTREATIN

G

R-001

Press

Kg/cm2 g

Temp

(deg C)

Press

Kg/cm2 g

Temp (deg C)

Leng

th (TT) mm

Dia

(ID) mm

Shell/

head

Wt(Ton) Erec/Ope

rating

VENDOR

MOC

DESIGNOPERATINGSIZE THICKNESS

SERVICEEQ. NO.

REACTOR CATALYST LOADING

DETAILS

Reactor - 1

TK-10, 1.75 m3, Sock, 115mm

TK-711, 10.58 m3, Sock, 680mm

HC-DM, 10.58 m3, Sock, 680mm

HC-DM, 10.58 m3, Sock, 680mm

HC-T, 13.26 m3, Dense, 1140mm

Ceramic, Sock, 75 / 75mm

Bed 1A

Bed 1B

Bed 1C

Bed 1D

Bed 1E

3mm Dia

6mm Dia

HC-T, 59.16 m3, Dense, 5140mm

Ceramic, Sock, 75mm

Ceramic, Sock, 75 / 75mm

6mm Dia

3mm Dia

6mm Dia

Ceramic, Sock, 75 / 75mm

3mm Dia

6mm Dia

6mm Dia

HC-T, 29.58 m3, Dense, 2545mm

Ceramic, Sock, 75mm

Ceramic, Sock, 19mm Dia

Inlet Diffuser

Liquid Distributor

Bed 2

Bed 3

Outlet Collector

Liquid Distributor

Liquid Distributor

Reactor - 2

DHC-32, 96.27 m3, Dense, 6415mm

Ceramic, Sock, 75 / 75mm

Bed 1

3mm Dia

6mm Dia

Ceramic, Sock, 75 / 75mm

3mm Dia

6mm Dia

Ceramic, Sock, 75mm6mm Dia

Ceramic, Sock, 19mm Dia

Inlet Diffuser

Liquid Distributor

Bed 2

Outlet Collector

DHC-32, 96.27 m3, Dense, 6465mm

6mm Dia Ceramic, Sock, 75mm

Liquid Distributor

Unit’s Reaction Philosophy

A. HydroTreating Metal-Catalysed Co-Mo / Ni-Mo Catalyst

B. HydroCracking Acid-Catalysed-cum- Low Zeolite with Metals

Metal-Catalysed

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 Net Exothermic in nature

Heteroaromatic Easiest

Multiring aromatic followed by Hydrogenation

Monoaromatic reactions for Saturation of

Multiring Naphthene cracked unsaturated molecules

Mononaphthene

Paraffin Most Difficult

Introduction: PREP UOP’s HCU

Unit Design Capacity 1.7 MMTPA [212.5 TPH Fresh Feed]

• Licensor UOP , USA

• PMC EIL , INDIA

• LSTK Contractor DICL , KOREA

• Main Sub-contractor Toyo , Japan

• Construction Agencies involved Punj Lloyd , Petron , others

DCS Implementation (on Conventional Mode)

• PMC EIL , INDIA

• DCS YIL , INDIA

• PLC Triconex , USA

• Vibrn Monitoring 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) ASI Robicon, ……

• RGC with HP LP Turbine BHEL(4448 kW, 11670 max cont rpm)

(DG Seal by Burgman)

• Feed & Amine Pumps & PRTs EBARA, Japan

Feed / Amine Motors (3.7/1.55 MW) Toshiba, Japan

• Wash Water Pump PERONI POMPE SpA, Italy

• PF Bottom Pump KSB

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 80:20 :: VGO:HCGO

B. 50:50 :: AL:AH AMC 42:30:20:8 :: LVGO:HVGO:HCGO:HGO

Both Feedstocks bearing similar characteristics –

‘S’ content wt% 3.3

Total N ppmw 1800

Broad TBP cut oC 370 – 550

Metals [Ni+V / Total] ppmw 1.0 / 2.0 (max)

CCR wt% 0.5 (VGO) / 1.0 (HCGO)

C7 insolubles wt% 0.05 (VGO) / 0.12 (HCGO)

Product Characteristics

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

50 ppmw (max)SUCO Bleed

350 / 370 oC (max)D86 85/95 LV%

2-5 cStkV @ 40oC

36oC // 15/0 oC S/WFlash (min) // Pour (max)

50 ppmw (max)S

56 (min) EURO IVCetane no (SOR & EOR)HCU Blended HSD Pool

[Total HSD + Total HN +

part Kero]

-51oC / 40oC / 21mm(min)Freez / Flash / Smoke pt

20 (min)Color (Saybolt)

8 cSt (max)kV @ -20oC

30 ppmw (max)SKero / ATF

5 ppmw (max)SHN

0.4 kg/cm2A (max)RVP

5 ppmw (max)SLN

Not worse than No. 1Cu Strip Cor (1 hr @38oC)

95 LV% (min)Vaprsn @ 2oC, 760 mmHG

16.87 kg/cm2gVap Pr @ 67oC LPG

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

* Total HSD + Total HN + Part KERO MU H2 @ 6,366 kg/h (or 68,406 NM3/h)

3.353.34Balance (H2S + others)

2.942.94UCO Bleed

54.2456.89HCU DIESEL POOL *

46.0048.76HSD

18.9919.15KERO/ATF

23.7423.94Kero/ATF

3.493.34PF HN

15. 2313.24NAPHTHA

8.267.58PF LN

6.975.66DeB Naph

3.052.41LPG

2.192.03OFFGASES

1.521.40CFD offgas

0.670.63S Ab + DeE offgas

212.5 + 6.4212.5 + 6.4FF+MU H2 rate, T/h

EORSORStreams

Catalyst Specifications

15.25SockHC-KFuture BED

Rx- 3 (75-V-003)

DHC-32

185020192.54Total Catalyst

96.27DenseDHC-32BED-2

96.27DenseDHC-32BED-1

Rx- 2 (75-R-002)

135.49Total Catalyst

59.16DenseHC-TBED-3

29.58DenseHC-TBED-2

HC-T

91815

13.26DenseHC-T

10.58SockHC-DM (1/16”)

HC-DM

11215

10.58SockHC-DM (1/10”)

TK-711 525010.58SockTK-10, TK-711

TK-10 14101.75SockTK-10, TK-711BED-1

Rx- 1 (75-R-001)

Catalyst Volume,

M3 Weight, Kg

Loading

Method

Catalyst TypeReactors

Rx Secn PFDVGO FG

N2 [Split range] Hot ex Units Cold ex Strg

CGO B/W Surge drum

Liq Recycle

Feed Filter SM

150 C Coalescer

Slop

FCC

HS DCU

HFD

PRT P 002

R 001 R 002

RG ex E 001

E 004 E 002 RG-Q

RG-Q

To HS

RG

Heater

F 001

RG-Q

RG-Q

42.5

42.5

127.5

155.3 @ 177 C

367.8 T/h

197 kg

162 C

366 C

235 C 337 C 452 C

387 C

38 T/h

9.3 T/h

9.7 T/h

3.4 T/h

5.8 T/h

Total Rx RG-Q

28.2 T/h @ 64 C

405 C

169.3 kg

399 C

409 C

162.2 kg434 T/h

@ 271 C

150 C [Ratio Control] 80 C

319 C

264 C

325 C 341 C 400 C 409 C

10.52 DUTY

TC

C/V

Feed

Surge

drum

P 001 A/B

172.1 kg 169.1 kg

177.5 kg

3.5 kg

5 kg

E 005 A/B/C E 003 A/B/C

31.35 DUTY 24.37 DUTY

413 C, 173.3 KG 419 C, 170.2 KG

430 C, 170.4 KG 428 C, 162.8 KG

R 001/002 Design Temp = 454 oCR 001/002 Design Pr = 189.5 / 186 kg/cm2g

RG Loop PFD

*

*

*

MUG

RGC

PRT

Rx eff ex

E 005 A/B/C

E 001

A/B

E 009

RG to

E 004

E 002

F 001

RG to F 001,

E 005 A/B/C To Stripper

To Stripper

Wash water injnEA 001 A-H

To SWS

17.4 T/h

EA 002

Spillback

CW E 006

To DHDT PRT

P 004

RA to

ARU

LA ex

ARU

BFW

Bleed

Rx Quench

269 C

201 C 172 C

16 T/h @ 66 C

146 C

55 C 154.7 kg

42 C

40 C 45 C

19 T/h

51 C

45 C

153.7 kg

64 C, 179 kg

105 C

74 C

235 C

53 C

52 C

177 C

226.5 T/h

60 T/h

6.4 T/h

28.2 T/h

291 T/h

73 T/h

HS

HFD

CS

CFD

RG

Scrub

KOD

RGC

KOD

RG

Scrub

LA

Surge

drum

LC

LC

LC LC

LC

LC

P 003 A/B

P 113 A/B

LC

N2 [Split range]

157.3 kg

32 kg

31.6 kg

2 kg

23.82 DUTY

DV

LSSHSS

Bleed C/V MUG Spillback C/V

CS PRC

Bleed FRC

MUG 1st SucPRC

S/R

LER PFD

CorInh

STR

DeE

DeB

SAb

LPG

Amine

Abs

Ex CFD

ExHFD

SM @ 3.6 T/h

To PF

LPG

r/d

Sand

Filter

Sweet FG

SW

Sour FG

toDHDT

CW

HSD r/d

UCO

SW

Unstab Naph

Stab Naph

LPG

5.94T/h

33.3 kg

ex LA

Surge

drum

45 C

20 T/h

RA to ARU

Mixer

DMWRA

LPG W/w

LPG

Caustic

wash

10 Beo

Caustic

To & Fro

CW

CWPF

LN

Naphtha r/d

CW CW

CW

SW

268 C

174 C

246 C346 T/h

126 C, 9.5 kg

41 C

20 T/h

17 T/h

8.8 kg

0.45 T/h

41 C

8.5 kg 55 C, 31 T/h

46 C, 29 T/h

48 C

1.2 T/h

160 C

194 C

198 C

12.4 T/h

81 C

18.3 kg

17.6 kg

28 T/h

41 C

49 C

5.43 T/h

41 C

2 T/h

98 C

110 C

113 C

5.27 T/h

40 C, 20 kg

64 C

29.9 kg29.2 kg

0.17 T/h

0.66 T/h

40 C

185 C

161 C

16.6 T/h

@ 29 T/h16.9 kg

2.7 T/h

PF Circuits

To HGU

KERO PA

PF BOT PUMP

PF FEED

KERO STR RBLR DeB RBLR

BFW

SL

EA 111

CW

Liq Recycle Oil

UCO Bleed

HSD PA

IRBFWSLSM

HSD PA

HSD R/DHN STR RBLR DeB FEED

DMW

CW HSD RDCoalescer

KERO RDCW KERO RD

KERO to HSD

IR

KERO PA

HN R/D HN R/D

HN to HSD

CW

P 105 A/B

E 104

359 C, 14 kg 278 C

246 C

To F 101

285 C

258 C

208 C

213 C

225 C

194 C

198 C

177 C

80 C 80 C

B B B

270 C, 4.6 kg 228 C 191 C 178 C

170 T/h

148 T/h9.4 T/h 8 T/h

169 C

P 106 A/B

P 111 A/B

243 C, 11 kg

STR = SL @ 3.3 t/h

VAP RTN 261 C

B

214 C

6.4 T/h

155.3 T/h

164 C

165 C

189 C

B

81 C @ 48 T/h

160 C

65 C

45 C 107 T/h

@ 10.5 T/h

@ 7.3 T/h

124.5 T/h

P 108 A/B

206 C, 8 kg 65 C 52.4 T/h

42 T/h

P 107 A/B

181 C, 6 kg234 T/h

121 C256 T/h

VAP RTN 195 C

P 110 A/B

164 C, 9 kg

7.3 T/h

HN REFLUX @ 214 T/h @ 145 C

VAP RTN 157 C

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

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 T’s , Rx P’s , 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 = 8.32 wt%

• RGC normal Process Load = 59,900 kg/h (or 3,70,841 NM3/h)

RG MW / H2S = 3.62 / Nil

• Wash water injection rate = 18 T/h , and HP Sour Water NH3 / H2S load = 2.61 / 5.38 wt%

• Lean Amine to RG Scrubr = 226.5 T/h (DEA)

Lean Amine to LPG Wash = 19.7 T/h (DEA)

LA / RA H2S load = 0.24 / 2.60 wt%

• CFR = 1.8 [This helps towards LOW TEMP OPRN & Higher HSD Selectivity]

- FF = 212.5 T/h

- LR = 155.3 T/h

Combined Feed = 367.8 T/h

• UCO Bleed = 3 wt% on FF rate

• CPP = 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 Rx’s 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