# 7, HYDROROCESSING Part 1 Final Slide for Presentation Final

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Training Programme Mumbai July,2007

HYDROCRACKING-Fundamentals, catalysts, process technologies and recent

developments.

Part 1

Sobhan Ghosh

Managing I nnovation

Process & research Consultant




PERSPECTIVESPERSPECTIVES IN MODERN PETROLEUM REFININGIN MODERN PETROLEUM REFINING

Deteriorating Crude Oil Quality and Fluctuating

Prices in International Markets

Constraint of Source of Crudes and Market Demand

Increasing Environmental Regulations For

Cleaner Products/ Processes And Growing

Demand For Quality Products

Declining Refining Margins




UP GRADATION P ROCESSES

� Carbon rejection

± Visbreaking , Hsc - ROSE, ART, FCC

±

Delayed coking, fluid coking, Fexi coking,

� Physical separation

± Solvent deasphalting, ROSE, DEMEX

� Hydrogen addition ± Hydrocracking,Resid hydrotreating, LC

Fining, H ± oil etc.




CDU

VDU SecondaryProcessing

Resid

Processing

Crude

Atmospheric Resid

Gases and LPG

Light Naphtha(C5-85)

Hy Naphtha (85-127)

Kerosene( 127-293)

Diesel ( 293-370)

HGO

VGO

Vac.Resid

Hydrocracker/FCC




Chemical transformations

in Different Processes

� 1. FCC : Cracking: Isomerisation, Aromatisation

etc.

� 2. Hydricracking : Cracking and hydrogenation

� 3. Reforming : Isomerisation, Cyclization,

Aromatization, Hydrogen

removal & olefinbuilding

� 4. Coking: Severe cracking leading to

coke formation




Carbon

( C )(Solid) Gas Gas

Hydrogen

( 2H2 )

Methane

( CH4 )




Saturated Straight Chain HydrocarbonC7 H16 ( Cn H 2n+2)





Removed




Unsaturated Straight ChainHydrocarbon (C7 H14 ( Cn H 2n)

Removed




Unsaturated Straight ChainHydrocarbon: C7 H14 ( Cn H 2n)

Double bond





Removed

Result?




TOLUENE: C7 H8




?




TWO ATOMS OF HYDROGEN MUST BE PROVIDED, OR,
















Net result: one Saturated and one unsaturated compound

Formation of double bond

Saturated Unsaturated




HYDROPROCESSING/HDROREFINING

DIS I E E

HYDROCR CKING HC

HDS

HDN

HD

HYDROGEN ION

HYDROFINISHING

HYDROISO ERIS ION

HYDRO RE ING

HYDROPROCESSING






T ypical Prod ct slate ydrocracki g

Gasoline

Boili g ra ge, o

ield, vol%

5-220

55

5-180

30

Diesel

Boili g ra ge, o

ield, vol%

, ppm

romatics, wt%

eta e I dex

220-360

20

5000

70

21

180-370

80

<5

20

56

Feed stock California VGO

Boiling range, oC 238-562

N, wppm 2660

S, wt% 1.18

Aromatics, wt% 32




Hydrocracking

� Feed : VGO, Resid, Distillates

�Typical Operating Conditions:

Conversion: 50 ± 100%

(normally lo for once thru¶ high for recycleconfiguration)

Temperature: 350 ± 425oc

H2 Pressure: 100 ± 200 bar

LHSV: 0.5 ± 2.0 h-1

H2:Oil Ratio: 700 ± 2000 nm3 / m3

�Catalyst: Ni/Mo or Ni/W on amorphous SiO2/Al2O3 or,

Zeolite




HYDROCRAC ING

CATALYST

(dual function)

Cracking Function

( acid support)

Hydrogenation Function

(metals)

POROUS SUPPORT HAVING

ACIDIC SITES

ZEOLITE>SILICA-ALUMINA

METALS DISPERSED

ON POROUS SUPPORT

Pt or Pd>Ni-W>Co-Mo



Training Programme Mumbai July,

2007

Chemistry of Hydroprocessing

1. S²Org. --------- H2 S + Org.

+ H 2

2. M ± Org. -------- M + Org.

3 N ± Org ------- NH3 + Org.

4. Olefin ---------- Parafin

5. Aromatics --------- Cyclic compounds ----

Parafins




2007

MAJOR REACTIONS IN A

HYDROCRAC ER

Hydrocracking

Demetallisation>Olefin Saturation > desulfurisation >

Denitrogenation > Aromatic saturation>Cracking of

naphthenes>Cracking of paraffins

� Isomerisation

� Hydrocracking� Aromatic ring saturation and opening

� Dealkylation

� Naphthenic ring opening




2007

Hydrotreatment

M AJOR REACTIONS IN

HYDROCRACKING

� Hydrodesulfurisation

� Hydrodenitrogenation

� Olefin saturation

� Hydrodemetallisaion Hydrotreating is a lo er pressure operation than

Hydrocracking. Higher Hydrogen P ressure± Higher

Severity




2007

Coke formation

Polyaromatics Alkylation CyclizationCoke

precursor

+ Olefins - H2 - H2

Resins, asphaltenes & otherpolyaromatics have strong coking

tendency

Polynaphthenes & Polyaromatics are

converted on large pore amorphouscatalyst.




2007

HYDROCRAC ING

CATALYST

Gasoline & light

products

Middle-distillate

Strong cracking activity

- Zeolites

Moderate hydrogenation

- Ni/Mo sulfides

Weaker acidity

Weaker zeolite

Strong hydrogenation

- Ni/W, Pd, Pt




2007

NiMo promoted(1st step HCK)

NiMo(Resid HDS)

NiMo/ CoMo

(GASOLINE)

CoMo promoted(Diesel)

NiMo promoted(Diesel,

Cracked GO,VGO)

HYDRO P ROCESSING CATALYSTS

Hydrotreating catalysts

for various feedstocks




2007

CATALYT CO M P ONENTS FOR

HYDRO P ROCESSING

� Metals of group vi-a with

group - VIIIA metals as promoter

- W / Mo promoters Ni / Co

� Noble metals

- Pt, Pd

� Supports

- alumina- silica alumina

- zeolites

� Non noble metal catalysts are active in sulfided form




2007

ROLE OF SUPPORT

� Diffusivity

� Dispersion of active metals

� Provides acidity

� Structural Integrity

�Wetting of Oil on the Catalyst surface

�Low pressure drop and good Radial mixing




2007

Important Prameters of Catalystsupport

� Pore structure & pore size distribution

� Surface area

� Acid strength & acid sites distribution

�Crush Strength

�Metal dispersion




2007

TYPICAL PORE SIZE DISTRIBUTION OF

HYDROTREATING CATALYSTS




2007

TYPICAL SHAPE OF CATALYST PARTICLES

size and shape influences the pressure drop in the reactor

and for effective reactant contact




2007

CLASSIFICATION OF HYDROCRAC ING PROCESSES

( HC: Hydrocracking; HT: Hydrotreating; R: Reactor)

Hydrocracking Processes

Single-stage ( no intermediate

separation of products)

HT +HC (2R)

� Dual catalyst

�Fractionation of HT

effluent ( separate HT)

� Recycle to HC reactor

HT+HC (2R or 3R)

� Dual or triple catalyst

�Fractionation of

effluent from 1st HC

reactor

� Recycle to 2nd HC

reactor

Without recycle

(³ once-through´)

With recycle to HC

reactor

HT + HC ( 1R or 2R)

� Dual catalyst

� High N & S feed

HC only ( 1R)

� Single catalyst

�lo N & S feed

Two stage ( separations of

products between stage 1 &2)




2007

ACTIVATION OF CATALYSTS

Commercial catalysts are supplied in calcined (oxide)form having no/less activity

To be activated prior to their use in reactors

In-situ activation

± Non-noble metal catalysts (Co/Mo, Ni/Mo)

� sulfiding with H2S, DMS, DMDS etc. ± Noble metal catalysts (Pt, Pd)

� reduced to zero valent state




2007

CATALYST REGENERATION AND

REACTIVATION

Regeneration of catalyst bed when ³end of run´

condition is reached

Burning of deposited coke bed

± Metal sulfides are converted to oxides

Reactivation

± Sulfiding for non-noble metal catalysts

± Reduction for noble metal catalysts

Rejuvenation

± Restoration of hydrogenation activity lost due to

agglomeration of noble metals




2007

CATALYST DEACTIVATION & P OISONING

Loss of catalyst activity due to

� Deposition of coke

� Poisoning of active sites

± Basic nitrogen compounds

± Sulfur compounds

� Deposition of coke or metal at pore mouth

� Sintering & volatilisation of active material at high

temperature.




2007

Hydrocracking Reaction

� Tpical Gas -Solid ±Liquid three Phase reaction� Trickel Bed Reactor

� Activation energy for VGO = 47.7 cal/gm-mole

� 15 oC rise in Temp. doubles the Reaction rate

� High Pressure ± Higher Reaction Rate, low coke

make and lower severity.

Individual reaction rates vary with reactant type and

boiling range

Ratio of hydrocracking rate for

C20:C15:C10:C5 $$ 120:72:32:1




2007

HYDROCRACKING KINETICS

Adsorption strength :

Heteroatomic > Multi-ring aromatic >

Monoaromatic > Multi-ring naphthene >

Mononaphthene > Paraffin

Reaction dependent on strength of

adsorption on catalyst surface




2007

Higher SurfaceArea

Optimum PoreSize Distribution

Modification of Chemical Nature

Shaped Carrier (trilobe,quadrilobe)

Goodmechanicalstrength

Optimum MetalsDispersion

Enhancement of Promoter Effects

FACTORS INFLU ENCING

HYDRO P

ROCESSING CATALYSTS P ERFOR M ANCE






2007

In P art 2 e shall deal ith the

hard are and integration of HC ith other processes.

Documents

# 7, HYDROROCESSING Part 1 Final Slide for Presentation Final