Seminar report

HYDROCRACKING TECHNOLOGY

PREPARED BY:
PATEL VISMAYKUMAR RAJESHBHAI

GUIDE:
DR. RANJAN SENGUPTA

INTRODUCTION :

Commercially developed by I. G. Farben Industries (1927) (lignite into gasoline)

First modern distillate hydrocracker Chevron (1958)
(Mid-1950s) The automobile industry started the manufacture of high performance cars
High-compression ratio engines that required high-octane gasoline.
Fluid catalytic cracking (gasoline, by-product high-boiling oil called cycle oil)
Cycle oil (was difficult to convert to gasoline and lighter products). Hydrocracking can crack that oil.
Switch of railroads from steam to diesel engines after World War II
Introduction of commercial jet aircraft (late 1950s) increased the demand for diesel fuel and jet fuel.
The rapid growth of hydrocracking (1960s) (by the development of new, zeolite based hydrocracking
catalysts.)
Improvement in performance characteristics : Higher activity, Better ammonia tolerance, and Higher
gasoline selectivity.
Primarily for the production of middle distillates (1970)

DAVID S. J.STAN JONES , PETER R. PUJADO , Handbook of Petroleum Processing, Springer.Netherlands.2006 ; 287-288.

HYDROCRACKING :

Catalytic petroleum refining process

Convert heavy , high boiling point hydrocarbons into more valuable smaller , low boiling hydrocarbons.
In presence of Hydrogen
At high temperatures(365 441oC) & high pressures (170-200 Kg/cm2g)
In presence of catalyst
Hydrocracker gives Eco friendly Products ( saturated hydrocarbons & low to ultra low sulfur)
Hydrocracking = Catalytic cracking + Hydrogenation

Catalytic cracking is the breaking of a carboncarbon single bond, and hydrogenation is the addition of
hydrogen to a carboncarbon double bond.

Glenn E. Handwerk , James H. Gary. Petroleum Refining Technology and Economics , Marcel Dekker, Inc. New York. 2001, 139-140

CHEMISTRY :

Converts the heavy feed stock to lower molecular weight products

Removes sulfur , Nitrogen , Saturates olefins and Aromatics.

Organic sulfur (H2S), nitrogen (NH3) and oxygen compounds (H2O.)

Reactions in hydrocracking : Desirable and Undesirable.

Desirable : Treating, Saturation, and Cracking reactions.
Undesirable : Contaminant poisoning , Coking of the catalyst.
Treating reactions : (Organic) Metals removal, Olefin saturation, Sulfur removal (HDS), Nitrogen removal
(HDN), Oxygen removal, and Halides removal.
Cracking reactions : Bi-functional mechanism (requires two distinct types of catalytic sites)
Acid function (cracking and isomerization) and Metal function (olefin formation and hydrogenation.)
Cracking reaction (requires heat), Hydrogenation reaction (generates heat). Overall, heat release in
hydrocracking

DAVID S. J.STAN JONES , PETER R. PUJADO , Handbook of Petroleum Processing, Springer.Netherlands.2006 ; 292-295.

Mary P. McGuiness, Terry E. Helton, Thomas F. Degnan Jr., et al. (1998,july), Catalytic hydro processing a good alternative to solvent processing- retrieved from
http://www.ogj.com/articles/print/volume-96/issue-29/in-this-issue/refining/catalytic-hydroprocessing-a-good-alternative-to-solvent-processing.html

CATALYST :

Bi-functional Catalyst
Metal function (for Hydrogenation) :
Platinum , Palladium
Sulfide metals of Nickel , Molybdenum , Tungsten as Base Metal
Key requirement : Must activate hydrogen and catalyze dehydrogenation and hydrogenation reactions.
Acidic function (for cracking) :
Amorphous silicaalumina, zeolites

DAVID S. J.STAN JONES , PETER R. PUJADO , Handbook of Petroleum Processing, Springer.Netherlands.2006 ;298.

FLOW SCHEMES :

Single Stage Once through

Single Stage with recycle

DAVID S. J.STAN JONES , PETER R. PUJADO , Handbook of Petroleum Processing, Springer.Netherlands.2006 ;288-290

Two stage recycle

PROCESS :
Isocracking :
Same process as hydrocracking but at a lower temperature and pressure.
High ratio of isoparaffins to normal paraffin in its light products
A high percentage of isoparaffins increases light naphtha product octane numbers.
Isocracking removes heavy aromatic compounds and creates isoparaffins to produce middle distillates with
outstanding burning and cold flow properties
Kerosene with low freeze points and high smoke points
Diesel fuels with low pour points and high cetane numbers
Light naphthas with a high isoparaffin content
Unicracking
Carried out at moderate temperatures(280-475C) and pressures(35-219 kg/cm 2)
UOP continues to develop catalysts that provide enhanced performance without sacrificing yield or activity.
Improve Cetane and improve diesel cold flow properties by the simple expedient of a catalyst change-out in
the same reactor

Robert A. Meyers, Handbook of petroleum refining process , McGraw-Hill. New York.1997,7.3-7.4,7.25

PROCESS VARIABLES :

Reactor Temperature
Reactor Pressure
Space Velocity
Nitrogen Content
Hydrogen sulfide
Recycle Gas rate
Hydrogen Purity

Glenn E. Handwerk , James H. Gary. Petroleum Refining Technology and Economics , Marcel Dekker, Inc. New York. 2001, 146-148.

HYDROCRACKING REACTOR :

Fixed-bed catalytic reactor

High Temperature for the catalyst to hydrocrack the feed.
High Temp. - Increase the catalyst activity.
1st bed => Not active catalyst but functions as rust/particulate arrestor
and prevents early deterioration of catalyst.
MOC - 2Cr1Mo or 3Cr1Mo
Small amount of vanadium is added (to increase its strength characteristics)
4.9 m ID (Commercially) & 30 cm Thickness( depending on design P and
Diameter)

Middle distillate (3 or 4 beds)

Naphtha (5 or 6 beds)

DAVID S. J.STAN JONES , PETER R. PUJADO , Handbook of Petroleum Processing, Springer.Netherlands.2006 ;308-309

Exothermic process
To avoid overheating and to provide a safe and stable operation quenching zones.
(a) To cool the partially reacted fluids
(b) To assure a uniform temperature distribution
(c) To mix efficiently
Unbalanced temperatures in a catalyst bed => Different reaction rates in the same bed
Different deactivation rates of the catalyst => Temperature excursions
During operation, the hydrocracking catalyst gradually loses some of its activity.
To maintain the conversion of feedstock to products constant, the average bed temperature is gradually
increased. (1C/month)
Average bed temperature = Design maximum, the catalyst has to be replaced or reactivated.

DAVID S. J.STAN JONES , PETER R. PUJADO , Handbook of Petroleum Processing, Springer.Netherlands.2006 ;310

ADVANTAGES AND DISADVANTAGES OF HYDROCRACKING :

Advantages :
Its flexibility with respect to production of gasoline and middle distillates,
Ability to handle a wider range of feedstock like cycle oils from other cracking units
Does not yield any coke as by-product
Better conversion of the gas oil and residues into useful products.
No Sox , No2 production
Middle distillate yield is 80% as compared to 45% in FCCU.
The products are clean, saturated & high in value.
Disadvantage :
High capital and operating cost
Pressure generation
Equipment safety
Lower gasoline quality in terms of octane number

Glenn E. Handwerk , James H. Gary. Petroleum Refining Technology and Economics , Marcel Dekker, Inc. New York. 2001, 137-138.