Seminar report

HYDROCRACKING TECHNOLOGY

PREPARED BY: GUIDE:

PATEL VISMAYKUMAR RAJESHBHAI 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. PUJAD´O , 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 carbon–carbon single bond, and hydrogenation is the addition of
hydrogen to a carbon–carbon 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. PUJAD´O , 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 silica‐alumina, zeolites

DAVID S. J.“STAN” JONES , PETER R. PUJAD´O , Handbook of Petroleum Processing, Springer.Netherlands.2006 ;298.
 FLOW SCHEMES :

Single Stage Once through Single Stage with recycle Two stage recycle

DAVID S. J.“STAN” JONES , PETER R. PUJAD´O , Handbook of Petroleum Processing, Springer.Netherlands.2006 ;288-290
 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(280-475°C) 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 - 2¼Cr–1Mo or 3Cr–1Mo
• 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. PUJAD´O , 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. (1◦C/month)
• Average bed temperature = Design maximum, the catalyst has to be replaced or reactivated.

DAVID S. J.“STAN” JONES , PETER R. PUJAD´O , 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.