Hydroprocessing:

Hydrocracking & Hydrotreating

Chapters 7 & 9

1
 Petroleum Refinery Schematic
Gasses

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant
Alkyl Butanes Fuel Gas
Feed
LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Isomerate
Light Naphtha Alkylate
Aviation
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Cat Solvents
Distillate Hydro-
AGO Naptha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
Gas Oil Fluidized treating
LVGO Hydro- Catallytic Diesel
treating Cracking
Cat
Vacuum Distillates
Distillation HVGO
Fuel Oil
Cycle Oils
Residual
DAO Fuel Oils

Solvent
Coker SDA
Deasphalting
Naphtha Bottoms Naphtha Asphalts

Visbreaking Distillates
Fuel Oil
Bottoms
Coker Lubricant
Vacuum Residuum Lube Oil
Gas Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking
Coke

2
 Hydroprocessing

Process Purpose Feedstock Products Underlying Prinicples Configuration Other Considerations

Gas Oil Gas Oil Gas Oil Gas Oil

Naphtha Hydrotreating Atmospheric Residuum
Residuum Residuum Residuum Residuum
Atmospheric & DAO DAO DAO DAO
Distillate Hydrotreating
Vacuum Residuum Bottoms Bottoms Bottoms Bottoms
Gasses Gasses Gasses Gasses
Cat Naphtha Cat Naphtha Cat Naphtha Cat Naphtha
Gas Oil Hydrotreating Gas Oil Cat Diesel Cat Diesel Cat Diesel Cat Diesel
Cycle Oils Cycle Oils Cycle Oils Cycle Oils
Slurry Slurry Slurry Slurry

Hydrocracking Gas Oil Distillates Distillates Distillates Distillates

3
 Purpose
•Hydrotreating
» Remove hetero atoms & saturate carbon-carbon bonds

Sulfur, nitrogen, oxygen, & metals removed

Olefinic & aromatic bonds saturated
» Reduce average molecular weight & produce higher yields of fuel products
» Minimal cracking
» Minimal conversion – 10% to 20% typical
» Products suitable for further processing or final blending

Reforming, catalytic cracking, hydrocracking
•Hydrocracking
» Severe form of hydroprocessing

Break carbon-carbon bonds

Drastic reduction of molecular weight
» 50%+ conversion
» Products more appropriate for diesel than gasoline

4
Characteristics of Petroleum Products

Refining Overview – Petroleum Processes & Products,

by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000

5
 Hydroprocessing Trends

• Hydrogen is ubiquitous in refinery & expected to increase

» Produces higher yields & upgrade the quality of fuels
• The typical refinery runs at a hydrogen deficit
» As hydroprocessing becomes more prevalent, this deficit will increase
» As hydroprocessing progresses in severity, the hydrogen demands
increase dramatically
• Driven by several factors
» Heavier & higher sulfur crudes
» Reduction in demand for heavy fuel oil
» Increased use of hydrodesulfurization for low sulfur fuels
» More complete protection of FCCU catalysts
» Demand for high quality coke
» Increased production of diesel

6
 Sources of Hydrogen
• Catalytic Reformer
» The most important source of hydrogen for the refiner
» Continuously regenerated reformer: 90 vol%
» Semi-continuously regenerated reformer: 80 vol%
• FCCU Offgas
» 5 vol% hydrogen with methane, ethane & propane
» Several recovery methods (can be combined)

Cryogenic

Pressure swing adsorption

Membrane separation
• Steam-Methane Reforming
» Most common method of manufacturing hydrogen
» 90 to 95 vol% typical purity
• Synthesis Gas
» Gasification of heavy feed
» Hydrogen recovery – pressure swing adsorption or membrane separation
» More expensive than steam reforming but can use low quality by product
streams

7
 Steam-Methane Reforming

• Reforming. Endotherm catalytic reaction. 1400 – 1500°F

CH4 + H2O → CO + 3 H2
• Shift conversion. Exothermic fixed-bed catalytic reaction. 650°F
CO + H2O → CO2 + H2
• Gas Purification. Absorption of CO2 in amine or hot KCO3 solution.
• Methanation. Trace amounts of carbon monoxide & carbon
dioxide removed. Exothermic fixed-bed catalytic reactions, 700 –
800°F.
CO + 3 H2 → CH4 + H2O
CO2 + 4 H2 → CH4 + 2 H2O

8
 Steam-Methane Reforming

Petroleum Refining Technology & Economics, 5th ed.,

by J.H. Gary, G.E. Handwerk, & M.J. Kaiser, CRC Press, 2007

9
 Hydroprocessing Catalysts
• Hydrotreating
» Desired function

Cobalt molybdenum : sulfur removal & olefin saturation

Nickel molybdenum: nitrogen removal & aromatic saturation
» Reactor configuration

Fixed bed – temperature to control final sulfur content
» Selective catalysts for sulfur removal without olefin saturation

Maintaining high octane rating
• Hydrocracking
» Crystalline silica alumina base with a rare earth metal deposited in the lattice

Platinum, palladium, tungsten, and/or nickel
» Feed stock must first be hydrotreated
» Catalysts deactivate & coke does form even with hydrogen present

Hydrocrackers require periodic regeneration of the fixed bed catalyst systems

Channeling caused by coke accumulation a major concern

Can create hot spots that can lead to temperature runaways
» Reactor configuration

Ebullient beds – pelletized catalyst bed expanded by upflow of fluids

Expanded circulating bed – allows continuous withdrawal of catalyst for
regeneration

10
 Characteristics of Hydrotreating

Refining Overview – Petroleum Processes & Products,

by Freeman Self, Ed Ekholm, & Keith Bowers, AIChE CD-ROM, 2000

11
 Hydrodesulfurization
• Sulfur
» Sulfur converted to hydrogen sulfide (H2S)

Added hydrogen breaks carbon-sulfur bonds & saturates remaining hydrocarbon
chains
» Form of sulfur bonds

Sulfur in naphtha generally mercaptans (thiols) & sulfides

In heavier feeds, more sulfur as disulphides & thiophenes
» Light ends

Heavier distillates make more light ends from breaking more complex sulfur
molecules
• Unsaturated carbon-carbon bonds
» Olefins saturated – one hydrogen molecule added for each double bond

Olefins prevalent in cracked streams – coker or visbreaker naphtha, catalytic cracker
cycle oil, catalytic cracker gasoline
» Aromatic rings hydrogenated to cycloparaffins (naphthenes)

Severe operation

Hydrogen consumption strong function of complexity of the aromatics

prevalent in heavy distillate hydrotreating, gas oil hydrotreating, hydrocracking
• Selective catalysts available for hydrotreating cat gasoline for sulfur removal but
not saturate olefins
» Maintain high octane ratings

12
 Hydrogen Consumption

• Chemical consumption due to hydrogenation reactions

» Cracking reactions of carbon-carbon bonds minimal in hydrotreating,
even during aromatic saturation
• Hydrogen is lost in equilibrium with light gases
» Amount is significant & may double amount required for sulfur
removal
• Hydrogen absorbed in liquid products
» Usually small compared to sulfur removal needs – 1 lb/bbl
• Hydrogen removed with purge gas
» Used to maintain a high purity of hydrogen — light ends dilute the
hydrogen concentration
» Usually small compared to sulfur removal needs

13
 General Effects of Process Variables
•Reactor inlet temperature & pressure
» Increasing temperature increases hydrogenation but decreases the number of
active catalyst sites
» Temperature control is used to offset the decline in catalyst activity
» Increasing pressure increases hydrogen partial pressure & increases the severity
of hydrogenation
•Recycle hydrogen
» Require high concentration of hydrogen at reactor outlet

Hydrogen amount is much more than stoichiometric

High concentrations required to prevent coke laydown & poisoning of
catalyst
 Particularly true for the heavier distillates containing resins and
asphaltenes
•Purge hydrogen
» Removes light ends & helps maintain high hydrogen concentration

14
 Increasing Severity

• Naphtha hydrotreating
• Distillate (light and heavy) hydrotreating
• Gas oil hydrotreating

15
 Naphtha Hydrotreating

• Naphtha hydrotreated primarily for sulfur removal

» Mostly mercaptans (RSH) & sulfides (R2S)
» Some disulfides (RSSR), & thiophenes (ring structures)
• Cobalt molybdenum on alumina most common catalyst
• Chemical hydrogen consumption typically 50 to 250 scf/bbl
» For desulfurization containing up to 1 wt% sulfur — 70 to 100 scf/bbl
» Significant nitrogen & sulfur removal — 250 scf/bbl

16
 Naphtha Hydrotreating Process

• Liquid hourly space velocity ~ 2

• Hydrogen recycle about 2,000 scf/bbl
• Stripper overhead vapor to saturates gas plant
» Recovery of light hydrocarbons & removal H2S
• Fractionator Pentane/hexane overhead to
isomerization
» Bottoms to reformer

17
 Distillate Hydrotreating
• In general, all liquid distillate streams contain sulfur compounds
that must be removed
• Saturate olefins in diesel to improve the cetane number
• Hydrogenation at the high pressure produces small amounts of
naphtha from hydrocracking
» Required to get at the embedded sulfur
» Diesel hydrotreater stabilizer will have an upper sidestream draw
producing the naphtha which is recycled to motor gasoline processing

18
 Distillate Hydrotreating Process

• Hydrogen recycle starts at 2,000 scf/bbl;

consumption 100 to 400 scf/bbl
• Conditions highly dependent upon feedstock
» Distillate (jet fuel & diesel) with 85% - 95%
sulfur removal — 300 psig & hydrogen
consumption of 200 - 300 scf/bbl
» Saturation of diesel for cetane number
improvement — over 800 scf/bbl hydrogen &
up to 1,000 psig

19
 Gas Oil Hydrotreating
• Catalytic cracker feedstocks (atmospheric gas oil, light vacuum gas oil,
solvent deasphalting gas oil) hydrotreated severely
» Sulfur removal
» Opening of aromatic rings
» Removal of heavy metals
• Desulfurization of gas oil can be achieved with a relatively modest
decomposition of structures
• Gas oils can be contaminated with resins & asphaltenes
» Deposited in hydrotreater
» Require catalyst replacement with a shorter run length than determined by
deactivation
» Guard chamber may be installed to prolong bed life
• Nickel molybdenum catalyst system for severe hydrotreating
• Gas oil units more expensive because of more intensive hydrogenation
» Quench
» Multi-stage flash
» More complex strippers

20
 Gas Oil Hydrotreating Process

• Normally two reactor beds – temperature rise

• Hydrogen partial pressure related to ring saturation & amount of sulfur
» For low ring saturation 300 psig may be sufficient
» 1,200 psig will convert 25% ring saturation & somewhat less than 95% sulfur
removal
» Pressures as high as 1,500 psig can achieve saturation of 30% of aromatic rings
• Hydrogen absorption of 300 scf/bbl could give about 80% sulfur removal &
only require 300 psig
» No ring saturation at these mild conditions

21
 Hydrocracking
• Purpose: process gas oil to break carbon-carbon bonds of large aromatic
compounds & remove contaminants
» Hydrogenation (addition of hydrogen)
» Cracking (carbon-carbon scission) of aromatic bonds
• Typically creates distillate range products, not gasoline range products

• Yields — see textbook

22
 Use of Yield Charts & Equations
Volume Mass Density Ave BPT Watson K

Hydrogen

For cracking

Sulfur

Dissolved in
product

H2S

C3-

IC4 Pure

NC4 Pure

C5 to 180°F

180 to 400°F

400 to 520°F

23
 Reproduction of Figure 7.3
C5 to 180-°F Yield (vol%)

100%
2750

2500

2250
Light Naphtha Yield [vol%]

2000

1750

10% 1500

1250

1000

750

500

Feed

1%
5 10 15 20 25 30 35 40
API Gravity of Feed [°API]

24
 Reproduction of Figure 7.4
Heavy Naphtha Yield

90%

Watson K = 10.90
Heavy Naphtha Vol% Yield (180° to 400°F)

80%
Watson K = 11.30
Watson K = 11.75
70% Watson K = 12.10
Feed
60%

50%

40%

30%

20%

10%

0%
0% 10% 20% 30% 40% 50% 60% 70%
Light Naphtha Vol% Yield (C5 to 180°F)

25
 Reproduction of Figure 7.5
Characterization of Hydrocracker Products

13.0
Watson K = 12.5
12.8 Watson K = 12.0
Watson K = 11.5
12.6 Watson K = 11.0
Watson K = 10.5
12.4 Feed
Watson K of Products

12.2

12.0

11.8

11.6

11.4

11.2

11.0
100 200 300 400 500 600 700
Mid Boiling Point (°F)

26
 Reproduction of Figure 7.6
Hydrogen Content of Hydrocarbons

15%
100°F

14% 400°F
500°F

13% 600°F
700°F

12% 800°F
900°F
Wt% H2

11% 1000°F

10%

9%

8%

7%

6%
9.5 10.0 10.5 11.0 11.5 12.0 12.5
Watson K Factor

27
 Transformation of Figure 7.6
Hydrogen Content of Hydrocarbons

15%

14%

13%

12%
Wt% H2

11%
K=12
10%
K=10

9%

8%

7%

6%
100 200 300 400 500 600 700 800 900 1000
Average Boiling Point (°F)

28
 Use of Yield Charts & Equations
Volume Mass Density Ave BPT Watson K

Hydrogen

For cracking

Sulfur

Dissolved in
product

H2S

C3-

IC4 Pure

NC4 Pure

C5 to 180°F 7.3 7.5

180 to 400°F 7.4 7.5

400 to 520°F 7.5

29
 Use of Yield Charts & Equations
Volume Mass Density Ave BPT Watson K

Hydrogen

For cracking

Sulfur 2 mol/mol S

Dissolved in
1 lb/bbl feed
product

H2S Sulfur in Feed

1.0 + 0.09*(LN-Vol-
C3-
Yield)

0.377*
IC4 Pure
(LN-Vol-Yield)
0.186*
NC4 Pure
(LN-Vol-Yield)

C5 to 180°F 7.3 7.5

180 to 400°F 7.4 7.5

400 to 520°F 7.5

30
 Use of Yield Charts & Equations
Volume Mass Density Ave BPT Watson K

Hydrogen

For cracking ∆

Sulfur 2 mol/mol S

Dissolved in
1 lb/bbl feed
product

H2S Sulfur in Feed

0.01 + 0.09*(LN-
C3-
Vol-Yield)

0.377*
IC4 Pure
(LN-Vol-Yield)
0.186*
NC4 Pure
(LN-Vol-Yield)

C5 to 180°F 7.3 131°F 7.5

180 to 400°F 7.4 281°F 7.5

400 to 520°F 460°F 7.5

31
 Use of Yield Charts & Equations
Volume Mass Density Ave BPT Watson K

Hydrogen

For cracking ∆

Sulfur 2 mol/mol S

Dissolved in
1 lb/bbl feed
product

H2S Sulfur in Feed

0.01 + 0.09*(LN-
C3-
Vol-Yield)

0.377*
IC4 Pure
(LN-Vol-Yield)
0.186*
NC4 Pure
(LN-Vol-Yield)

C5 to 180°F 7.3 Calculate 131°F 7.5

180 to 400°F 7.4 Calculate 281°F 7.5

400 to 520°F Calculate 460°F 7.5

32
 Use of Yield Charts & Equations
Volume Mass Density Ave BPT Watson K

Hydrogen

For cracking ∆

Sulfur 2 mol/mol S

Dissolved in
1 lb/bbl feed
product

H2S Sulfur in Feed

0.01 + 0.09*(LN-
C3-
Vol-Yield)

0.377*
IC4 Calculate Pure
(LN-Vol-Yield)
0.186*
NC4 Calculate Pure
(LN-Vol-Yield)

C5 to 180°F 7.3 Calculate Calculate 131°F 7.5

180 to 400°F 7.4 Calculate Calculate 281°F 7.5

400 to 520°F Calculate 460°F 7.5

33
 Use of Yield Charts & Equations
Volume Mass Density Ave BPT Watson K

Hydrogen

For cracking ∆

Sulfur 2 mol/mol S

Dissolved in
1 lb/bbl feed
product

H2S Sulfur in Feed

C3- 1.0+0.09*(YLN)

IC4 0.377*(YLN) Calculate Pure

NC4 0.186*(YLN) Calculate Pure

C5 to 180°F Fig. 7.3 (YLN) Calculate Calculate 131°F Fig. 7.5

180 to 400°F Fig. 7.4 Calculate Calculate 281°F Fig. 7.5

400 to 520°F ∆ Calculate 460°F Fig. 7.5

34
 Hydrocracking Feeds

• Typical feeds
» Cat cracker “cycle oil”

Highly aromatic with sulfur, small ring & polynuclear aromatics,
catalyst fines; usually has high viscosity

Hydrocracked to form high yields of jet fuel, kerosene, diesel, &
heating oil
» Gas oils from visbreaker

Aromatic
» Gas oil from the delayed coker

Aromatic, olefinic, with sulfur
• Usually more economical to route atmospheric & vacuum gas oils
to the cat cracker to produce primarily gasoline & some diesel

35
 Gas Oil Hydrocracker Feed
• Hydrocracking does a better job of processing aromatic rings without
coking than catalytic cracking
» Hydrogen used to hydrogenate polynuclear aromatics (PNAs)
» Reduces frequency of aromatic condensation
• Hydrocracking not as attractive as delayed coking for resids high in resins,
asphaltenes & heteroatom compounds
» Heteroatoms & metals prevalent in resins & asphaltenes poison
hydroprocessing catalysts
» High concentrations of resins & asphaltenes will still ultimately coke
• Feeds limited to a Conradson Carbon Number (CCR) of 8 wt%
• Feeds require high pressures & large amounts of hydrogen

36
 Gas Oil Hydrocracker Products

•Hydrocracking primarily to make distillates

» In US hydrocracking normally a specialized operation used to optimize
catalytic cracker operation
» In US cat cracking preferred to make gasoline from heavier fractions
•Hydrocracking capacity is only about 8% of the crude distillation
capacity
» Not all refineries have hydrocrackers
•Intent is to minimize the production of heavy fuel oil
» Light ends are approximately 5% of the feed.
» Middle distillates (kerosene, jet fuel, diesel, heating oil) still contain
uncracked polynuclear aromatics
•All liquid fractions are low in sulfur & olefins

37
 Hydrocracking Chemistry

• Cracking reactions
» Saturated paraffins cracked to form lower molecular weight olefins &
paraffins
» Side chains cracked off small ring aromatics (SRA) & cycloparaffins
(naphthenes)
» Side chains cracked off resins & asphaltenes leaving thermally stable
polynuclear aromatics (PNAs)

But condensation (dehydrogenation) also occurs if not limited by
hydrogenation

38
 Hydrocracking Chemistry

• Hydrogenation reactions
» Exothermic giving off heat
» Hydrogen inserted to saturate newly formed molecule from aromatic
cracking
» Olefins are saturated to form light hydrocarbons, especially butane
» Aromatic rings hydrogenated to cycloparaffins (naphthenes)
» Carbon-carbon bonds cleaved to open aromatic & cycloparaffins
(naphthenes) rings
» Heteroatoms form hydrogen sulfide, ammonia, water, hydrogen
chloride

39
 Hydrocracking Chemistry

• Isomerization Reactions
» Isomerization provides branching of alkyl groups of paraffins and
opening of naphthenic rings
• Condensation Reactions.
» Suppressed by hydrogen

40
 Hydrogen Consumption

• Carbon bonds with heteroatoms broken & saturated

» Creates light ends

Heavier distillates make more light ends from breaking more
complex molecules
» Sulfur converted to hydrogen sulfide
» Nitrogen converted to ammonia
» Oxygen converted to water
» Organic chlorides converted to hydrogen chloride

41
 Hydrogen Consumption

• Saturation of carbon-carbon bonds

» Olefins saturated to form light hydrocarbons.

Consumption stoichiometric — one hydrogen molecule added for
each double bond
» Aromatic rings hydrogenated to cycloparaffins (naphthenes).

Severe operation — hydrogen consumption strong function of
complexity of the aromatics
• Isomerization reactions generally not present
• Metals deposited directly on the catalysts
» Excess metals reduce catalyst activity & promote dehydrogenation
(produces coke & hydrogen)

42
 Hydrogen Consumption

• Have cracking of carbon-carbon bonds

Severe operation — hydrogen consumption strong function of
complexity of the aromatics
• Hydrogen lost in mixture with products
» Equilibrium with light gases

Significant — may double amount required for sulfur removal
» Absorbed in liquid products

Usually small compared to hydrogen used for sulfur removal
» Lost with purge gas

43
Single Stage Hydrocracking

44
Severe Two Stage Hydrocracking

45