Section 6 - Page 1

SECTION 6

TREATING PROCESSES
Section 6 - Page 2
GAS OIL CONVERSION REFINERY: REVIEW
Naphtha
Kerosene
Naphtha
Hydrofiner
Kerosene
Hydrofiner
Distillate
Hydrofiner
Distillate
A
P
S
Crude
Atm.
Residue
VGO
V
P
S
Vacuum
Residue
S
p
l
i
t
t
e
r
C
a
t
C
r
a
c
k
e
r
Cat. Naphtha
(Mogas)
LPG/Gas
Cat.
Bottoms
LPG
Light
Naphtha (Mogas)
Reformate
(Mogas)
Kerosene
(Jet Fuel)
Fuel Oil
Catalytic
Reformer
Cat
Distillate
Diesel
Heating Oil
Section 6 - Page 3
COMPLEX CONVERSION REFINERY: REVIEW
Naphtha
Kerosene
Naphtha
Hydrofiner
Kerosene
Hydrofiner
Distillate
Hydrofiner
Distillate
A
P
S
Crude
Atm.
Residue
VGO
V
P
S
Vacuum
Residue
C
O
K
E
R
S
p
l
i
t
t
e
r
C
a
t
C
r
a
c
k
e
r
Cat. Naphtha
(Mogas)
LPG/Gas
Cat.
Bottoms
to Fuel
LPG
Light
Naphtha (Mogas)
Reformate
(Mogas)
Kerosene
(Jet Fuel)
Coke
KN
LKGO
HKGO
Cracked
Distillate
Reformer
Cat
Distillate
Diesel
Heating Oil
Gas
Section 6 - Page 4
PRODUCT QUALITY TRENDS FOR ALL REFINERIES
ENVIRONMENTAL CONSIDERATIONS HAVE HISTORICALLY
DICTATED REDUCED CONTAMINANT LEVELS IN FUELS
PRODUCTS, PRIMARILY SULPHUR

AT SAME TIME, AVERAGE REFINERY CRUDE SLATES HAVE
BEEN GETTING HEAVIER AND HIGHER IN SULPHUR

HEAVY OIL TREATING PROCESSES WERE DEVELOPED TO
DESULFURISE FUEL OIL PRODUCTS FOR SALE (HYDRO-
DESULPHURISATION OR HDS)

AS FUEL OIL DEMAND HAS DECREASED, HEAVY OIL
PROCESSES HAVE BEEN ADAPTED TO SERVE OTHER
PURPOSES AS PART OF REFINERY OPTIMISATION

DISTILLATE HDS UNITS DESIGNED FOR 0.3 WT% S ARE NOW
BEING PUSGED TO ACHIEVE LOWER SULPHUR (0.05 WT%)
TARGETS
Section 6 - Page 5
HYDROTREATING PROCESSES
HYDROTREATING IS THE MOST IMPORTANT EXXON PRODUCT
AND FEED QUALITY IMPROVEMENT PROCESS
TREAT PETROLEUM FRACTION WITH HYDROGEN IN THE
PRESENCE OF CATALYST
FEEDSTOCKS INCLUDE VIRGIN AND PROCESSED STREAM IN
NAPHTHA AND DISTILLATE BOILING RANGE
SIGNIFICANTLY REDUCES SULFUR, NITROGEN AND OTHER
HETEROATOMS
GENERALLY IMPROVES COLOR, ODOR, STABILITY AND
COMBUSTION CHARACTERISTICS

GROWTH STEMMED FROM AVAILABILITY OF HYDROGEN AND
REDUCTION IN SULFUR SPECIFICATIONS
REPLACED OLDER CHEMICAL TREATING METHODS IN MOST
CASES
Section 6 - Page 6
CHEMICAL TREATING STILL USED IN CERTAIN
CASES
CHEMICAL TREATING USED IN SPECIAL SITUATIONS
HYDROGEN AVAILABILITY
IMPROVE SPECIFIC PRODUCT QUALITY
SOMETIMES MORE ECONOMICAL

CAUSTIC (NAOH) / WATER WASH
USED TO REMOVE MERCAPTANS IN LIGHT ENDS STREAMS

MEROX (MERCAPTAN OXIDATION) PROCESS (UOP)
USES CAUSTIC + CATALYST
SWEETENING PROCESS
CONVERTS MERCAPTANS (ODOUR) TO DISULPHIDES
EXTRACTIVE PROCESS
REMOVES DISUPHIDES
Section 6 - Page 7
PROCESSED DISTILLATE HYDROFINER
Make-up
Gas
Compressor
Recycle
Gas
Compressor
Feed
Pump
Make-up
Treat Gas
Reactors
Furnace
MEA
Scrubber
Rich
MEA
MEA Regeneration
Purge to
Fuel Gas
Stripper/
Hot and Cold
Separators
Steam
Wild Naphtha
to APS
Water
Fuel Gas to
MEA Scrubbing
Distillate
Product
To Tankage
Lean
MEA
Feed
Section 6 - Page 8
OPERATING CHARACTERISTICS OF HYDROFINERS
OPERATE AT HIGH (95+%) SERVICE FACTORS
ONE YEAR CYCLE TYPICAL, BUT LONGER CYCLES OFTEN
ACHIEVED

FLEXIBLE - CAN HANDLE MORE THAN ONE TYPE OF FEED

OPERATING TEMPERATURE INCREASED DURING CYCLE TO
COMPENSATE FOR CATALYST DEACTIVATION
HYDROGEN PARTIAL PRESSURE MINIMIZES DEACTIVATION
AT END OF CYCLE, CATALYST REGENERATED BY BURNING
OFF COKE
Section 6 - Page 9
LOW SULPHUR DIESEL LATEST CHALLENGE FOR
HYDROFINING

LEGISLATION LOWERING SULPHUR SPECIFICATIONS FOR
DIESEL PRODUCTS (0.05 WT% SULPHUR)
EXISTING DIESEL H/FS DESIGNED TO ACHIEVE 0.3 WT%

SOME EXISTING UNITS CAN BE OPERATED AT HIGHER
SEVERITY TO ACHIVE NEW SPECIFICATIONS

OTHER UNITS REQUIRE REVAMPING
ADDITIONAL REACTOR VOLUME
OTHER FACILITIES (PREHEAT, TREAT GAS, ETC.)
Section 6 - Page 10
COMPONENT SULPHUR CONTRIBUTIONS TO FUEL OIL POOL
ARAB HEAVY CRUDE (HYDROSKIMMING BASIS)
WT% POUNDS SULPHUR/
KB/D SULPHUR FUEL OIL BARREL
VIRGIN KERO FLUX 7 0.2 0.1
VGO 26 3.0 4.5
VAC RESID 23 6.0 9.0
TOTAL POOL 56 4.0 13.6
TYPICAL SPEC. FOR RSFO 3.9 10.2

RESID CONTRIBUTES BULK OF SULPHUR TO FUEL OIL POOL

REMOVING 25% OF TOTAL SULPHUR IN COMPONENTS REQUIRED
TO MEET SPECIFICATION
75% OF VGO SULPHUR OR
38% OF RESID SULPHUR
Section 6 - Page 11
MAJOR FUEL OIL DESULPHURIZATION PROCESSES
GO-FINING (EXXONMOBIL TRADE NAME FOR GAS OIL HYDRO-
DESULPHURISATION)
GAS OIL RANGE FEED STREAMS
VACUUM GAS OIL (VGO)
HEAVY COKER GAS OIL (HKGO)
CAT CYCLE OILS (HCCO)

RESIDFINING (EXXONMOBIL TRADE NAME FOR RESID HYDRO-
DESULPHURISATION)
RESID FEEDSTOCKS

BOTH PROCESSES RESEMBLE HYDROFINERS, BUT AT MORE
SEVERE CONDITIONS AND WITH GREATER PROCESS COMPLEXITY
Section 6 - Page 12
GO-FINING
Sour
Water
Product
Stripper
Wild
Naphtha
Stripper
Off Gas
Lean
MEA
Purge
Gas
H2S
Absorber
Rich
MEA
Hot
Separator
HDS
Reactors
Preheat
Furnace
Go-finer
Feed
MEA
Regenerator
H2S
Sour
Water
Cold
Separator
Water
Wash
H2O
Sour
Water
Hydrogen
Make-up
Desulfurized
Gas Oil
Product
MEA
Make-up
Steam
Steam
Generation
Recycle Gas
Compressor
Section 6 - Page 13
GAS OIL CONVERSION REFINERY WITH HYDRODESUFURIZATION
Naphtha
Kerosene
Naphtha
Hydrofiner
Kerosene
Hydrofiner
Distillate
Hydrofiner
Distillate
A
P
S
Crude
Atm.
Residue
VGO
V
P
S
Vacuum
Residue
S
p
l
i
t
t
e
r
C
a
t
C
r
a
c
k
e
r
Cat. Naphtha
(Mogas)
LPG/Gas
Cat.
Bottoms
LPG
Light
Naphtha (Mogas)
Reformate
(Mogas)
Kerosene
(Jet Fuel)
Low Sulfur
Fuel Oil
Catalytic
Reformer
Cat
Distillate
Diesel
Heating Oil
Residfiner
Gofiner
Section 6 - Page 14
HYDROTREATING PROCESSES REQUIRE
SUPPORT PROCESSING
REFINERY TREAT GAS SYSTEM PROVIDES HYDROGEN TO
HYDROTREATING/ HYDROCONVERSION UNITS
INCLUDES H2 GENERATION, DISTRIBUTION AND RECOVERY

SULPHUR REMOVAL FROM REFINERY TREAT GAS STREAMS
REQUIRED BY ENVIRONMENTAL LIMITATIONS ON REFINERY
SULPHUR EMISSIONS
INCLUDES RECOVERY OF ELEMENTAL SULPHUR AS
REFINERY BYPRODUCT

CONTAMINANT REMOVAL FROM REFINERY EFFLUENT WATER
ONSITE SOUR WATER STRIPPING
OFFSITE WASTE WATER TREATING
Section 6 - Page 15
RESIDFINING
MEA
Scrubbing
MEA
Regeneratio
n
Guard
Chamber
Feed
Furnace
HDS
Reactors
Hot
Separator
Quench
Water
Treat Gas
Furnace
Product
Stripper
Cold
Separator
Sour Water
(To Stripping)
Hot Sep. Vapor
Codenser
Trim
Cooler
Steam
Generation
CW
Sour Water
(To Stripper)
C1-C4
Fuel Gas
CW
Compressor
400/650 HAGO
(Optional)
400+
Product
C5-400
Wild Naphtha
CW
Purge
Gas
KO Drum
Recycle Gas
Compressor
Make-up H
2
from
H
2
Plant 950 psig
Feed
Filter
Feed
Surge
Drum
Hot Feed
(350F)
Hot Sep. Vapor
Cold Sep. Liquid
Hot Sep.
Vapor Feed
Hot Sep. Vapor
Treat Gas
MEA
Section 6 - Page 16
CAT FEED HYDROTREATER (CFHT)
The conversion of cat cracking feed to higher value gasoline and light ends can be
significantly improved by severe hydrotreating of the more aromatic gas oils,
particularly those that contain nitrogen and/or heavy metals (which are different
types of catalytic cracking catalyst poisons). If the multi-ring aromatics in the gas
oils can be saturated such that only one core aromatic remains in the molecular
structure. That molecule will eventually be converted to gasoline or light-ends. Also,
higher cat cracking conversion can be achieved if three ring (cores) aromatics can
he reduced because of lower coke yields. Coke burning capacity often limits the cat
cracking unit conversion level.

In order to hydrotreat PGO at this severity, it is necessary to operate around 1500
psig and below 1 V/V/hr. Operating temperatures are in the range of 670-730F EIT
(a kinetic average). For typical feed stocks, we expect 600-1100 SCF/barrel of
hydrogen consumption. Typical run lengths are from less than 1 year to over 3
years.

Section 6 - Page 17
CAT FEED HYDROTREATER (CFHT)
Figure 4 is a flow plan of the Baytown Cat Feed Hydrotreater. The feed is mixed
with hot hydrogen at the exit of the recycle H2 furnace. Because of possible fouling
of the catalyst beds, the feed goes through a filter to remove particulates before the
hydrogen is added. The H2 and feed go through a small reactor, filled with the
catalyst, which acts as a guard reactor to remove metal contaminants. Then the
mixture goes through the reactor train. After the reactors, the liquid and gas are
separated in flash drums, and the hydrogen is recycled to the furnace. On the way,
it passes through an amine scrubber to remove the H2S formed in the reactors.
The liquid goes to the fractionator, where an overhead stream is taken which is
separated into gas and naphtha. The fractionator bottoms is the hydrotreated
product that can be used as high quality catalytic cracking feed.

Section 6 - Page 18
FIG 4 - CAT FEED HYDROTREATER (CFHT)
MAIN REACTORS
SEPARATORS
AMINE
SCRUBBER
RECYCLE HYDROGEN
FRACTIONATOR
GAS AND
NAPHTHA
CAT CRACKER
FEED
FILTER
FEED
COMP
MAKEUP
HYDROGEN
FURNACE
GUARD
REACTOR
Section 6 - Page 19
GO-FINING
GO-fining is a process for sulphur reduction in gas oils. It is an Exxon Engineering
process, and several units have been built world-wide, especially in Venezuela. The
only one in the Exxon Company, U.S.A. is at Baytown (HU6A/6B now in diesel and
jet fuel service).

Previously, the process application is for reducing sulphur in fuel oil by
desulphurizing the flux oil to be blended with vacuum residuum. Now because of
poor quality crude and tighter diesel specifications, these two units are used for
severe hydrotreating of middle distillates.

Typically operating conditions for Go-finers are 600 PSIG, and 650F. The catalyst
is cobalt/molybdenum or nickel/molybdenum, and can be regenerated and reused.
Regeneration is done offsite. This is required after about 18 months onstream. The
treat gas rate is normally about 1000 SCF per barrel of feed, and hydrogen
consumption ranges from about 200 to 500 SCF/B.

Feedstock used to be 650-1050F cut range gas oil, from any source. Sulphur in
the feed was reduced by 75 percent. Now the feeds are 350-520F and 520-620F
distillate.
Section 6 - Page 20
GO-FINING
A small yield of gas and naphtha occur, but the 350F + cut is usually 100 percent
on feed.

A flow plan is shown in Figure 5.

Feed exchanges heat with the reactor effluent and is mixed with the recycle
hydrogen stream. This goes through the furnace, and then through the reactors in
series. The reactor effluent is separated from recycle hydrogen in the hot separator.
The hydrogen is cooled and goes to the cold separator, where more liquid is
separated out. The hydrogen goes then to a water wash and an amine scrubber
before being compressed for recycle. Liquid from both the hot and cold separators
goes to the product stripper. By steam stripping, the light ends are separated from
the gas oil product.
Section 6 - Page 21
GO-FINING
Section 6 - Page 22
Hydrofining and Hydrotreating
Hydrofining and hydrotreating are broad terms which in general refer to processes
that remove or convert impurities by catalytic treatment with hydrogen. The effect is
primarily In the reaction of hydrogen with sulphur and nitrogen in heavier molecules
to produce hydrogen sulfide and ammonia. For example:

2 RNH2 + H
2
=> 2 NH
3
+ 2RH
Amine Ammonia + Paraffin
and
2 RSH + H
2
=> 2 H
2
S + 2 RH
Mercaptan

Other reactions include saturation of olefins and reduction of oxygen compounds,
such as:

R C = C + H
2
=> R - C - C
Olefin Paraffin
and
Section 6 - Page 23
The net result is an improvement in many properties, such as odour, colour,
corrosivity, gum formation, stability, burning characteristics, cracking quality and
carbon forming in cracking. It has largely replaced the old process of acid treatment
and clay percolation. In general, hydrotreating refers to any process short of
conversion, while hydrofining usually means relatively mild conditions for colour
improvement, and hydro-desulphurization means more severe treatment required
for deep desulphurisation of heavier oils. Hydrofining is an Exxon Engineering
process, which is very similar to a number of other processes developed by other oil
companies.

The process flow in a hydrotreater is essentially the same regardless of the
operating conditions or catalyst. Please refer to the flow plan in Figure 6 on the next
page.

The feed is heated to reaction temperature in a furnace, and is joined by a stream of
hydrogen. The mixture flows down through the fixed bed of catalyst in the reactor.
The effluent is cooled and the liquid is separated from the gas in a separator, which
usually (but not always) provides a hydrogen recycle stream. The liquid is again
separated at lower pressure, and the product is stripped for flash correction.

Hydrofining and Hydrotreating
Section 6 - Page 24
The catalyst may be cobalt/molybdenum, or nickel/molybdenum, depending on the
feedstock and the purpose of the unit. For but desulphurization, cobalt/
molybdenum is the more common. Nickel catalysts are core effective in removing
nitrogen than cobalt molybdenum, and are usually used with heavier feedstocks.
Catalysts are usually in the form of 1/60 extrudate. Most catalysts are now
regenerated ex-situ (offsite).

When either new or regenerated catalyst is loaded in the reactors, it is necessary to
activate the metal oxides (cobalt, nickel, or molybdenum) by carefully controlled
sulphiding. This is done in a hydrogen rich environment, but if the metals are
reduced before they are completely sulphided, a large loss of catalyst activity will
result. Operating conditions also depend on the feedstock. In general, the range of
conditions are these:

Hydrofining Hydrodesulphurization
Temperature F 500 - 700 600 - 800
Pressure, PSIG 200 - 600 600 - 3,000
Feed Rate, V/Vlhr 0.5 - 5.0 0.2 - 1.2
H2 Treat SCF/B 200 - 1,000 1,000 - 3,000
H2 Consumption SCF/B 10 - 500 200 - 1,000
Hydrofining and Hydrotreating
Section 6 - Page 25
Figure 6 - Hydrotreater flow plan
SEPARATORS
FUEL GAS
REACTORS
FURNACE
HYDROGEN
DEHYDRATOR
PRODUCT
Section 6 - Page 26
Some of the operating variables and the effects of changing them are:


Variable Effect

Increased feed rate Reduce sulphur and nitrogen removal

Increased temperature Increase sulphur and nitrogen removal

Increased pressure Increase sulphur and nitrogen removal

Increased hydrogen purity Increase sulphur and nitrogen removal

Increased treat gas rate Increase sulphur and nitrogen removal

Hydrofining and Hydrotreating
Section 6 - Page 27
CAT FEED HYDROTREATER
Section 6 - Page 28
HYDROFINING REACTIONS
Section 6 - Page 29
HYDROFINING REACTIONS
Section 6 - Page 30
FIGURE 1 - SCHEMATIC FLOW PLAN -
HYDROTREATER
Section 6 - Page 31
GO-FINER FLOW DIAGRAM