PROCESS AND CATALYST INNOVATIONS IN

HYDROCRACKING TO MAXIMIZE HIGH QUALITY

DISTILLATE FUEL
Vasant Thakkar, Jill M Meister, Richard J Rossi and Li Wang
UOP LLC, a Honeywell Company
Des Plaines, Illinois, USA

INTRODUCTION
Steady worldwide economic growth continues to drive ever-increasing demand for transportation
fuels, and in particular, diesel. Consumption of low-sulfur, high-quality diesel is projected to
grow at a faster rate than both fuel oil and gasoline over the next 10 years. Of particular interest,
distillate demand in Asia is expected to increase by over 2.5 million barrels per day during that
period. Much of this growth in demand and stricter product quality requirements requires
increased conversion and upgrading of heavy low-quality feeds such as vacuum gas oil, heavy
coker gas oil, and deasphalted oils (DAO). Hydrocracking and hydrotreating technologies and
catalyst innovations have taken on an increasingly prominent role as solutions in many refinery
configurations.

UOP has an outstanding level of commercial experience in delivering hydrocracking process and
catalyst technology solutions. This paper will present process and catalyst solutions for cases
where hydrocracking is used for full conversion of VGO and heavy feedstocks to high quality
distillate fuel product, with specific focus on process innovations embodied in enhanced two-
stage and UOP HyCycle Unicracking Process designs. The enhanced two-stage UOP
Unicracking process design provides a significant increase (up to 5 7 wt%) in distillate yields
by incorporating process and catalyst innovations while processing difficult high nitrogen heavy
feedstocks. Discussion of distillate production options must also consider how refiners will
process low cetane, highly aromatic light cycle oil (LCO). Therefore this paper will also discuss
the UOP LCO-X Process which allows value to be added to LCO by converting it into blend
stocks or aromatics production in a Petrochemical complex.

2008 UOP LLC. All rights reserved. Page 1

At the same time, the production of biofuels is expanding at a rapid pace worldwide as a result of
increasing petroleum prices, government regulations, and initiatives to reduce greenhouse gas.
Future widespread use of biofuels depends on developing new technology to produce high
quality transportation fuels from highly oxygenated, biologically derived, feedstock. UOP and
Eni, S.p.A. recognized the need for a different processing route to convert vegetable oils into
high quality diesel fuel or diesel blend stock that is fully compatible with petroleum derived
diesel fuel. As a leading provider of technologies for the refining industry UOP has developed
the Ecofining Process technology in collaboration with Eni.

In addition, several new catalysts have been developed for these new and existing hydrocracking
units. The catalysts are designed for optimal performance in varying reaction environments while
accomplishing controlled addition of hydrogen to the products.

MARKET SITUATION
Refined Products Demand

The growth of refined products demand varies geographically (Figure 11). The growth rates are
slowest in the Americas, Europe and the developed countries in Asia. However, rapid economic
development in China, India and the Middle East will help total refined products demand grow
nearly 14 million barrels per day, a 1.7% average rate, over the next 10 years. This 10 year
demand represents an average worldwide growth rate essentially the same as has been seen over
the past 10 years. It is worth noting that world wide demand for diesel has exceeded the gasoline
demand since 2000 and that this trend is projected to continue through 2015.

Figure 1: Worldwide Refined Products Demand

35,000 Americas EAF Middle East China India OAP

1.0% 1.1% 2.5% 6.1% 2.4% 1.0%

30,000
Total
Total Refined
Refined Products
Products Demand
Demand
2007:
2007: 78
78 million
million BPSD
BPSD
25,000
2017:
2017: 92
92 million
million BPSD
BPSD

20,000
KBPSD

15,000

10,000

5,000

0
2007 2017 2007 2017 2007 2017 2007 2017 2007 2017 2007 2017
Gasoline Jet/Kero Distillate Fuel Oil Naphtha Other

Page 2
The pattern of refined fuels demand in Asia has changed substantially in recent years. With the
automobile fleet expanding in developing Asian economies as well as the rural areas of more
advanced Asian economies, refined products demand is forecasted to grow at a rate of 3.4%
annually over the next ten years (Figure 2). The distillate demand has a ten-year growth rate of
3.6% and gasoline demand increase is forecasted at 4.8%, both above the growth rate of refined
products. Since base distillate demand is significantly higher than gasoline, these growth rates
equate to 2.7 million barrels per day (Mb/d) distillate demand versus 1.6 Mb/d of gasoline
demand over the ten year period.

Figure 2: Asian Refined Products Demand

12,000
Thailand
Taiwan
10,000 South Korea
Japan
Indonesia
India
8,000 China
KBBL/SD

6,000

4,000

2,000

0
2007 2017 2007 2017 2007 2017 2007 2017
Gasoline Distillate Naphtha RSFO

Source: P&G GPMO Update 2007

Environmental Regulations

Motor fuel specifications have changed significantly over the past 10 to 15 years and are
continuing to evolve. The World Wide Fuel Charter Initiative is helping to set advanced
emission control requirements, and thus drive fuel qualities. Sulfur and aromatics contents are
being reduced in most developed countries and the trends are spreading to other regions. The
Clean Air Initiative for Asian Cities (CAI-Asia) is developing a road map for cleaner fuels and
vehicles in Asia2. The most notable changes govern the sulfur content of both gasoline and diesel
fuel. Tier II regulations in the U.S. have driven gasoline sulfur down to < 30 ppm. Europe has
reduced sulfur to 50 ppm with further tightening to 10 ppm scheduled to take place later this
decade. Japan already has very low sulfur levels in its gasoline while other countries are moving

Page 3
in the same direction, but most at a slower pace. The evolution of gasoline sulfur specifications is
shown in Figure 33.
Figure 3: Changing Gasoline Sulfur Standards
1000
USA

Europe U.S. Tier 2

Japan 150
100
Sulfur, ppm

Germany
California 50
30
15
10 10
5
Automobile
Manufacturers

1
1999 2001 2003 2005 2007
Source: AM-02-36, NPRA 2002 Annual Meeting

Diesel fuel sulfur content is being reduced at a similar pace to gasoline with Germany mandating
maximum sulfur levels of 10 ppm in January 2003, the U.S. mandating 15 ppm in 2006, Japan
planning to go to 10 ppm, as well as other Asian countries are following a similar trend. Several
other European countries are voluntarily switching to 10 ppm sulfur in diesel ahead of a 2009
deadline (Figure 4)2.

Figure 4: Changing Diesel Sulfur Standards

10000

Indonesia

1000
Vietnam
PRC-Nationwide Phillipines
PRC-Beijing India-Nationwide
Sulfur, ppm

Thailand
Malasia
100
India-Metro
Singapore Taiwan

USA
Japan EU South Korea
10

1
2000 2001 2002 2003 2004 2005 2006 2007 2008 2009 2010 2011

Page 4
By the end of the decade, 80% of the worlds gasoline consumption will be ultra-low sulfur (< 50
ppm). Currently, ~65% of the world road diesel is refined to low and ultra-low sulfur diesel. This
percentage is projected to rise to approximately 75% by 2015.
History of the Hydrocracking Technology

Hydrocracking is one of the oldest hydrocarbon conversion processes. In the late 1950s and early
1960s hydrocracking of petroleum fractions at moderate pressure became a commercial reality4.
During this time frame, UOP announced the Lomax hydrocracking process enabling refiners to
produce any desired ratio of motor fuels to heating oils within extremely wide limits and so
permitted the production of more gasoline in summer and more fuel oil in winter without the
usual seasonal surpluses. The UOP Isomax process, in partnership with Chevron until the mid
70s, was a similar system that could be operated to directly desulfurize fuel oils so that refiners
could make them burn cleaner for domestic and industrial uses and to crack gas oils to more
valuable products5. During the mid 50s, Union Carbide laboratories and pilot plants were
exploring a fourth general catalyst category: synthetic zeolites, or molecular sieves. These
products would become particularly important to UOP several decades later with the joint
venture involving UOP and the Catalysts, Adsorbents, Processes and Systems division of Union
Carbide5. Beginning in 1961, UOP scientists and engineers also created a series of hydrocracking
processes. The purpose was to produce higher yields of gasoline and other distillates.
Hydrocracking is a generic term that covered numerous UOP processes, among them the Lomax,
Isomax, HDC Unibon, HC Unibon, and Unicracking (in partnership with Unocal) Processes.5
In 1990, UOP and Unocal entered a joint venture in the hydroprocessing technology area and
began jointly developing and licensing the Unicracking Process. Recently, UOP and Albemarle
have entered into an alliance enabling the enhancement and optimization of process and catalyst
solutions in hydroprocessing technologies. These continual technology and catalyst innovations
are a mainstay within the UOP hydrocracking history. This effort is reflected by the fact that
UOP has licensed over 185 hydrocracking units world wide covering over 40 countries.

UNICRACKING PROCESS FLOW SCHEMES

UOP has offered hydrocracking processes since the inception of commercial hydrocracking.
There are several Unicracking flow schemes presently offered to meet individual refinery needs
and project objectives. The basic flow schemes considered are single-stage or two-stage design.
The single-stage Unicracking Process can be once through hydrocracking for partial conversion
or a recycle flow scheme for full conversion as shown in Figure 5. These flow schemes are
simple and cost effective designs widely used in the refinery.

The once-through Unicracking process will produce hydrocracked products as well as high
quality unconverted oil that can be excellent feed for FCC or ethylene cracking units. The
unconverted oil can also be used as a high quality lube base stock. When high conversion is

Page 5
desired, the single-stage recycle flow scheme offers a simple and cost effective design for
moderate capacity hydrocracking designs.

Figure 5: Single-Stage Unicracking Process Flow Schemes

H2 Once Through
y Lowest cost
R y Can process very heavy, high boiling
F feedstocks
Products y Produces high value bottoms
product for:
To other FCC

Once Through units Olefins plant

Lube oil

Single Stage
H2
y Least costly 100% conversion
configuration
F y Moderate product slate and quality
R flexibility
Recycle
y Most cost effective 100% conversion
Oil Products configuration for moderate capacity
units

Single Stage

Alternatively, two-stage flow schemes can be employed in specific situations. UOP two-stage
Unicracking process flow schemes can be a separate hydrotreat or a two-stage Unicracking
process as shown in Figure 6. In the separate hydrotreat flow scheme the first stage provides only
hydrotreating while in the two-stage Unicracking process the first stage provides hydrotreating
and partial conversion of the feed. The second-stage of the two-stage design provides the
remaining conversion of recycle oil so that overall high conversion from the unit is achieved.
These flow schemes offer several advantages in processing heavier and highly contaminated
feeds. Two-stage flow schemes are economical when the through put of the unit is relatively
high.

Page 6
 Figure 6: Two-Stage Unicracking Process Flow Schemes

H2 Separate Hydrotreat
H2
y Used when special product quality or
product slate requirements exist
R
R y Used when special feed
considerations are present
F
Large amount of product in feed
Products
Separate Very high nitrogen level in feed
Hydrotreat
Recycle Oil

Two Stage
H2 y Most cost effective for large capacity
units
y Provides high product quality and
R R F product slate flexibility

Products y Efficient to process difficult

feedstocks
y Low NH3 environment in second
Two Stage stage
Recycle Oil

As discussed above, the design of hydrocracking catalyst changes depending upon the type of
flow scheme employed. The hydrocracking catalyst needs to function within the reaction
environment and severity created by the flow scheme that is chosen. As indicated in Figure 6,
two-stage flow schemes provide a unique reaction environment for the second-stage
hydrocracking catalyst. The second-stage reaction environment is cleaner and significantly
boosts the cracking activity of the catalyst.

UOP has extensive experience designing various hydrocracking flow schemes as discussed
above. In the hydrocracking area UOP offers a comprehensive portfolio of process and catalyst
technology. As a leading licensor of refining technology UOP is committed to continuous
advancement and innovating process and catalyst to benefit refiners. In the following section we
will review recent advancements in the two-stage Unicracking process and catalyst.

Page 7
Enhanced Two-Stage Unicracking Process
During the early years of hydrocracking, refiners were mainly interested in maximizing
production of naphtha for reforming to high octane gasoline. UOP has designed many two-stage
units for the North American market for this purpose. However with advancements in
hydrocracking catalyst technology, and the demand for maximizing distillate yields from heavier
feedstocks two-stage design offers a cost effective option for a larger capacity maximum
distillate unit operation.

As part of continual renewal and advancement of technology, UOP has recently advanced the
two-stage Unicracking process. The following section will review the developments of an
enhanced two-stage hydrocracking process.

As shown in Figure 7, a typical two-stage hydrocracking design consists of the first stage that
provides hydrotreating and hydrocracking of the feed using two types of catalysts in one or two
reactors. The feed is hydrotreated and hydrocracked followed by separation of gas and liquid
effluents. The hydrocracked liquid effluent is fractionated into products and unconverted oil. The
unconverted oil is recycled to the second-stage hydrocracking reactor. The second-stage reactor
provides hydrocracking of unconverted oil so that overall conversion from the unit can be as
high as 100%.
Figure 7: Two-Stage Unicracking Flow scheme

Reactors
Recycle gas
Scrubber
Vent Gas

Cold
Separator Product
Separation

Butanes
Flash
Hot Drum
Separator Naphtha

Feed
Jet
Hot
H2 Flash
Drum
Distillate

Recycle UCO

HPNA RM
Control

Page 8
A major difference between the first and second stage hydrocracking reactor reaction
environments lies in the very low concentrations of ammonia, and hydrogen sulfide in the
second-stage. The first-stage reaction environment is rich in both ammonia and hydrogen sulfide
generated by hydrodenitrogenation and hydrodesulfurization of the feed. This significantly
impacts on the reaction rates, particularly cracking reaction rates, leading to different product
selectivity and catalyst activity between the two stages. This knowledge can be utilized in
conjunction with our understanding of catalyst design to optimize the catalyst system to obtain a
highly distillate selective overall yield structure. We can also take advantage of the impact of the
reaction environment on catalyst activity to set optimum severity for each stage and enable
achievement of catalyst life target with minimum catalyst volume. Overall the two-stage design
allows us to optimize conversion severity between the two-stages and thus maximize overall
distillate selectivity.

To more thoroughly understand how this is accomplished, let us explore what is occurring in a
bit more detail. The first-stage cracking catalyst, typically in series flow with pretreating catalyst,
receives a hydrotreated feed which is largely free of contaminants, except for small levels of very
refractory species. The feed to the hydrocracking section is rich in paraffins, isoparaffins,
naphthenes, naphtheno-aromatics, and alkyl aromatics. The predominant reactions are aromatic
hydrogenation, ring opening, and de-alkylation along with further isomerization and cracking of
paraffins. The hydrocarbon stream that exits the first-stage cracking reactor is rich in medium to
short chain paraffins and isoparaffins, naphthenes and alkyl aromatics with short to moderate
length side chains.

The distribution of these components is a strong function of catalyst type and reaction severity in
the hydrotreating reactor section, and the depth of conversion in the first stage cracking reactor.
An interesting consequence of the paraffin reaction chemistry is its dependence of the product
composition on the depth of conversion, or reaction severity. Due to the sequential nature of the
isomerization, primary cracking and secondary cracking of paraffins, preservation of heavier
products is enhanced at lower rather than higher conversion. In maximum distillate operation,
this implies that reducing conversion severity can achieve a highly distillate selective product
slate while increasing heavy diesel yields and reducing hydrogen consuming gas make.

First-stage cracking reactor effluent is then fractionated to recover cracked products and
unconverted oil. The composition of the unconverted oil, or fractionator bottoms, varies
depending on the unit feed and the processing objectives. It is usually rich in isoparaffins,
naphthenes, and single-ring aromatics and, in units processing heavy gas oils, can contain
refractory polynaphthenic compounds. In two-stage designs, unconverted oil is recycled back to
the second-stage hydrocracking reactor section for further conversion. Conditions in the second-
stage are more favorable to conversion of the refractory components of recycle oils due to the
relatively clean nature of this oil and the near-absence of ammonia and hydrogen sulfide in the
recycle gas after water wash and amine scrubbing. Proper design of the second-stage catalyst that

Page 9
has a balanced acid and metal function in the second-stage environment results in higher
distillate selectivity.

New advances in the two-stage Unicracking process design include several innovations in each
reaction section of the design. The pretreating section uses a high activity pretreating catalyst
that allows hydrotreating at a higher severity which provides good quality feed for the first-stage
hydrocracking section, thus enabling maximum first-stage selectivity to high quality distillate.
The second-stage is optimized by use of second-stage hydrocracking catalyst that is specifically
designed to take advantage of the cleaner reaction environment. The second-stage catalyst is
designed so that the cracking and metal functions are balanced. At the same time the second-
stage hydrocracking severity is optimized so that maximum distillate selectivity is obtained from
the second-stage of hydrocracking.

Second-Stage Catalyst Development

Hydrocracking catalysts are typically dual function catalysts, containing an acid-function for
cracking and a metal-function for hydrogenation. As shown in Figure 8, a good hydrocracking
catalyst, amorphous or zeolitic, is designed to balance these two functions for optimum
performance. In the figure two arrows indicate the type of functions (acid and metal) and the
height of the arrows indicates the strength of the individual functions. A catalyst with proper
balance of these two functions performs optimally in terms of desired product selectivity and
catalyst temperature activity/stability. However if a catalyst, designed for the first-stage sour
reaction environment typical of first-stage operation, is put in the cleaner reaction environment
of the second-stage, a significant boost in the cracking function is observed while the
performance of the metal-function remains basically unchanged. Thus the catalyst that was in
good balance for the first-stage environment becomes unbalanced for the second-stage
environment resulting in sub-optimal performance. This difference is exacerbated, as the
temperature required to achieve desired conversion is reduced. On the other hand the reduction
in temperature reduces the metal functionality thus reducing hydrogenation. Therefore, for ideal
second-stage catalyst, it is desired that the acidity of the cracking material is weak with a
stronger metal-function so that even though the catalyst may appear imbalanced for the first-
stage sour environment it will be in balance in the second-stage reaction environment. Applying
this design approach, UOP recently developed a new second-stage catalyst achieving higher
distillate selectivity than the current UOP standard design.

Enhanced two-stage performance is achieved by optimized first- and second-stage conversion

severity and application of the new second-stage catalyst. This results in significantly improved
overall C5+ yields and a product slate which is more selective to a high quality heavy diesel
product.

Page 10
 Figure 8: Second-Stage Unicracking Catalyst Design

Acid cracking activity

Metal activity
Temperature

Target
Amorphous

Low Zeolite

Low Zeolite
Amorphous

Target
Imbalance
between metal
and acid
function

1st Stage NH3 Removed Lower Temperature required for desired conversion

Pilot plant testing comparing the enhanced two-stage design relative to a standard baseline two-
stage design was carried out on heavy high sulfur, high nitrogen containing VGO feed. The pilot
plant tested VGO feed properties are in Table 1.

Table 1: Pilot Plant Test Feed Properties

Pilot Plant Test Feed VGO

API 22.37
Sp. Gr. 0.9196
Sulfur, wt% 2.33
Nitrogen, ppm 1121
Conradson Carbon, wt% 0.55
Distillation, (D2887), C
5% 320
50% 433
95% 547
EP 596

Page 11
The tests were run at 150 kg/cm2 pressure at 98-99% conversion. The total distillate yield
performance as compared in Figure 9 shows a 5-7 wt% increase in total distillate yield compared
to the baseline.

Figure 9: Enhanced Two-Stage Yield Improvement

+30
Enhanced Two Stage
Total Distillate Yield, wt%

Baseline Two Stage Yields

+25

Enhanced Two Stage

+20

+15

+10

+5 Baseline Two Stage

Base
0 200 400 600 800 1000
Time on Stream, hrs.
The product qualities from the enhanced two-stage operation were excellent, producing low
aromatics, high cetane with ultra low levels of sulfur in the diesel product as shown in Figure 10.

Figure 10: High Quality of Diesel Produced from Enhanced Two-Stage Design

30 75
Cetane Index (D4737)
Heavy Diesel Aromatics, wt%
Sulfur, ppm / Aromatics, wt%

25 Heavy Diesel, sulfur, ppm 70 Cetane Index

20 Cetane 65

15 60
Aromatics
10 55

5 ULSD 50

0 45
0 200 400 600 800 1000
Time on Stream, hrs

Page 12
The product qualities were similar or better when comparing kerosene and diesel cut properties
to the baseline, as shown in Figure 11.

Figure 11: Kerosene and Diesel Cut Properties

80
Baseline
70 Enhanced Two Stage
67.7 66.5

60

50

40
34.3
31.3
30

20

10

0
Jet Fuel Cut Smoke Diesel Cut
Point, mm Cetane Index
The enhanced two-stage design has improved distillate selectivity and the product slate is diesel
selective with lower light-end production resulting in 7-10% lower hydrogen consumption. The
product qualities are similar or better. The improved performance is achieved by optimum
processing severity and use of new second-stage hydrocracking catalyst.

Process Innovations

UOPs continued commitment to advance hydrocracking technology is evident from recent

introduction of various other innovations. UOP develops these process and catalyst innovations
using a state of the art research facilities and access to a large commercial operating data base.
These innovations have been incorporated into economic flow schemes such as the UOP
HyCycle Unicracking process, UOP Advanced Partial Conversion Unicracking process, and
LCO Unicracking process. UOP recognized the need for a process to convert vegetable oils into
a high quality diesel fuel for diesel blend stock to assist the rapidly developing market. As a
leading provider of technologies for the refining industry UOP has developed the UOP/Eni
Ecofining Process technology in collaboration with Eni. In the following sections these
innovations are reviewed and, where applicable, updates provided on the commercial status of
these technologies.

Page 13
HyCycle Unicracking Process

Development of the HyCycle Unicracking process is based on UOPs understanding of the

interactions between the catalyst functions and the reaction environment. This flow scheme
allows the refiner to achieve higher yields in a low-pressure operation and, therefore, more cost
effective design. The HyCycle Unicracking process flow scheme shown in Figure 12
incorporates engineering innovations such as the Enhanced Hot Separator (EHS) to permit low
conversion per pass, resulting in an economic and energy efficient design. The hydrotreating and
hydrocracking reactions are carried out in a back-stage design that takes advantage of the catalyst
activity in an improved hydrocracking reaction environment. The HyCycle Unicracking Process
design includes a post treating stage that decouples the cracking and hydrogenation reaction
stages. The post-treating stage in the HyCycle Unicracking process allows hydrocracked product
to be hydrogenated in an optimized environment and offers a co-processing option for other
distillate streams in the same unit.

The first fully integrated HyCycle Unicracking process unit is under construction in Asia and
scheduled to start-up in the third quarter of 2008. In addition, several licensees have chosen
selected HyCycle process innovations in their units.

Figure 12: UOP HyCycle Unicracking Flow Scheme

H2
Fuel Product
Gas Fractionator
HC Amine
Rx Scrubber To LPG
Recovery
Feed
EHS HPS S
HT
Rx
PT CF
Rx
HF

Short Recycle 0.5%

UCO
Long Recycle

Page 14
Advanced Partial Conversion Unicracking (APCU) Process

The Advanced Partial Conversion Unicracking process is one example of an innovative flow
scheme developed by utilizing concepts from the HyCycle Unicracking process. In this specific
case, HyCycle Unicracking process innovations were extended to allow production of ultra low
sulfur diesel (ULSD) at low conversion in a lower pressure design while pretreating FCC
feedstock. The design concept allows the refiner to optimize hydrogen addition to FCC feed
while maintaining the proper level of hydrogenation for high quality distillate. This innovation is
important because the unit pressure is often set by the need to produce low-aromatic, high-cetane
diesel. Consequently, the unit would produce unconverted oil with a higher than optimal
hydrogen content in the FCC feed, thus resulting in higher overall hydrogen consumption. The
APCU process flow scheme depicted in Figure 13 is designed to produce ULSD and
hydrotreated FCC feedstock as primary products, while operating at a significantly lower
pressure. This enables the refiner to achieve increased production of ULSD, and improve the
quality of FCC feedstock without consuming more hydrogen than is required.

Figure 13: Advanced Partial Conversion Unicracking Process Flow Scheme

H2
Raw Co-feed
Feed
AMINE

HT PT
Rx Rx
Naphtha
SEP
HC E F.G.
Rx H
S
ULSD

FCC Feed

Separation of cracked products from the desulfurized FCC feed in the Enhanced Hot Separator
(EHS), followed by hydrotreating allows distillate quality to be controlled independently of FCC
feed quality. Over-treating of FCC feed is avoided thus hydrogen consumption is minimized.
Hydrogen savings are significant as the APCU process can reduce hydrogen consumption by five
to ten percent compared to a conventional mild hydrocracking unit. Integration of a separate
hydrotreating reactor in the process provides benefits as well as it enables post-treating of other
refinery middle distillate streams in a single unit.

Page 15
LCO Unicracking and LCO-X Processes

As refiners move to higher conversion in the FCC process, increased amounts of light cycle oil
(LCO) is produced. At the same time, the LCO being produced is of lower blend quality (i.e.
reduces cetane) and typical outlets for it are shrinking due to the limited market for fuel oil. The
LCO Unicracking process offers a value added option to convert LCO into blendable gasoline
and ULSD. The LCO Unicracking process combines low pressure operation with catalyst
innovations that allow effective processing of highly aromatic feed like LCO to convert LCO
into high octane gasoline and ULSD blend stocks6.

Taking this technology one step further, the LCO Unicracking process has been integrated with
petrochemical processes to maximize aromatics production as shown in Figure 14. The UOP
LCO-X process achieves synergy between refining and petrochemicals to produce high-quality
petrochemical-grade xylenes while avoiding the problems associated with finding a suitable
outlet for low-quality LCO. A reasonably sized LCO-X plant can easily supplement the xylene
feed for a world-scale para-xylene facility. These supplemental xylenes can be produced at a
lower cash cost than the xylenes derived from naphtha reforming. As a result, the LCO-X
process offers a sustainable competitive advantage for refiners who are integrated with aromatics
production7.

Figure 14: LCO-X Process Flow Scheme

LCO
Feed

HT Light
LPG Naphtha

HC
Aromatics
Off Maximization Benzene
HPS Gas
Mixed
LPS
Xylenes

ULSD
Blend
Stock

Page 16
Ecofining Process

As a leading provider of technologies for the refining industry UOP has developed the Ecofining
process technology in collaboration with Eni S.p.A.. The process converts vegetable oils, spent
oils and animal fats into green diesel fuel. The quality of the resulting green diesel fuel is
exceptionally high and can be readily blended in any proportion into the petroleum diesel pool
without requiring major changes in vehicle technology or distribution systems8. This technology
is now available for license and commercial operation is expected by 2009.
The Ecofining process flow scheme is illustrated in Figure 15. The Ecofining process is a
standalone process designed to convert biomass feedstocks to green diesel.
Figure 15: Ecofining Process Flow Scheme

Vegetable Make-up
Oil Hydrogen

Acid
Acid Gas
Gas
Reactor Removal CO2
Removal

Propane
and
Light Ends
Separator
Naphtha
or Jet

Water Stripper

Diesel
Product

Page 17
 Table 2: Petroleum Diesel, FAME, and Green Diesel Product Property Comparison
Petroleum ULSD Biodiesel (FAME) Green Diesel

Oxygen Content, % 0 11 0

Specific Gravity 0.84 0.88 0.78

Sulfur content, ppm <10 <1 <1

Heating Value MJ/kg 43 38 44

Cloud Point, C -5 -5 to +15 -30 to -10

Cetane 40 50-65 70-90

Lubricity Baseline Good Baseline

NOx & PM Baseline Higher Lower

Tank Heating No Yes No

Refinery Blending & Yes No Yes

Pipeline Shipping

Stability Baseline Poor Baseline

Catalyst Innovations
Designing catalysts which can be successfully used for processing heavy feeds requires an
understanding of the interactions of many factors. Detailed knowledge is increasingly important
for controlling reaction pathways to achieve specific product types to meet todays market
demands. The key considerations for optimal catalyst design require good understanding of the
molecular transformations of feed to product with respect to catalyst functions and process
variables as listed in Table 3.

Table 3: Catalyst Design Considerations

Catalyst Process

Acid Flow scheme design

Metal Hydrotreating severity
Porosity Hydrocracking severity
Stacking Temperature
Pressure and hydrogen availability

Page 18
One such consideration involves process severity and its impact on the extent of secondary
cracking in the hydrocracking reactor. The key steps in the mechanism of hydrocracking
paraffins consists of a sequence of steps beginning with dehydrogenation at metal sites to form
olefinic intermediates which are then protonated at the acid sites to form the reactive carbenium
ions. These, in turn, can isomerize and leave the catalyst surface without cracking after picking
up a hydride ion at the metal sites. Alternatively, they can crack to form smaller alkanes which
then leave the catalyst surface as hydrocracked products9-11. This process of isomerization and
cracking to primary cracked products is referred to as ideal cracking and therefore it does not
involve secondary cracking of the initially formed product. Secondary cracking often results in
the formation of light ends which are of low value to a unit operating to make liquid
transportation fuels.

Control of this sequence of steps to stop the reactions after formation of primary products is
accomplished by careful selection of catalyst properties such as the strength and distribution of
acid sites and tailoring the hydrogenation function to fit the acidity on the catalyst. In addition,
particularly when heavy feedstocks are being processed, elimination of diffusion constraints
which contribute to secondary cracking is accomplished by strict control of pore size and pore
geometry of the catalyst to match the molecular dimensions of a given feed. These catalyst
properties must also be matched to the service environment in which the catalyst is intended to
function, including the recycle gas composition and the reactor pressure. Thus, detailed
knowledge of molecular types and size in the feed is incorporated into catalyst selection criteria
in order to make critical determination of the appropriate catalytic components to match feed for
a given unit.

With better understanding of the process chemistry and the advent of sophisticated tools, UOP
has been successful in innovating improved Unicracking catalysts at an accelerated pace. Figure
16 shows the introduction of new Unicracking catalysts on a time line demonstrating that the rate
of new inventions has increased significantly over the years. Recently, UOP has commercialized
nine new catalysts and these catalysts have met or exceeded refiners expectations.

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 Figure 16: UOP Hydrocracking Catalyst Commercialization Timeline
HC 22 DHC 32 HC 115
DHC 2 DHC 6 DHC 8 HC 215 HC 120
Distillates
HC 53
HC 35
HC 16 HC 26 HC 43 HC 150
Flexible

HC 190
HC 14 HC 28 HC 24 HC 29 HC 185
Naphtha

1960 1970 1980 1990 2000

UOP has been successful in designing catalyst characteristics that are critical for processing
heavy feeds like high nitrogen containing difficult feedstocks and DAO.

CONCLUSIONS

Growth in the demand and stringent quality requirements for transportation fuel make
hydrocracking a technology of choice. Hydrocracking of heavier and highly contaminated
feedstocks require optimal technical solutions that include catalyst and flow scheme
consideration.

Utilizing state-of- the-art research facilities in combination with a large commercial experience
base, UOP is developing process innovations that use our understanding of complex process
reaction chemistry. These innovations have been incorporated into economic flow schemes as
evidenced by the recent introduction of HyCycle and Advanced Partial Conversion Unicracking,
LCO-X processes and development of the Ecofining process. These flow schemes and catalyst
innovations provide an opportunity to optimize hydrogen utilization depending on the refiners
operating objectives.

Renewal of technology like the two-stage Unicracking process has demonstrated significantly
improved total distillate yields while processing difficult feedstocks and producing excellent
product qualities.

Catalyst innovations have taken a critical look at not only improving activity and increased yield
performance but also optimizing hydrogen usage. UOP has been successful in designing and
introducing nine new catalysts in the last seven years. These catalysts have been successful in
meeting or exceeding expectations.

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REFERENCES
1. Purvin & Gertz Inc., Global Petroleum Market Outlook: Prices And Margins, Fourth
Quarter 2007 Update
2. Asian Development Bank and Clean Air Initiative for Asian Cities Center, Inc., A
Roadmap for Cleaner Fuels and Vehicles in Asia, Second Consultation Draft, December
19, 2007
3. Thakkar V. P. et al, Innovative Hydrocracking Applications For Conversion of Heavy
Feedstocks, AM-07-47 NPRA 2007 Annual Meeting
4. Scherzer, Julius and Gruia, A. J., Hydrocracking Science and Technology, Chemical
Industries; v. 66, pg. 9 (1996)
5. Remsberg, Charles and Higdon, Hal, Ideas for Rent The UOP Story, p. 326, 1994
6. Thakkar V. P. et al, LCO Upgrading - A Novel Approach for Greater Added Value
and Improved Returns, AM-05-53 NPRA 2005 Annual Meeting
7. Johnson, J. et al, Unlocking High-Value Xylenes From Light Cycle Oil, AM-07-40,
NPRA 2007 Annual Meeting
8. Holmgren J. et al, A New Development in Renewable Fuels: Green Diesel, AM-07-10
NPRA 2007 Annual Meeting
9. Coonradt, H. L. and Garwood, W.E., Mechanism of Hydrocracking Reactions of
Paraffins and Olefins, Ind. Eng. Chem. Process Des. Dev., 3 (1964) 38
10. Steijns, M. S et al, Ind. Eng. Chem. Prod. Res. Dev. 20, (1981) 654
11. Martens, J. A. et al, Appl. Catal. 20, (1986) 239

UOP LLC
25 East Algonquin Road
Des Plaines, IL 60017-5017
Tel: 847.391.2000 2007 UOP LLC. All rights reserved.
January 2007
www.uop.com UOP 4706B

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