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Fuels For The 21st Century

Fuel Sulfur Solutions Hydrogen Solutions MTBE Solutions Benzene Solutions

Changing regulations about Fuel Sulfur Solutions


fuel sulfur have refiners
concerned about what Within the next few years, European and U.S. governmental
might be needed to meet regulations will require refiners to drastically lower the sulfur
them. Here are some ideas: content of gasoline as part of the continuing effort to reduce
air pollution from gasoline and diesel engines. Sulfur is tar -
geted because it significantly reduces the efficiency of vehi -
Refinerywide Implications of cle catalytic converters. Emissions of SO and other contami -
2
Producing Low-Sulfur Fuels nants from the fluid catalytic cracking (FCC) regenerator and
from refinery heater stacks continue to be an issue with refin -
Exploiting Synergy between ers throughout the United States and the rest of the world.
FCC and Feed
Hydroprocessing to Improve For most refiners, the major source of sulfur in gasoline and
diesel fuels comes from components produced by the FCC
Refinery Margins and
unit. Regenerator stack emissions also contribute significant -
Produce Low-Sulfur Fuels ly to overall stationary-source emissions from the refinery.
Options for reducing sulfur focus on changing crude slates,
The Lower It Goes, the changing product fractionation, treating the FCC feed or
Tougher It Gets products, and treating other fuel blendstocks.

Even in light of the new environmental regulations, which, in


Meeting Gasoline Pool
most cases, will require increased capital expenditures, refin -
Sulfur and Octane Targets ers are feeling increased pressure to increase profits and
with the ISAL Process return on investment. The challenge is to meet the new prod-
uct requirements and at the same time improve refinery prof -
More on the ISAL process itability.

FCC Light Cycle Oil: Diesel may soon be filling the tanks of our sport utility vehi -
Liability or Opportunity? cles, light trucks, and passenger cars. With its better fuel
economy, diesel makes an ideal fuel. But before diesel dis -
places gasoline, it must be reformulated to reduce its emis -
sions.

One of the first steps in reformulating diesel will be to reduce


its sulfur content from the current maximum of 500 ppm in
the U. S. to probably less than 20 ppm to meet pending U.S.

more
requirements, and from the current limit of 350 ppm sulfur to
less than 50 ppm to meet upcoming European requirements

Will this reformulation be sufficient? Automobile and diesel


engine manufacturers dont think so. They believe that to
achieve U.S. market acceptance for light duty diesel engines,
consumers will demand higher quality diesel similar to
what is available in Europe. As a result, aromatics concentra-
tion, cetane, specific gravity, and distillation are under scruti-
ny. Implementation mandates may be just around the corner!

With increased demand for diesel, you will be under pressure


to find ways of making more high quality diesel from your
existing gasoline oriented refinery. Flexibility will be essen -
tial and UOP has the distillate technology to provide you
with this flexibility.

Maximum Quality Distillate (MQD) Unionfining


is a family of processes that upgrades difficult diesel
blendstocks, such as light cycle oil, into valuable high-
quality diesel. MQD Unionfining is an integrated
approach that can be tailored to meet your specific
needs and enable you to produce more high-quality
diesel.

The Partial-Conversion Unicracking process


enables you to produce low-sulfur, high-quality diesel
while at the same time improving FCC yields and
reducing FCC naphtha sulfur so that it can be blended
directly into your gasoline pool. With the Partial-
Conversion Unicracking process, you now have the
flexibility to meet the demand for more higher-quality
diesel while simultaneously meeting lower gasoline
sulfur requirements.

Diesel Fuel: Specifications and Demand for the


21st Century
EXPLOITING SYNERGY BETWEEN FCC AND FEED PRETREATING
UNITS TO IMPROVE REFINERY MARGINS AND PRODUCE
LOW-SULFUR FUELS

Scott W. Shorey, David A. Lomas, and William H. Keesom


UOP, LLC
Des Plaines, Illinois

Print This Section

Presented at the
1999 NPRA Annual Meeting
San Antonio, Texas
March 21-23, 1999
`

EXPLOITING SYNERGY BETWEEN FCC AND FEED PRETREATING


UNITS TO IMPROVE REFINERY MARGINS AND PRODUCE
LOW-SULFUR FUELS

Scott W. Shorey, David A. Lomas, and William H. Keesom


UOP LLC
Des Plaines, Illinois

INTRODUCTION

Fuel specifications now being considered may require reducing the sulfur content for both
gasoline and high-speed diesel fuels to less than 50 wppm. Even though the FCC unit is the
major source of gasoline, it is also the major source of sulfur in gasoline and diesel fuels. In
some locations, limits on SOx emissions are more restrictive than limits on sulfur in gasoline and
diesel. Also, because the sulfur content in fuel oil is expected to decline, the clarified slurry oil
(CSO) produced by the FCC unit may need to be considered as part of any sulfur-management
strategy.

Lower sulfur in the fuel means either treating the FCC feed or treating its products.
Treating the FCC products requires multiple process solutions: naphtha treating, light cycle oil
(LCO) treating, and some form of flue gas treating for control of SOx emissions. Treating the
feed to the FCC unit can increase yields and at the same time reduce sulfur levels in gasoline
and diesel fuels, and reduce SOx emissions. The increased conversion in the FCC unit
resulting from feed treatment helps improve refinery margins. Product treatment, however,
offers no yield benefits and is simply a cost to the refiner.

The title of this paper contains a key word: synergy. The word is derived from the
Greek word synergos meaning working together. Synergy is achieved when the combined
action of two or more processes produces benefits greater than when each is operated
separately. In the context of FCC feed pretreating, synergy is achieved by adding hydrogen
to the FCC feed to increase the yield of high-value products.

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Like the FCC unit, the integrated complex of pretreating unit (PTU) and FCC unit can
produce primarily gasoline or a more-balanced slate of gasoline and diesel fuels. Depending on
the desired mode of operation, the FCC feed PTU can be a hydrotreating unit or a partial-
conversion hydrocracking unit. The gasoline mode of operation is best achieved when the feed
PTU is a vacuum gas oil (VGO) hydrotreating unit. Although some additional low-sulfur diesel
fuel can be produced with this approach, the low cetane index of the diesel limits the quantity
that can be blended into the diesel pool. Raising the cetane index requires that the PTU be a
conversion unit.

This paper illustrates how FCC feed treatment helps meet the new fuel specifications and
also improve refinery economics. Initially, the paper shows the impact of hydrotreating severity
on FCC performance. Next, it shows the benefit achieved from partial-conversion hydrocracking
instead of hydrotreating the FCC feed. The level of conversion achieved from partial-conversion
hydrocracking is greater than from the conventional mild hydrocracking approaches of the past,
and the distillate quality is also much higher. Several new partial-conversion hydroracking flow
schemes that can produce diesel with 50 wppm sulfur and 50 cetane index are introduced.

SULFUR-REDUCTION OPTIONS

Roughly 400 FCC units are operating worldwide. As shown in Figure 1 more than two-
thirds of these units are in locations facing restrictions on motor fuel sulfur. Because not
even one in three units operates with any kind of feed or product treatment system, sulfur
reduction is a challenge.

The majority of FCC units produce naphtha as the primary product for blending into
the gasoline pool. The light olefins from the FCC unit can be used for motor fuel alkylation,
oxygenates, or petrochemical applications. An example of the blending components that
make up a modern refinery gasoline pool is shown in Table 1.

The FCC naphtha makes up 30 to 40% of the gasoline in a typical refinery pool. For the
example shown in Table 1, the FCC unit contributes 36% of the gasoline and 98% of the sulfur
in the pool. Meeting a gasoline sulfur specification of 50 wppm means that the FCC naphtha
sulfur is limited to about 135 wppm in this example. Lower gasoline sulfur requirements or
higher FCC naphtha content requires further reduction in FCC naphtha sulfur.

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Table 1. Typical Gasoline Pool Composition

Percent of Pool Percent of Pool


Gasoline Blendstocks Volume Sulfur
Alkylate 12
Coker naphtha 1 1
Hydrocracked naphtha 2
FCC naphtha 36 98
Isomerate 5
Light straight-run naphtha 3 1
Butanes 5
MTBE 2
Reformate 34
Total 100 100

A number of options for directly controlling the FCC product sulfur are available:

Crude selection
Fractionation for control of gasoline sulfur
Posttreat products
Pretreat feed

CRUDE SELECTION

Processing low-sulfur crude should be considered when crude prices are low and the
differential between sweet and sour crude is small. This approach can augment a sulfur-
reduction strategy but is not likely to be cost-effective for refineries where FCC naphtha is a
significant fraction of the gasoline pool or where gasoline sulfur must be less than 50 wppm.

FRACTIONATION

The sulfur content of the FCC naphtha can be reduced significantly by removing the
heaviest gasoline cut. Figure 2 shows how the sulfur, olefins, and aromatics in the FCC
naphtha distribute throughout the boiling range of a full-range FCC naphtha. Adjusting the
fractionation so that the heaviest 20% of the FCC naphtha is included in the LCO reduces
the gasoline endpoint and can reduce its sulfur content by as much as 60%. The drawbacks
to this approach are:

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Reduced gasoline yield


Increased LCO yield
No change in the sulfur content of the other products

POSTTREAT THE PRODUCTS

Posttreating the FCC products to meet the fuel sulfur specifications requires multiple
processes. The FCC naphtha must be fractionated, and the light and heavy portions treated
separately to reduce sulfur. The key to this approach is managing the sulfur-olefin
distribution shown in Figure 2 to minimize the octane loss from olefin saturation during
desulfurization. The LCO can be hydrotreated and blended into the distillate pool. Sulfur in
the CSO can be diluted with a lower-sulfur blendstock such as distillate. Scrubbing or some
other form of SOx control can reduce FCC flue gas emissions.

PRETREAT THE FCC FEED

All of the previous options for reducing fuel sulfur increase refining costs without increasing
refinery revenue. An alternative is adding hydrogen to the FCC feed to increase conversion
and yield of light products.

IMPACT OF FEED PRETREATING ON FCC PERFORMANCE

As a result of changing refining needs, modern FCC feed pretreating units are being
designed to deeply desulfurize feeds that include blends of straight-run and cracked stocks.
Two examples of recently designed VGO hydrotreating units, summarized in Table 2, show
the degree to which some refiners are now pretreating FCC feedstocks. Both of these
commercial Unionfining units achieve product sulfur levels between 1,000 and
2,000 wppm from feeds with sulfur in the range of 2 to 3 wt-%. Part of the design basis for
the Asian unit is an SOx maximum of 300 mol-ppm in the FCC regenerator flue gas.

Commercial VGO hydrotreating units process a wide range of feedstocks over a wide
range of desulfurization and nitrogen removal levels. In the following examples, a single
feedstock definition is used for all cases so that a clear picture is presented of the benefits
that result from feed treating.

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Table 2. Commercial VGO Unionfining Units

Asian Refiner U.S. Refiner


Feed description HVGO + CGO HVGO + CGO
Feed capacity, BPSD 147,200 45,000
Separator pressure, psig 950 1,300
Recycle gas scrubbing Yes Yes
Feed Product Feed Product
Gravity, API 20.1 24.5 15.7 22.0
Sulfur, wt-% 3.1 0.2 2.34 < 0.12
Nitrogen, wppm 1,565 600 3,500 < 0.1
Carbon residue, wt-% 0.67 0.3 1.0 0.7
Metals (Ni + V + Fe), wppm 0.38 0.1 5 2
Distillation endpoint, F 1,100 1,085 1,075 1,060
UOP K factor 11.6 12.0 11.1 11.7

REFINERY STUDY BASIS

The feedstock to the FCC unit for the following analysis of pretreatment options is derived
from an untreated, sour Middle Eastern crude. The refinery configuration for this analysis
includes a delayed coker that supplies roughly 10% of the FCC feed (Figure 3). The balance
of the feed comes from straight-run VGO. The untreated feedstock properties are
summarized in Table 3.

Table 3. Untreated FCC Feedstock Properties

VGO CGO Blend


Feed capacity, BPSD 31,250 3,750 35,000
Blend contribution, wt-% 89.1 10.9 100.0
Feed properties
Gravity, API 20.9 17.5 20.5
Sulfur, wt-% 2.5 3.4 2.60
Nitrogen, wppm 700 2,350 880
Carbon residue, wt-% 0.4 0.2 0.4
Bromine number 3 25 7.5
Metals (Ni + V), wppm 0.2 1 0.36
Distillation, F
IBP 664 662 664
50% 830 788 817
90% 980 898 965
FBP 1050 950 1050

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The high levels of sulfur and nitrogen in the feed blend, 2.6 wt-% sulfur and 880 wppm
nitrogen, are indicators of the aromatic nature of the feed because a large fraction of both
sulfur and nitrogen are chemically bound in polycyclic aromatic species (PCAs) that are
difficult to convert in the FCC unit. Hydroprocessing the FCC feed reduces its sulfur and
nitrogen content and adds hydrogen to the PCAs, making them easier to crack in the FCC
unit.

HYDROTREATING BENEFITS

The impact of hydrotreating on FCC feedstock properties is shown in Table 4 for four levels of
hydrotreating: 0, 90, 98, and 99% desulfurization. The fact that the API gravity increases from
20.5 to 26.0 over this hydrotreating range clearly indicates that the feed is being progressively
saturated with hydrogen as the sulfur level is reduced from 2.6 to 0.02 wt-%. The hydrotreating
conditions range from 900 psig for the 90% desulfurization case to 1,000 psig for the 98 and
99% desulfurization cases.

Table 4. Impact of Desulfurization on FCC Feed Properties

Feed Desulfurization
Untreated 90% HDS 98% HDS 99% HDS
Operating pressure, psig 900 1000 1000
Feed properties
Gravity, API 20.5 23.5 24.8 26.0
Sulfur, wt-% 2.6 0.25 0.06 0.02
Nitrogen, wppm 880 500 450 400
Carbon residue, wt-% 0.4 .25 0.1 0.1
Metals (Ni + V), wppm 1 <1 <1 <1
Hydrogen addition to feed, wt-% 0 0.51 0.74 0.94

Impact on FCC Yield

Hydrotreating the feed directly improves FCC unit performance in several ways:

Increased conversion to naphtha and lighter products


Increased gasoline yield
Decreased LCO and CSO yield
Decreased coke yield

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The impact of hydrotreating on the FCC product-yield pattern and sulfur content is shown
in Table 5. Naphtha yield increases and LCO yield decreases with hydrotreating because the feed
is more easily converted in the FCC unit. The naphtha octane values do not change much
because partially saturated PCAs in the distillate boiling range are converted into additional
naphtha. Also, hydrotreating does little to improve the cetane quality of LCO because its
aromatics content still remains high. A major benefit of increased conversion is lower LCO
production and hence less impact from this stream on diesel pool quality. Another benefit is that
CSO yield decreases with hydrogen addition to the FCC feed.

Table 5. Impact of Hydrotreating on FCC Unit Performance

Feed Desulfurization
Untreated 90% HDS 98% HDS 99% HDS
Yields, wt-%
H2S 1.1 0.1 0.0 0.0
C2 3.3 3.5 3.2 2.8
C3+C4 16.3 17.6 18.7 19.9
Full-range naphtha 48.3 51.5 52.5 53.6
LCO 16.7 15.7 15.0 14.0
CSO 9.0 6.6 5.9 5.2
Coke 5.4 5.0 4.7 4.4
Total 100.0 100.0 100.0 100.0
Conversion, vol-% 74.3 77.7 79.1 80.8
Key product properties
Naphtha RON 93.2 93.0 92.9 92.7
Naphtha MON 80.5 80.8 81.1 81.0
LCO cetane index 25.7 25.7 26.4 26.5
Product sulfur, wppm
H2S 10,066 753 188 94
Naphtha 3,600 225 55 18
LCO 29,700 3,400 900 300
CSO 57,800 11,000 3,000 1,100
Coke 30,300 5,700 1,554 516
SOx, vppm 2,030 410 120 42

The results show that around 95% sulfur removal is needed to achieve a sulfur content
of less than 135 wppm in the FCC naphtha. The extent of desulfurization needed for other
feeds may be different, and the reader is referred to Reference 1 for an excellent discussion
of the relationship between feed and product sulfur.

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Impact on PTU-FCC Complex Yield

Because some conversion occurs in the FCC hydrotreating unit, additional gasoil feedstocks
were provided to the pretreating unit to keep the FCC feed rate at 35,000 BPSD. As shown
in Table 6, the feed to the PTU-FCC complex increased from 35,000 to 41,408 BPSD, or
475 to 563 M lb/hr, as the desulfurization increased from 0 to 99%. In addition, as a result
of adding hydrogen to the feed, the C5+ liquid yield from the complex increased from 74 to
75.5 wt-% of fresh feed.

Table 6. Impact of Hydrotreating on PTU-FCC Complex Yield

Feed Desulfurization
90% 98% 99%
Untreated HDS HDS HDS
Feed, BPSD
To Complex 35,000 40,029 40,884 41,408
To FCC unit 35,000 35,000 35,000 35,000
Complex material balance, M lb/hr
Feed 475 544 555 563
Products
C5+ Liquids 352 409 420 425
Naphtha + diesel 282 378 392 401
Fuel oil 70 31 27 24
Coke 26 23 22 20
Product yields, wt-% of total feed
C3-C4 16.3 15.2 15.8 16.6
C5+ Liquids 74.0 75.3 75.5 75.5
Naphtha + Diesel 59.3 69.6 70.7 71.3
Fuel oil 14.7 5.7 4.9 4.2
Coke 5.4 4.3 3.9 3.6
H2 consumption, wt-% of total feed 0.00 0.53 0.72 0.95

The net result from adding hydrogen and processing more feed is that the yield of C5+
liquids increased from 352 to 425 Mlb/hr. However, one of the most-significant benefits
from adding hydrogen to the feed is the shift in yield pattern to greater production of
transportation fuel and decreased production of fuel oil and coke. For 99% desulfurization,
the feed to the PTU-FCC complex is increased by 19%, the yield of motor fuel is increased
by 42%, and the yield of material in the fuel oil range decreased by 66%. Clearly, feed
utilization is more efficient as a result of hydrotreating.

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ECONOMICS OF FCC FEED HYDROTREATING

How deeply should the FCC feed be hydrotreated? Is sulfur control the proper basis for
determining the degree of feed pretreatment, or is conversion more important? To answer
these questions requires not only quantifying the changes in FCC performance as the
feedstock is hydrotreated but also the economics of installing and operating the feed
pretreating unit.

The economics in these examples is based on the costs and performance of the combined
PTU-FCC complex. Product pricing for the U.S. Gulf Coast, first quarter 1998 is used for this
analysis; a crude price of $14/bbl has been assumed. Definitions of the terms used in the
economic calculations are summarized in Table 7.

Table 7. Definitions of Economic Terms

Term Abbreviation Definition


Cash cost of production CCOP Fixed costs + variable costs
Fixed cost Labor + maintenance + overhead + capital expense
Variable cost of production VCOP Net feed + utilities + consumables
Net cost of production NCOP CCOP + capital charges
Net feed Feedstock costs by-product credits
Inside battery limits ISBL Inside battery limits
Total plant investment (ISBL + 30%) + capitalized inventory + technology fees
Pretax profit Sum of product revenues NCOP
Simple payback Total investment / annual pretax profit
Pretax return on ROI Pretax profit / (capital investment + incremental working
investment capital)

The economics for each case is determined by using pretax profit, pretax return on
investment (ROI), and simple payback. The results, summarized in Table 8, show a positive
pretax profit and pretax ROI for all the hydrotreating cases relative to the base case (no
hydrotreating). The highest return is achieved when the FCC feedstock is hydrotreated to a
sulfur level of 600 wppm, or 98% desulfurization. Although yields increase at higher
desulfurization, costs increase faster than revenue. Payback of the investment for the 98%
desulfurization case occurs in less than a year and a half.

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Table 8. Hydrotreating Economics

Feed Desulfurization
Untreated 90% HDS 98% HDS 99% HDS
Total installed cost, $MM 61.8 70.3 72.2
Incremental profit, $MM Base 30.2 54.6 54.2
Pretax ROI, % Base 33.0 50.2 47.4
Simple payback, yr 2.04 1.29 1.33

Hydrotreating the FCC feed can increase transportation fuel yields and improve
refinery economics, especially for gasoline refineries. However, the chemistry that produces
an acceptable gasoline blendstock from the FCC unit also produces LCO and CSO products
that contain high levels of aromatics. Consequently, LCO blending into the diesel pool is
constrained not only by its sulfur content but also by its low cetane value.

PARTIAL-CONVERSION HYDROCRACKING

Several issues need to be considered in producing additional high-quality diesel fuel. First is the
need to meet the current sulfur specification, 500 wppm for on-road diesel, and to consider the
future direction, which is heading toward 50 wppm, at least in Europe. Second is the need to
produce diesel with higher cetane. Although the United States has not specified a higher cetane
target, cetane number in Europe is going to at least 51 by the year 2000 and may go as high as
58 by 2005. The FCC-based refineries will be particularly hard pressed to meet these targets.

IMPROVING DISTILLATE QUALITY

Hydrocracking improves product quality through a combination of hydrogen partial


pressure and conversion. Higher product quality, and in this context, distillate product
quality, is achieved by hydrogen addition and conversion in the presence of a catalyst.
Extremely high-quality distillates, including Jet A-1 quality kerosene, can be produced from
heavy feeds in traditional high-conversion or full-conversion hydrocracking units that
operate at pressures from 2,000 to 2,500 psig. When the hydrocracking unit is an FCC-feed
PTU, the conversion is limited by the amount of feed required for the FCC unit. Figure 4
shows how kerosene and diesel properties improve with operating pressure for an operation
in which the conversion is 40% to diesel and lighter products.

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MILD HYDROCRACKING

Because high-conversion hydrocracking units are expensive to build, refiners have added
incremental conversion to their refineries since the early 1980s by revamping existing VGO
hydrotreating units into mild hydrocracking units. These units operate at pressure ranges of 800
to 1200 psig, which is consistent with the typical design pressures for existing hydrotreating
units. The diesel yield and quality are limited by constraints of existing equipment, and the
primary objective is often to merely improve the level of conversion and not the product quality.

Operation at low pressure and conversion limits the product quality from mild
hydrocracking units, which typically produce diesel with a cetane index around 39 to 42.
Kerosene smoke point is often 10 mm, which is far below the 19 mm specification for jet
fuel. Although full-range diesel from mild hydrocracking can be used in blending road diesel
that meets current U.S. diesel specifications, the longer-term demand for premium diesel
coupled with the possibility of higher cetane specifications limits its use.

The addition of difficult-to-convert materials such as LCO and coker gas oils (CGO) to
the FCC-PTU feed makes improving diesel quality from mild hydrocracking units even
more difficult. Two other refinery streams that are often considered for upgrading because
of their poor quality are LCOs and light coker gas oils (LCGOs).

The performance characteristics for a conventional mild hydrocracking unit and a once-
through hydrocracking unit designed to make diesel with a 50 cetane index are shown in
Table 9. Although both units are operated to achieve 40% conversion, the much-higher
operating pressure used in once-through hydrocracking results in higher hydrogen partial
pressure, better aromatics saturation, and much better diesel quality than from mild
hydrocracking. Greater hydrogen addition in once-through hydrocracking also improves the
quality of the FCC feed. However, the cost for higher product quality is reflected in the 1.5
times higher investment for the high-pressure unit and the nearly 2 times higher hydrogen
consumption.

PARTIAL-CONVERSION FLOW SCHEMES

A lower-cost alternative to full hydrocracking is partial-conversion hydrocracking, which


results in greater yield improvement and higher product quality than from mild
hydrocracking but at significantly lower investment than for full hydrocracking. Partial-

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Table 9. Comparison of Mild and High-Pressure Hydrocracking

Conventional Mild Once-Through


Hydrocracking Hydrocracking
Operating pressure, psig 800 1,000 2,300
Hydrogen consumption, SCFB 650 1,200
Conversion to 650 F-, vol-% 40 40
Yield of full-range diesel, vol-% 30.0 42.0
Diesel cetane index (D-976) 40 51
FCC feed quality
API gravity 26.5 34.0
Sulfur, wppm 3000 80
Nitrogen, wppm 500 10
UOP K 12.1 12.75
ISBL estimated erected cost, Base 1.5 x base

conversion hydrocracking is used commercially for the production of lubricating oils and
light olefins and in preparing FCC feeds.

Conventional Partial-Conversion Flow Schemes

Conventional partial-conversion hydrocracking flow schemes are similar to full-conversion


hydrocracking schemes except that the operating pressure is in the range of 1,500 psig
instead of 2,000 to 2,500 psig. Distillate product quality is somewhat lower because of the
lower pressure. In addition, distillate product quality is also limited by the degree of
conversion that can be achieved because the bottoms product from the hydrocracking unit is
a feed to another unit. Although higher conversion can be achieved in partial-conversion
units that are integrated with FCC units, this conversion is achieved at the expense of feed
to the FCC unit. Even with higher conversion, the distillate quality from conventional
partial-conversion hydrocracking units is not sufficient to meet the higher diesel cetane
requirements.

New Flow Schemes

UOP has recently developed three new flow schemes for partial-conversion hydrocracking
that allow refiners to produce low-sulfur, high-cetane diesel and low-sulfur, high-quality
FCC feedstock at lower conversion than in conventional partial-conversion operations.
These new partial-conversion Unicracking schemes operate at the same pressures as

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conventional partial-conversion hydrocracking. However, distillates from these new


schemes can be produced with less than 50 ppm sulfur and greater than 50 cetane index.

The new flow schemes, highlighted in Figures 5 to 7, contain two common design
features. First, all three options use two reactors. Second, each flow scheme separates
hydrotreating and hydrocracking into distinct reaction zones so that not all of the fresh feed
is required to go through the hydrocracking reactor. This design feature is extremely
important and only possible because of the two reactor design.

The first flow scheme is a variation on the two-stage, full-conversion hydrocracking


design and uses common separation and fractionation (Figure 5). The second flow scheme
uses two parallel once-through reactors, again with common separation and fractionation
(Figure 6). The third flow scheme uses UOPs modified-flow, two-stage design (Figure 7).
Each of these options has advantages over conventional partial-conversion designs.

The two reactor design in these flow schemes provides much greater flexibility than a
single reactor design because the fraction of feed that is hydrotreated and the fraction that is
hydrocracked can now be customized to meet the specific needs of the refinery. Poor-
quality streams, such as LCO and heavy cycle oil (HCO), can be upgraded by sending them
to either Reactor 1 or 2, depending on the product quality targets. The VGO feedstocks can
be split into light and heavy fractions so that the feedstock fraction that is more readily
converted is sent to Reactor 2 and the more-difficult fraction is deeply hydrotreated in
Reactor 1.

The severity in Reactor 1, the hydrotreating reactor, is set primarily by the target sulfur
content in the unconverted oil product. The severity in Reactor 2, the conversion reactor, is
determined by the distillate quality requirements. Sending only part of the feed to Reactor 2
allows the second reactor to operate at the conversion needed to meet the required distillate
product quality. However, the conversion from the overall process is not so high as to
deprive the FCC unit of feed.

The key to achieving high product quality at low overall conversion is separating the
hydrotreating and hydrocracking functions into separate reactors. Using conversion to
achieve product quality is more cost-effective than using high-pressure. Although the
investment for these new partial-conversion flow schemes is about 15 to 20% lower than
traditional hydrocracking units, extremely high-quality diesel can still be produced from
low-quality feeds.

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These new partial-conversion Unicracking options offer flexibility to meet market demands
for high-quality middle distillates. This flexibility can also be used to vary the production between
gasoline and diesel. High-activity Unionfining catalysts and a wide array of Unicracking
catalysts give refiners the means to customize the product slate to a much greater extent
than was possible before.

COMMERCIAL PERFORMANCE

How do the economics of partial-conversion compare to simple hydrotreating of the FCC feed?
Two commercial examples are used to evaluate the benefits of partial-conversion hydrocracking
(Table 10).

Table 10. Commercial Partial-Conversion Unicracking Operation

Latin European Refiner


American Low High
Refiner Conversion Conversion
Start-up 1999 1993 1993
Feed description SR VGO HVGO HVGO
Feed capacity, BPSD 30,000 35,000 30,000
Separator pressure, psig 1,400 1,436 1,436
Recycle gas scrubbing Yes No No
Gross conversion, vol-% 40 36 67
Conversion cutpoint, F 700 700 700
Feed properties
Gravity, API 23.8 21.5 21.5
Sulfur, wt-% 1.0 2.1 2.1
Nitrogen, wppm 1,000 1,190 1,190
Carbon residue, wt-% 0.25 0.7 0.7
Metals (Ni + V), wppm 0.97 1.1 1.1
Distillation endpoint, F 995 1,083 1,140

These two Unicracking units operate in conventional partial-conversion modes to produce


an unconverted oil product for feed to the FCC unit. Both units are designed to operate in the
range of 1,400 to 1,450 psig, and both units are designed to use zeolitic Unicracking catalysts. A
high-activity hydrotreating catalyst ahead of the zeolitic cracking catalyst ensures low product
sulfur and nitrogen content, even when operating at moderate hydrocracking pressures.

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The Latin American unit is designed to use a low-zeolite hydrocracking catalyst for distillate
production and to produce an FCC feed with less than 0.1 wt-% sulfur and diesel with less than
100 wppm sulfur and a minimum cetane index of 45.

The European unit was designed to use a high-zeolite hydrocracking catalyst for more-
balanced production of naphtha and diesel and is operated in two conversion modes: low
conversion, (35%) and high conversion (65%). At low conversion, the distillate yield is not much
different than from the Latin American unit. At high conversion, distillate yield increases by
about 14 vol-% and naphtha yield by 20 vol-%. The European refiner has operated this unit
primarily in high-conversion mode. The FCC feed from this unit is extremely low in sulfur and
nitrogen, and the kerosene and diesel both contain less than 10 wppm sulfur. The kerosene
smoke point is 19 mm, and it can be blended directly into Jet A-1. The diesel cetane index is 54.

Yields and product properties from these two units are shown in Table 11. Because jet fuel
is an important product, the European refiner produces both jet and diesel. The Latin American
refiner is interested in only producing full-range diesel. The split between kerosene and diesel for
the Latin American refiner is shown for comparison purposes.

ECONOMIC BENEFIT OF PARTIAL-CONVERSION

The next step in the evaluation of the PTU-FCC synergy is to replace the FCC feed
hydrotreating unit with a partial-conversion unit that is based on the two commercial
examples shown above.

Higher Feed Quality

The results in Table 12 compare the FCC properties from 98% desulfurization with the two
partial-conversion cases: 40% conversion to diesel and 40% conversion to diesel and
naphtha. As shown by the increase in feed API gravity, the combination of higher pressure
and higher conversion in partial-conversion hydrocracking achieves higher FCC feed quality
for about the same level of desulfurization as conventional hydrotreating.

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Table 11. Yields and Product Quality from Partial-Conversion Hydrocracking

Latin European Refiner


American Low High
Refiner Conversion Conversion
Yields, vol-%
C5-260 F naphtha 3.2 6.6 17.3
Kerosene (260-500 F) 12.9 9.2 20.7
Diesel (500-700 F) 26.9 24.6 30.1
Total middle distillate 39.8 33.8 50.8
Product properties
Kerosene
Sulfur, wppm < 100 < 15 < 10
Smoke point, mm 15 15 19.0
Heavy diesel
Sulfur, wppm <100 < 20 < 10
Cetane index 49 48 54
Full-range diesel
Sulfur, wppm < 100
Cetane index 45
700 F+ FCC feed
Gravity, API 30 28 31
Sulfur, wppm < 1,000 < 50 < 30
Nitrogen, wppm < 300 < 10 <5

Table 12. Impact of Partial-Conversion on FCC Feed Properties

Hydroprocessing
Base Hydrotreat Partial-conversion
Feed treatment Untreated 98% HDS 40% to diesel 40% to naphtha
+ diesel
Operating pressure, psig 1,000 1,450 1,450
Gravity, API 20.5 24.8 28.5 29.5
Sulfur, wt-% 2.6 0.06 0.05 0.004
Nitrogen, wppm 880 450 440 10
Carbon residue, wt-% 0.4 0.1 0.1 0.1
Metals (Ni + V), wppm 1 <1 <1 <1
Hydrogen addition, wt-% 0 0.74 1.13 1.40

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Increased Yield from PTU-FCC Complex

The greater efficiency of hydrogen addition achieved by partial-conversion hydrocracking


translates into the ability to process more feed with no increase in FCC unit capacity. Table 13
shows the material balance from the PTU-FCC complex. The feed rate to the PTU-FCC
complex is increased by 43% relative to the 98% desulfurization case and 67% relative to the
base case. However, one of the more-significant benefits of partial-conversion hydrocracking is
shown by the large increase in the yield of naphtha plus distillate. With partial-conversion
hydrocracking, the yield of naphtha and distillate is 60% higher than with desulfurization and
more than twice the yield for the base case. In addition, better hydrogen addition to the FCC
feed results in less fuel oil and coke production.

The other significant benefit of partial-conversion hydrocracking is the production of diesel


that is much higher quality. Table 14 shows how the production of 50 cetane index diesel
increases by adding hydrogen to the feed to the PTU-FCC complex. For partial-conversion to
diesel and naphtha, the yield of 50 cetane index diesel increases by 50% relative to the base case.
The cetane index of the blendstocks in this example is as follows: hydrotreated straight-run
distillate (HDS SR diesel) at roughly 55; hydrotreated light coker gas oil (LCGO) at 42; and
hydrotreated LCO at 26. Distillate from the FCC feed treater varies between 38 and 50 cetane
index, depending on the extent of hydroprocessing.

Economics of Partial-Conversion Hydrocracking

Better feed utilization through increased hydrogen addition translates directly into improved
refinery economics. Table 15 compares the economics for the two partial-conversion cases with
the other desulfurization cases.

Because the increased demand for hydrogen in partial-conversion hydrocracking


increases the need for supplemental hydrogen to the refinery, a small hydrogen plant has
been included in the economic analysis for the partial-conversion cases. As hydrogen
demands increase, refiners should review their existing hydrogen network to ensure that the
available hydrogen is used in the most-effective manner. Reference 2 introduces a new
technique for improving refinery economics through better hydrogen utilization.

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Table 13. PTU-FCC Complex Material Balance for Partial-Conversion

Hydroprocessing
Base Hydrotreat Partial-Conversion
Feed treatment Untreated 98%HDS 40% to diesel 40% to naphtha
+ diesel
Feed, BPSD
To complex 35,000 40,884 58,343 58,232
To FCC unit 35,000 35,000 35,000 35,000
Complex material balance, M lb/hr
Feed 475 555 792 790
Products
C5+ liquids 352 420 643 637
Naphtha + diesel 282 392 623 619
Fuel oil 70 27 20 18
Coke 26 22 20 19
Product yields, wt-% of total feed
C3-C4 16.3 15.8 12.8 13.6
C5+ liquids 74.0 75.5 81.2 80.6
Naphtha + diesel 59.3 70.7 78.6 78.3
Fuel oil 14.7 4.9 2.6 2.3
Coke 5.4 3.9 2.5 2.5
H2 consumption, wt-% of total feed 0.00 0.72 1.13 1.40

Table 14. Production of 50 Cetane Index Diesel

Hydroprocessing
Base Hydrotreat Partial-Conversion
Feed treatment Untreated 90% 98% 99% 40% to 40% to
HDS HDS HDS diesel naphtha
+ diesel
PTU distillate cetane index 38 39 40 45 50
Diesel pool
Production rate, BPSD 34,646 35,690 36,257 36,956 47,432 53,297
Cetane index 50 50 50 50 50 50
Blendstock volume in pool, vol-%
HDS SR diesel 68.5 66.5 65.5 64.2 50.1 44.5
HDS LCGO 26.3 20.4 18.8 18.5 1.0 17.1
VGO HP diesel 0.0 13.1 15.7 17.3 49.0 34.7
HDS LCO 5.2 0.0 0.0 0.0 0.0 3.6
Available LCO used, vol-% 32 0 0 0 0 100
Available CGO used, vol-% 100 100 100 100 5 100

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Table 15. Economics of Hydrogen Addition to FCC Feeds

Hydroprocessing
Base Hydrotreat Partial-conversion
Feed treatment Untreated 90% 98% 99% 40% to 40% to
HDS HDS HDS diesel naphtha
+ diesel
Total installed cost, $MM 61.8 70.3 72.2 126.4 127.4
Incremental profit, $MM Base 30.2 54.6 54.2 99.8 100.9
Pretax ROI, % Base 33.0 50.2 47.4 41.2 41.0
Simple payback, yr 2.04 1.29 1.33 1.27 1.26

Higher conversion clearly increases the pretax profit of the conversion complex.
Because the level of capital investment required for partial-conversion hydrocracking is
greater than for conventional hydrotreating, the ROI is somewhat lower. However, simple
payback, for partial-conversion hydrocracking is equivalent to simple payback for the best
hydrotreating case.

CONCLUSION

The synergy from hydroprocessing FCC feed is demonstrated by improved refinery


economics and increased production of high-quality transportation fuels. Adding hydrogen
to the feed reduces the sulfur in all the FCC products so that they meet upcoming
regulations on fuel sulfur. The major benefit of adding hydrogen to the feed is the
improvement in refinery economics as a result of increased refinery production of gasoline
and diesel fuels at the expense of LCO and CSO. Conventional hydrotreating in the range of
95 to 98% desulfurization is sufficient to meet the new sulfur product specifications. Partial-
conversion hydrocracking can further improve refinery economics and is necessary to
increase refinery yield of high-cetane diesel.

New partial-conversion hydrocracking flow schemes offer increased flexibility in


making high-quality diesel from sour gasoils without needing to go to full-hydrocracking
pressures. By separating the hydrotreating and hydrocracking reactions, these new schemes
eliminate the constraint on conversion seen with conventional partial-conversion and mild
hydrocracking designs. The resulting diesel contains less than 50 ppm sulfur and has a
cetane index of 50.

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REFERENCES

1. T.A. Nguyen and M. Skripek, Reducing Sulfur in FCC Gasoline via Hydrotreating,
AICHE Spring National Meeting, Apr.17 -21, 1994.

2. A. Zagoria, G.P. Towler, B.M. Wood, and F.M. Hibbs, If Youre Burning Hydrogen,
Youre Burning Money, AM-99-08, NPRA Annual Meeting, San Antonio,
Mar.21-23, 1999.

BIBLIOGRAPHY

Gieseman, J.C., Rybarczyk, T.M., and Banks, D.M., Refinerywide Implications of Meeting
Low Sulfur Fuel Specifications, AM-99-44, 1999 NPRA Annual Meeting, San Antonio,
Mar. 21-23, 1999.

Krenske, L.D., Kennedy, J.E., Baron, K., and Skripek, M., Hydrotreating Technology
Improvements for Low-Emissions Fuels, AM-96-67, NPRA Annual Meeting, San
Antonio, Mar. 17-19, 1996.

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Figure 1. Geographical Breakdown of Operating FCC Units

Rest of Asia
49

PRC 43

India 8
Middle East 9 Americas
183
FSO 26

Europe & Africa


79
UOP 3135-1

Figure 2. FCC Naphtha Composition


70 7,000

60 6,000
Aromatics
Olefins-Aromatics, vol%

50 5,000
Olefins

Sulfur, ppm
40 4,000

30 3,000

20 2,000

10 Sulfur 1,000

0 0
120 210 300 390 480
Distillation Endpoint, F
UOP 3135-2

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Figure 3. FCC-Based Refinery

8,625 Light Naphtha


HDS Penex Unit

22,400 Heavy Naphtha 26,899 26,899 Platforming


HDS Unit Gasoline

125,000 Crude 6,900 Kerosene


Treating Jet Fuel

23,743 Diesel 32,843 36,506

22
HDS Diesel

AM-99-55
58,794
9,520 C 3-C4
Alkylation
31, 250 35,000 20,687 Gasoline
Vacuum FCC Unit
5,635 LCO

2,673 Clarified Oil


4,499 9,101 LCGO HCGO Fuel Oil
HCN Coke
27,544 Delayed 3,750
Coke
Coke
`

Figure 4. Effect of Pressure on Product Quality


30 80

25
Kerosene Smoke Point, mm

70

Diesel Cetane Index


20
Smoke Point 60
15
Cetane Index 50
10

40
5

0 30
0 1,000 1,500 2,000
Pressure, psig
At 40% conversion UOP 3135-7

Figure 5. Two-Stage, Partial-Conversion Unicracking Process


Fresh Feed

Recycle Gas

R2 R1

Light Naphtha
Separation
Heavy Naphtha
Fractionator

Kerosene

Diesel

Bottoms

UOP 3135-8

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Figure 6. Once-Through Unicracking Process with Parallel Reactors


Fresh Feed

Recycle Gas

R2 R1

Light Naphtha
Separation
Heavy Naphtha

Fractionator
Kerosene

Diesel

Bottoms

UOP 3135-9

Figure 7. Modified-Flow, Two -Stage Unicracking Process


Fresh Feed

Recycle Gas

R2 R1

Light Naphtha
Separation
Heavy Naphtha
Fractionator

Kerosene

Diesel

Bottoms

UOP 3135-10

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