Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 7.2
UOP UNICRACKING PROCESS
FOR HYDROCRACKING
Donald Ackelson
UOP LLC
Des Plaines, Illinois

INTRODUCTION

Hydrotreating and hydrocracking are among the oldest catalytic processes used in petro-
leum refining. They were originally employed in Germany in 1927 for converting lignite
to gasoline and later used to convert petroleum residues to distillable fractions. The first
commercial hydrorefining installation in the United States was at Standard Oil Compan y
of Louisiana in Baton Rouge in the 1930s. Following World War II, growth in the use of
hydrocracking was slow. The availability of Middle Eastern crude oils reduced the incen-
tive to convert coal to liquid fuels, and new catalytic cracking processes proved more
economical for converting heavy crude fractions to gasoline. In the 1950s, hydrodesulfur-
ization and mild hydrogenation processes experienced a tremendous growth, mostly
because large quantities of by-product hydrogen were made available from the catalytic
reforming of low-octane naphthas to produce high-octane gasoline.
The first modern hydrocracking operation was placed on-stream in 1959 by Standard
Oil Company of California. The unit was small, producing only 1000 barrels per stream-
day (BPSD). As hydrocracking units were installed to complement existing fluid catalytic
cracking (FCC) units, refiners quickly recognized that the hydrocracking process had the
flexibility to produce varying ratios of gasoline and middle distillate. Thus, the stage w as
set for rapid growth in U.S. hydrocracking capacity from about 3000 BPSD in 1961 to
about 120,000 BPSD in just 5 years. Between 1966 and 1983, U.S. capacity grew eight-
fold, to about 980,000 BPSD.
Outside the United States, early applications involved production of liquefied petrole-
um gas (LPG) by hydrocracking naphtha feedstocks. The excellent quality of distillate
fuels produced when hydrocracking gas oils and other heavy feedstocks led to the choice
of the hydrocracking process as a major conversion step in locations where diesel and jet
fuels were in demand. Interest in high-quality distillate fuels produced by hydrocracking
has increased dramatically worldwide. As of 2002, more than 4 million BPSD of hydroc-
racking capacity is either operating or is in design and construction worldwide.

7.23
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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

7.24 HYDROCRACKING

PROCESS APPLICATIONS

Hydrocracking is one of the most versatile of all petroleum refining processes. Any frac-
tion from naphtha to nondistillables can be processed to produce almost any desired prod-
uct with a molecular weight lower than that of the chargestock. At the same time that
hydrocracking takes place, sulfur, nitrogen, and oxygen are almost completely removed,
and olefins are saturated so that products are a mixture of essentially pure paraffins, naph-
thenes, and aromatics. Table 7.2.1 illustrates the wide range of applications of hydroc-
racking by listing typical chargestocks and the usual desired products.
The first eight chargestocks are virgin fractions of petroleum crude and gas conden-
sates. The last four are fractions produced from catalytic cracking and thermal cracking.
All these streams are being hydrocracked commercially to produce one or more of the
products listed.
This flexibility gives the hydrocracking process a particularly important role as refiner-
ies attempt to meet the challenges of today’s economic climate. The combined influences
of low-quality feed sources, capital spending limitations, hydrogen limitations, environ-
mental regulatory pressures, and intense competition have created a complex optimization
problem for refiners. The hydrocracking process is uniquely suited, with proper optimiza-
tion, to assist in solving these problems. UOP, with its broad background and research
capabilities, has continued to develop both catalyst and process capabilities to meet the
challenges.

PROCESS DESCRIPTION

The UOP* Unicracking* process is carried out at moderate temperatures and pressures
over a fixed catalyst bed in which the fresh feed is cracked in a hydrogen atmosphere.
Exact process conditions vary widely, depending on the feedstock properties and the prod-
ucts desired. However, pressures usually range between 35 and 219 kg/cm2 (500 and 3000
lb/in2 gage) and temperatures between 280 and 475°C (536 and 887°F).

*Trademark and/or service mark of UOP.

TABLE 7.2.1 Applications of the Unicracking Process

Chargestock Products
Naphtha Propane and butane (LPG)
Kerosene Naphtha
Straight-run diesel Naphtha and/or jet fuel
Atmospheric gas oil Naphtha, jet fuel, and/or distillates
Natural gas condensates Naphtha
Vacuum gas oil Naphtha, jet fuel, distillates, lubricating oils
Deasphalted oils and demetallized oils Naphtha, jet fuel, distillates, lubricating oils
Atmospheric crude column bottoms Naphtha, distillates, vacuum gas oil, and
low-sulfur residual fuel
Catalytically cracked light cycle oil Naphtha
Catalytically cracked heavy cycle oil Naphtha and/or distillates
Coker distillate Naphtha
Coker heavy gas oil Naphtha and/or distillates

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

UOP UNICRACKING PROCESS FOR HYDROCRACKING 7.25

Chemistry

Hydrocracking chemistry is bifunctional catalytic chemistry involving acid-catalyzed iso-

merization and cracking reactions as well as metal-catalyzed hydrogenation reactions. The
resulting products are lower in aromatics and contain naphthenes and highly branched
paraffins due to the higher stability of the tertiary carbenium ion intermediate. For paraf-
fins, the reaction network, shown in Fig. 7.2.1, is postulated to begin with a dehydrogena-
tion step at a metal site forming an olefin intermediate, which is quickly protonated at an
acid site to yield a carbenium ion. This is quickly followed by a series of isomerization
reactions to the most stable tertiary carbenium ions and subsequent cracking to smaller
paraffin, which evolves off the catalyst surface and smaller carbenium ion intermediate.
The carbenium ion can then eliminate a proton to form an olefinic intermediate, which gets
hydrogenated at a metal site or directly abstract a hydride ion from a feed component to
form a paraffin and desorb from the surface.
A typical hydrocracking reaction for a cycloparaffin (Fig. 7.2.2) is known as a paring
reaction, in which methyl groups are rearranged and then selectively removed from the
cycloparaffin without severely affecting the ring itself. Normally the main acyclic product
is isobutane. The hydrocracking of multiple-ring naphthene, such as decalin, is more rap-
id than that of a corresponding paraffin. Naphthenes found in the product contain a ratio
of methylcyclopentane to methylcyclohexane that is far in excess of thermodynamic equi-
librium.
Reactions during the hydrocracking of alkyl aromatics (Fig. 7.2.3) include isomeriza-
tion, dealkylation, paring, and cyclization. In the case of alkylbenzenes, ring cleavage is
almost absent, and methane formation is at a minimum.

FIGURE 7.2.1 Postulated paraffin-cracking mechanism.

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

7.26 HYDROCRACKING

FIGURE 7.2.2 Postulated cracking mechanism for naphthenes.

FIGURE 7.2.3 Postulated aromatic-dealkyla-

tion mechanism. Isobutane is also formed follow-
ing butyl carbenium ion isomerization, olefin
formation, and hydrogenation.

Catalyst

Hydrocracking catalysts combine acid and hydrogenation components in a variety of types

and proportions to achieve the desired activity, yield structure, and product properties.
Noble metals as well as combinations of certain base metals are employed to provide the
hydrogenation function. Platinum and palladium are commonly used noble metals while
the sulfided forms of molybdenum and tungsten promoted nickel or cobalt are the most

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

UOP UNICRACKING PROCESS FOR HYDROCRACKING 7.27

common base-metal hydrogenation agents. The cracking function is provided by one or a

combination of zeolites and amorphous silica-aluminas selected to suit the desired operat-
ing and product objectives.
A postulated network of reactions that occur in a typical hydrocracker processing a
heavy petroleum fraction is shown in Fig. 7.2.4. The reactions of the multiring species
should be noted. These species, generally coke precursors in nonhydrogenative cracking,
can be effectively converted to useful fuel products in a hydrocracker because the aromat-
ic rings can be first hydrogenated and then cracked.
Amorphous silica-alumina was the first catalyst support material to be used extensive-
ly in hydrocracking service. When combined with base-metal hydrogenation promoters,
these catalysts effectively converted vacuum gas oil (VGO) feedstocks to products with
lower molecular weight. Over three decades of development, amorphous catalyst systems
have been refined to improve their performance by adjustment of the type and level of the
acidic support as well as the metal function. Catalysts such as UOP’s DHC-2 and DHC-8
have a well-established performance history in this service, offering a range of activity and
selectivity to match a wide range of refiners’ needs.
Crystalline catalyst support materials, such as zeolites, have been used in hydrocrack-
ing catalysts by UOP since the mid-1960s. The combination of selective pore geometry
and varying acidity has allowed the development of catalysts that convert a wide range of
feedstocks to virtually any desired product slate. UOP now offers catalysts that will selec-
tively produce LPG, naphtha, middle distillates, or lube base oils at high conversion activ-
ity using molecular-sieve catalyst support materials. The UOP zeolite materials used in
hydrocracking service are often grouped according to their selectivity patterns. Base met-
al catalysts utilized for naphtha applications are HC-24, HC-34, and HC-170. Flexible base
metal catalysts (naphtha, jet, diesel) include DHC-41, HC-43, HC-33, HC-26, and HC-29.
The distillate catalysts, which offer a significantly enhanced activity over amorphous cat-
alysts while maintaining the excellent middle-distillate selectivity, are HC-110, HC-115,
DHC-32, and DHC-39. Noble metal catalysts are also available for both naphtha (HC-28)
and jet/naphtha (HC-35) service. Unlike the amorphous-based catalysts, the zeolite-con-
taining materials are usually more selective to lighter products and thus more suitable
when flexibility in product choice is desired. In addition, zeolitic catalysts typically

FIGURE 7.2.4 Hydrocracking reactions.

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

7.28 HYDROCRACKING

employ a hydroprocessing catalyst upstream, specifically designed to remove nitrogen and

sulfur compounds from the feed prior to conversion. UOP catalysts such as HC-P, HC-R,
HC-T, UF-210, and UF-220 are used for this service. These materials are specifically
designed with high hydrogenation activity to effectively remove these compounds, ensur-
ing a clean feed and optimal performance over the zeolitic-based catalyst.
One important consideration for catalyst selection is regenerability. Hydrocracking cat-
alysts typically operate for cycles of 2 years between regenerations but can be operated for
longer cycles, depending on process conditions. When end-of-run conditions are reached,
as dictated by either temperature or product performance, the catalyst is typically regener-
ated. Regeneration primarily involves combusting the coke off the catalyst in an oxygen
environment to recover fresh catalyst surface area and activity. Regenerations can be per-
formed either with plant equipment if it is properly designed or at a vendor regeneration
facility. Both amorphous and zeolitic catalysts supplied by UOP are fully regenerable and
recover almost full catalyst activity after carbon burn.

Hydrocracking Flow Schemes

Single-Stage. The single-stage flow scheme involves full conversion through recycling
of unconverted product and is the most widely used because of its efficient design
resulting in minimum cost for a full-conversion operation. This scheme can employ a
combination of hydrotreating and cracking catalysts or simply amorphous cracking
catalysts depending on the final product required.

Once-Through. Unlike the single-stage flow scheme, the once-through flow scheme is
a partial conversion option that results in some yield of unconverted material. This
material is highly saturated and free of feed contaminants but is similar in molecular
weight to the feed. If a refinery has a use for this unconverted product, such as FCC feed
or high-quality lube base oil, this flow scheme may be preferred.

Two-Stage. In the two-stage flow scheme, feedstock is treated and partially converted
once-through across a first reactor section. Products from this section are then separated
by fractionation. The bottoms from the fractionation step are sent to a second reactor
stage for complete conversion. This flow scheme is most widely used for large units
where the conversion in the once-through first stage allows high feed rates without
parallel reactor trains and the added expense of duplicate equipment.

Separate-Hydrotreat. The separate-hydrotreat flow scheme is similar to single-stage,

but is configured to send reactor effluent that has been stripped of hydrogen sulfide and
ammonia to the cracking catalyst. This configuration allows the processing of feedstocks
with very high contaminant levels or the use of contaminant-sensitive catalysts in the
cracking reactor if dictated by product demands.
The single-stage flow scheme is the most widely used hydrocracking flow scheme in
commercial service. The flow scheme allows the complete conversion of a wide range of
feedstocks and product recovery designed to maximize virtually any desired product. The
design of this unit configuration has been optimized to reduce capital cost and improve
operating performance. Greater than 95 percent on-stream efficiency is typical.
Figure 7.2.5 illustrates a typical single-stage flow scheme. Feedstock, recycle oil, and
recycle gas are exchanged against reactor effluent to recover process heat and are then sent
through a final charge heater and into the reactor section. The reactor section contains cat-
alysts that allow maximum production of the desired product slate. In virtually all hydro-
cracking systems, the combined reactions are highly exothermic and require cold hydrogen

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

UOP UNICRACKING PROCESS FOR HYDROCRACKING 7.29

FIGURE 7.2.5 Typical flow diagram of a single-stage Unicracking unit.

quench injection into the reactors to control reactor temperatures. This injection is accom-
plished at quench injection points with sophisticated reactor internals that both mix reac-
tants and quench and redistribute the mixture. Proper mixing and redistribution are critical
to ensure good temperature control in the reactor and good catalyst utilization through
acceptable vapor or liquid distribution.
In this typical configuration, reactor effluent is sent through exchange to a hot separator,
where conversion products are flashed overhead and heavy unconverted products are taken
as hot liquid bottoms. The use of a hot separator improves the energy efficiency of the
process by allowing hot liquid to go to the fractionation train and prevents polynuclear aro-
matic (PNA) fouling of cold parts of the plant. The overhead from the hot separator goes to
a cold separator, where recycle gas is separated from the product. The product is then sent to
fractionation, and recycle gas is returned to the reactor via the recycle compressor.
The fractionation train typically starts with a stripper column to remove hydrogen sul-
fide, which is in solution with the products. The removal ensures a relatively clean prod-
uct in the main fractionator column, thus reducing column costs and metallurgy
requirements. The stripper is followed by a main fractionating column with appropriate
stages and sidedraws to remove the desired products. The bottoms from this main column
is recycled back to the reactor section for complete feed conversion.
To allow complete conversion without PNA fouling or excessive catalyst coking, UOP
has developed several techniques to selectively remove PNAs from the recycle oil stream.
Some PNA removal is critical for successful operation at complete conversion. In earlier
designs, the unit was simply purged of PNAs by taking a bottoms drag stream. In newer
units, PNAs may be selectively removed by either fractionation or adsorption. The result
is an increased yield of valuable liquid product.

HyCycle. HyCycle typically uses back-staged, series-flow cracking and hydrotreating

reactors. The products and unconverted oil (UCO) from the hydrotreating reactor are
separated in the high-pressure section, creating the recycle oil for the cracking reactor.
Similar to separate-hydrotreat and two-stage configurations, the recycle oil is
contaminant-free. Because of the efficient separation of UCO from products, the recycle
oil rate can be increased above typical hydrocracking levels, allowing the cracking
catalyst to operate at lower severity and produce higher yields. The HyCycle
configuration provides the lowest operating and equipment cost for many operations.

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

7.30 HYDROCRACKING

The HyCycle process uses a combination of several unique, patented design features to
facilitate an economic full (99.5 percent) conversion operation at low (20 to 40 percent)
conversion per pass. Another important feature of the process is reduced operating pres-
sure. Relative to current practice, HyCycle Unicracking designs are typically 25 percent
lower in design pressure. The key benefits of the process are lower hydrogen consumption
and higher selectivity to heavier product. For example, up to 5 vol % more middle distil-
late yield with as much as a 15 percent shift toward diesel fuel can be achieved when com-
pared to other full conversion maximum distillate designs. This shift in selectivity coupled
with a more selective saturation of feed aromatics results in as much as a 20 percent reduc-
tion in process hydrogen requirement.
In the process, cracked products and unconverted oil are separated in the HyCycle
enhanced hot separator (EHS) at reactor pressure. The separated products are then hydro-
genated in a posttreat reactor. This unique processing step maximizes the quality of the dis-
tillate product for a given design pressure. It also provides a more efficient means of
recycling UCO to the cracking reactor, enabling a less severe (lower) per pass conversion
that results in improved selectivity and yield. The hydrocracking catalyst zone configura-
tion is referred to as back-staged because recycle oil is routed first to a hydrocracking cat-
alyst zone and then to a hydrotreating catalyst zone. The benefits of back-staging include
cleaner feedstock to the cracking catalyst and higher hydrogen partial pressure. The net
result is higher catalyst activity per unit volume, hence a lower catalyst volume require-
ment. The reactors use a common series flow recycle gas loop to maintain the economic
efficiency of a single-stage design. In addition, UOP low-temperature catalysts are used in
the reactor(s) to enable higher combined feed rates without increasing reactor diameter or
pressure drop. Figure 7.2.6 illustrates a typical HyCycle flow scheme.

Products from Hydrocracking

Hydrocracking units process lower-value, sulfurous feedstocks such as vacuum distillates
and cracked stocks to produce higher-value fuels. There is tremendous flexibility, through
choice of catalysts and unit configuration, to optimize product quality and yield structure.
The hydrocracking process has a well-demonstrated versatility. This can be shown in
the yield and product quality information shown in Table 7.2.2 for processing a Middle
East VGO for maximum distillate and for maximum naphtha, the two extremes of hydro-
cracking operation.

Improvements in Yield-Activity Relationships

One of the difficult decisions refiners face when selecting hydrocracking technology is
whether to sacrifice activity to gain yield, or sacrifice yield to gain activity. Many refiners
in North America, for example, would like to increase C6⫹ naphtha yield, but not at the
cost of lower activity. They may also like a flexible catalyst for seasonal shifts in their
product slate. Refiners in Europe and the Far East often ask for higher-activity distillate
catalysts.
To meet the needs of refiners around the world, UOP continues to develop catalysts that
provide enhanced performance without sacrificing yield or activity. Figure 7.2.7 shows rel-
ative activity-selectivity curves for previous and current generations of UOP hydrocrack-
ing catalysts. Selectivity to diesel product is shown on the vertical axis, and the catalyst’s
activity is shown on the horizontal axis. Each symbol on the curves represents a catalyst
in the UOP portfolio. New generations of catalysts are currently being developed to
improve these relationships.

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

UOP UNICRACKING PROCESS FOR HYDROCRACKING 7.31

H2
Feed
Gas
HC PT Amine Product
To LPG Fractionator
Rx Rx Scrubber
Recovery
Enhanced
Feed
Hot
Separator HPS S
HT
Rx CF

HF

0.5%
UCO

FIGURE 7.2.6 HyCycle Unicracking process schematic flow diagram.

TABLE 7.2.2 Typical Hydrocracker Yields*

Distillate Naphtha
Yield:
NH3, wt % 0.1 0.1
H2S, wt % 2.6 2.6
C2-, wt % 0.6 0.8
C3, wt % 1.0 3.3
C4, vol % 3.5 21.4
Light naphtha, vol % 7.5 39.1
Heavy naphtha, vol % 11.4 68.9
Distillate, vol % 94.0 —
Product properties:
Jet fuel cut:
Smoke point, mm 29 —
Freeze point, °C (°F) ⫺59 (⫺74) —
Aromatics, vol % 9 —
Diesel fuel cut:
Cetane no. 60 —
Total naphtha:
P/N/A, vol — 33/55/12
Research octane no. — 70

*Basis: Feedstock, Middle East VGO; density, 22.2 °API; sulfur,

2.5 wt %.
Note: P/N/A ⫽ paraffins/naphthenes/aromatics; °API ⫽
degrees on American Petroleum Institute scale.

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

7.32 HYDROCRACKING

Previous Generations
Current Generation

Distillates Selectivity Max

Flexible Naphtha

Max
Diesel Distillates

Activity
FIGURE 7.2.7 New generation Unicracking catalysts offer enhanced per-
formance.

INVESTMENT AND OPERATING EXPENSES

Capital investment and operating expenses for a hydrocracker are sensitive to

● The processibility of the feedstock
● The desired product slate
● The desired product specifications

The desired product slate has a profound effect on the arrangement of equipment, as dis-
cussed in the previous section. If the feed has demetallized oil or is more difficult to
process for some other reason, operating conditions can be more severe than in hydroc-
racking a VGO. This additional severity can be manifested in equipment, hydrogen con-
sumption, utilities, and additional catalyst. In general, a jet fuel operation is more severe
than an operation producing a full-range diesel product. Naphtha production requires a
higher hydrogen consumption than either jet fuel or diesel production.
Only typical examples can be given; not every case can be covered. The figures in the
accompanying tables are for illustrations only; variation may be expected for specific cas-
es. Typical capital investment guidelines are given in Table 7.2.3. Typical utility guidelines
are given in Table 7.2.4.

AKNOWLEDGMENTS

I wish to acknowledge Dr. Suheil Abdo for his comments on the chemistry and catalyst
sections of this chapter.

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 UOP UNICRACKING PROCESS FOR HYDROCRACKING

UOP UNICRACKING PROCESS FOR HYDROCRACKING 7.33

TABLE 7.2.3 Hydrocracker Capital Investment*

Operation Distillate Naphtha

Estimated erected cost, $/BPSD CF 2500–3500 2000–3000

*As of January 1, 2002, based on combined-feed (CF) rate; includes 20 per-

cent of material and labor as design engineering plus construction engineering
cost; does not include hydrogen plant; BPSD ⫽ barrels per stream-day.

TABLE 7.2.4 Typical Hydrocracker Utilities

Power, kW 200–450
Fired fuel, 106 Btu/h 2–6
Cooling water, gal/min 40–120
Medium-pressure steam, MT/h (klb/h) 0.11–0.22 (0.25–0.50)
Condensate, MT/h (klb/h) 0.08 (0.2)

Note: Based on 1000-BPSD fresh feed; MT/h ⫽ metric tons per hour.

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