Professional Documents
Culture Documents
Li Yilu
Unit Manager
CNOOC
Authors:
CNOOC:
Zhang Shuguang, Chief Engineer
Jiang Longyu, Operation Division Director
Hou Aiguo, Operation Division Director
Li Yilu, Unit Manager
DuPont:
Pam Pryor, Business Development Manager
Sarah Jertson, Proposal Manager
Huaping Chen, Senior Technical Consultant
Abstract:
The DuPont IsoTherming® liquid-full hydroprocessing technology is providing the refining industry with
proven utility and capital savings compared to its conventional trickle bed technology counterparts. This
paper will provide Chinese National Offshore Oil Company’s (CNOOC) firsthand experience with
successfully implementing the DuPont IsoTherming® technology at their Huizhou refinery. Operating
data and economic benefits for the grassroots diesel and vacuum gas oil hydrotreating units at the
CNOOC Huizhou refinery will also be discussed.
Project Background:
Phase II was designed to increase crude processing capacity at the refinery by 10 million ton/yr and
improve its flexibility to process a wider slate of more economically attractive sour Arab Gulf crudes. In
October 2017, after three years of construction, CNOOC claimed successful startup and testing of 15
processing units, auxiliary production units, and supporting public works for the Phase II refinery project.
The Phase II project included grassroots diesel and VGO hydrotreating units, which presented an
opportunity for CNOOC to evaluate their options considering new technology that has been
commercialized since 2005. Trickle bed hydroprocessing technology has been demonstrated globally
for decades in numerous refinery applications. However, trickle bed technology relies on maintaining a
high hydrogen to oil ratio. This leads to high energy consumption and capital investment arising from
the considerable amount of hydrogen circulation needed for the purpose of maintaining hydrogen partial
The CNOOC Phase II ULSD and VGO hydrotreating development process was carried out over a five-
year time frame as follows:
In a trickle bed reactor, combined hydrogen make-up and recycle gases and liquid feed are mixed,
heated to the desired reactor temperature and passed to a reactor fitted with an internal distribution
device on top of the catalyst beds. The distributor serves two purposes. First, it provides even
distribution of liquid reactants evenly across the catalyst bed. Secondly, it promotes mixing to pre-
saturate the liquid feed, to a certain degree, prior to entering the catalyst bed. From the perspective
of CNOOC, this reactor design has several fundamental shortcomings:
• As the reaction occurs at the catalyst surface between the dissolved hydrogen and the reactive
species in the feed, the hydrogen is depleted from the liquid. In most refinery applications, the
amount of hydrogen required for the reactions is greater than the solubility of hydrogen in the
fresh feed alone, or so-called gas-limited reaction zone. Thus, in order for the reaction to
continue to completion, additional hydrogen must be replenished from the vapor phase. This
in effect makes the rate of hydrogen mass transfer, or more accurately the creation of interfacial
area (due to interfacial hydrogen transfer coefficient typically high) into the liquid phase a factor
in the overall kinetics of the process.
• Once the interfacial area for hydrogen mass transfer is enough for the reaction to proceed, the
catalyst activity within this gas-limited reaction zone has to be reduced by grading catalysts.
Otherwise, excessive heat release from the reactions that occur in this zone would cause an
excessive temperature rise and subsequent premature catalyst coking. As a result, the reactor
volume is not effectively utilized.
• To ensure catalyst performance and longevity, excess hydrogen, often several times the
quantity required for the reactions, is recycled back to the reactor to maximize the hydrogen
partial pressure throughout the system. Hydrogenation reactions are highly exothermic. The
mass flow of hydrocarbon feed and recycle hydrogen through the reactor has a limited capacity
to adsorb the energy liberated and therefore hydrogen quench has to be used to control
temperature rise. In applications that involve high chemical hydrogen consumption it is
common to utilize a high hydrogen to oil flow ratio within the reactor to control the catalyst bed
temperature rise. The higher temperature at the bottom portion of reactor bed, together with
high gas flow, results in additional liquid feed vaporization. This phenomenon makes this
aspect of trickle bed reactor design and operation very difficult, leading to low hydrogen partial
pressure together with partially dry catalyst beds. This can seriously downgrade the reactor
• Two-phase flow through a heterogeneous catalyst is prone to liquid flow maldistribution. Any
slight variations in pressure drop through the bed, even an unlevel catalyst bed, will result in
liquid/vapor maldistribution. This results in inefficient use of the catalyst and results in hot spots
or coke formation.
Liquid distribution differences between IsoTherming® and trickle bed are illustrated in Figure 3.
Figure 3
IsoTherming® & Trickle Bed Liquid Distribution Differences
Heat capacity of the total liquid IsoTherming® reactor feed (fresh feed plus recycle) is considerably
greater than that of the mixed phase feed (combined fresh feed and the hydrogen gas recycle
stream) associated with trickle bed technology. As a result, the temperature rise across an
IsoTherming® reactor/bed is considerably less than that of a trickle bed reactor. This lower
temperature rise eliminates the need for inter-bed cooling, typically associated with trickle bed and
the additional complexity it brings to the reactor operation and design.
For particularly severe services such as hydrotreating cracked stocks (coker gas oils or light cycle
oils) or during mild hydrocracking, the considerably lower temperature rise minimizes catalyst
coking rates and offers conceptually longer catalyst life. The IsoTherming® technology also virtually
ensures that there can be no large thermal excursions and hence the chance of a runaway reaction
is minimised. CNOOC deduced that IsoTherming® technology is inherently safer than trickle bed.
The inherent differences between IsoTherming® and trickle bed technologies led CNOOC to conclude
that IsoTherming® has advantages over conventional hydroprocessing technology including:
The IsoTherming® technology offers a simplified process design with minimal high-pressure
equipment due to replacement of the recycle compressor gas loop with a canned motor pump.
By eliminating the hot and cold high-pressure separators, high-pressure condenser, recycle
gas amine scrubber and the recycle compressor, CNOOC expected significant capital savings
for both the ULSD and VGO hydrotreating projects. Table A provides a summary of differences
in high pressure equipment requirements for the IsoTherming® and trickle bed technologies.
From CNOOC’s perspective, the less complex IsoTherming® reactors and the absence of a
hydrogen recycle system result in a considerably smaller, simplified design. Depending on the
The IsoTherming® reactor feed/effluent heat exchanger is a key piece of equipment designed
to recover the heat of reaction energy by heating the reactor feed with the reactor effluent. A
heat exchanger of this kind operates at a high temperature and pressure and has limited
flexibility in operating conditions. The traditional hydrogenation unit adopts the thread locking
ring heat exchanger. CNOOC opted to incorporate a new spiral-wound high-efficiency heat
exchanger for this service.
The spiral-wound tube heat exchanger design includes direct welding of the tube sheet to the
shell rather than the traditional flange connection structure. This design minimizes the risk of
leaks seen with the HP thread locking ring heat exchanger. CNOOC Huizhou replaced two
traditional HP thread locking ring heat exchangers with one spiral-wound tube heat exchanger
in the ULSD IsoTherming® hydrotreater. This equipment selection lead to an equipment
investment savings of 3.88 million CNY (U.S.$577,232).
By eliminating the hydrogen recycle gas compressor and its ancillary recycle loop equipment,
significant maintenance and operating cost savings can be realized. Overall, the IsoTherming®
technology has consistently demonstrated a 40-60% utility savings over trickle bed technology
including:
• The IsoTherming® reactor canned motor pump consumes substantially less energy than a
comparable trickle bed recycle gas compressor. The IsoTherming® unit power consumption is
reduced, on average, by 30-40% for any application.
• The combined feed and reactor recycle volumes are sufficient to maintain low temperature
profiles across each catalyst bed. The traditional trickle bed hydrogenation technology must
control the bed temperature rise with chilled hydrogen, in which a large amount of reaction heat
is removed with the recycle hydrogen, and eventually the majority of heat is cooled in the HP
air cooler.
• In addition, the IsoTherming® technology recovers the heat of reaction by recycling a portion of
the hot hydrotreated reactor bottoms back to the inlet of the reactor. This direct transfer of heat
to the feed in turn reduces the fired heater duty, i.e. lowers fuel gas consumption. Overall, the
IsoTherming® technology has consistently demonstrated a 30-60% drop in fuel gas costs due
to the reactor feed/bottoms heat integration designed into each IsoTherming® unit. Any excess
reactor bottoms heat, beyond what is required to pre-heat the reactor feed, can be used to
generate steam.
The IsoTherming® hydrotreating technology was first commercialized in 2003 at the Giant refinery in
Gallup, New Mexico. DuPont acquired the IsoTherming® hydroprocessing technology in 2007 and has
since licensed more than twenty units globally. At the time CNOOC evaluated hydrotreating technology
options, DuPont had licensed seven (7) IsoTherming® units in China across a range of range of
capacities and applications as presented in Table B.
The IsoTherming hydrotreating process eliminates the recycle hydrogen system used in the trickle
bed process, thus leading to savings in energy consumption as well as savings in equipment
investment. CNOOC concluded “Thus, the DuPont process can operate with lower investment and
lower operating cost so that it is a state-of-the-art technology taking a leading position at home and
abroad.” CNOOC went on to state “The full liquid-phase hydrogenation technology is characterized by
The CNOOC Huizhou Phase II, 3.4 MTPA (71,639 bpd) IsoTherming® ULSD unit was designed to
operate with ADU/VDU straight-run diesel as feedstock to make a diesel product that complied with
China National V criteria. DuPont designed the IsoTherming® ULSD hydrotreater based on
feedstock properties, Table C, and product properties, Table D, provided by CNOOC.
The CNOOC Huizhou Phase II, 2.6 MTPA (59,105 bpd) IsoTherming® VGO unit was designed to
hydrotreat a ADU/VDU VGO feedstock to make VGO to be fed to the fluidized catalytic cracking
(FCC) unit and to make a diesel product to be fed to the 3.4 MTPA (71,639 bpd) diesel
hydrogenation unit for further processing. DuPont designed the IsoTherming® VGO hydrotreater
based on feedstock properties, Table F, and product properties, Table G, provided by CNOOC.
CNOOC broke ground for the ULSD unit on October 16, 2014 followed by a successful startup on
September 29, 2017. At the time of startup, the ULSD unit operation complied with the design and
the ULSD product met China V standards as well. The ULSD unit underwent a Performance
Calibration Test at full rate September 4-7, 2018. During the calibration test, all the products and
waste emissions met unit design criteria indicating the IsoTherming® technology operated per the
design intent. Historical diesel product sulfur content is presented in Figure 6.
Figure 6
CNOOC Phase II IsoTherming® ULSD Product Sulfur
WABT calculations for traditional trickle-bed technology are well documented for refinery
hydroprocessing. Hydrogen is in excess and once the reactor pressure is set, reaction rate is
typically governed by non-hydrogen reactants and reaction kinetics are most often represented
by targeted reactants such as sulfur, nitrogen etc. WABT calculations are in a power law format
when calculating catalyst deactivation. Results of operational WABT and normalized WABT
calculations for the CNOOC Huizhou Phase II ULSD unit using industry standard trickle bed
methodology are shown in Figure 7. The operational WABT is calculated as usual, i.e., 1/3 of
reactor inlet temperature plus 2/3 of the reactor outlet temperature. A linear trending line of the
normalized WABT is also shown. The slope of this normalized trending line shows about 1.3°C
(2.3°F) per month. In traditional trickle-bed technology, the slope of this trending line is viewed
as the catalyst deactivation rate.
The issue with applying trickle bed WABT methodology to IsoTherming® is that hydrogen is
also a variable, in addition to those mentioned above for trickle bed, (with even stronger
variation than other reactants along reactor beds) and needs to be represented in the kinetics
if the power law is to be used to determine catalyst deactivation. This creates some challenges.
Namely, in trickle-bed, normalized WABT is essentially an integral average of a single variable,
for example, sulfur concentration. While in the IsoTherming® technology, the normalized
WABT is an integral average of two variables in its product format (power law). So,
mathematically, one is a line integration average (trickle-bed), the other is surface integration
average (IsoTherming®). While integration average (normalized WABT) can always find a point
(operational WABT) on the line to establish correspondence, there will be a much wider area
to find a single corresponding point (operational WABT, most likely could be multiple points)
on a two-dimensional surface to the integration average (normalized WABT). This means if one
wants to find such a single and unique correspondence between operational WABT and
normalized WABT, the normalized WABT must be calculated close enough to operation points
where one of the variables, say, nominal hydrogen partial pressure more or less stays the
same. Only such a calculated normalized WABT can be used to realistically detect the actual
catalyst deactivation.
Figure 8 shows one such calculation and the slope indicated is 0.75 °C (1.35°F) per month.
This result corresponds closely to commercial observations for the CNOOC Phase II ULSD
IsoTherming® unit. A more intuitive way to look at this issue follows.
The hydrogen profile for any IsoTherming® bed, Figure 9, would show that roughly one-third of
the way down the bed, hydrogen has already been consumed to a significant level. Below this
point, the reaction rate will typically slow down due to lower hydrogen availability, not catalyst
deactivation.
Figure 9
IsoTherming® Hydrogen Profile
Attributing the slower reaction rate to catalyst deactivation, using the trickle-bed method, will
reflect an over, and unrealistic, correction. This over correction must be accounted for during
the normalization if trickle-bed normalization method is still to be utilized.
The design basis for the IsoTherming® ULSD hydrotreater did not account for the presence of
arsenic in the feed. As a result, the current ULSD catalyst loading does not have specific
arsenic guard material. Figure 10 illustrates the consistent presence of arsenic in the diesel
feed analysis since startup.
Figure 10
CNOOC Huizhou Phase II IsoTherming® ULSD Feed Arsenic Content
Arsenic is widely recognized as a strong hydrotreating catalyst poison and its destructive effect on
hydrotreating catalyst is regarded, by many, as permanent. The IsoTherming® Catalyst
Deactivation plot, Figure 8, and commercial operating data does not reflect the expected negative
impact of arsenic poisoning.
CNOOC broke ground on the IsoTherming® VGO hydrotreating unit on October 16, 2014 and
subsequently initiated a successful startup on October 1, 2017. CNOOC indicated it has
demonstrated a successful application of the DuPont IsoTherming® liquid-phase hydrogenation
technology in Huizhou Petrochemical, with all technical indicators proving the technology works
well. A performance test for this unit will be completed in 2019 once sufficient feedstock is available
to run the unit at maximum capacity.
CNOOC developed cost estimates for engineering and bare equipment during their
hydroprocessing technology option evaluation. Their results are summarized in Table I.
®
CNOOC Total Engineering & Bare Trickle bed IsoTherming Difference
Equipment Cost Estimate ¥362,759,800 ¥279,628,000 ¥83,131,800
$54,413,970 $41,944,200 $12,469,770
Figure 11
CNOOC Phase II ULSD Feed Heater Fuel Gas Consumption
The fuel gas savings combined with additional IsoTherming® operating cost advantages result
in total operating cost savings to CNOOC for the Phase II IsoTherming® ULSD unit of 65.7
million CNY/year (U.S.$9,853,200/year) compared to a trickle bed design.
A similar calculation was done by CNOOC for the Phase II IsoTherming® VGO hydrotreater.
CNOOC determined an average IsoTherming® VGO hydrotreater only requires approximately
60% of the energy consumption of a comparable Chinese trickle bed design. While a portion
of the IsoTherming® operating cost advantage comes from reduced fuel gas consumption, the
CNOOC IsoTherming® VGO unit, realizes total operating cost savings of 27.3 million CNY/year
(U.S.$4,095,000/year) compared to a trickle bed design.
C. Social benefit
CNOOC concluded that the projects, when built and put into operation, did yield a remarkable
reduction in energy consumption. The anticipated savings of large amounts of fuel gas and steam
were realized along with a considerable reduction in emissions. Overall the projects had a positive
impact on environmental protection.
Conclusion
Currently two hydrogenation options are available for production of ULSD, including traditional trickle
bed technology and liquid-phase hydrogenation technology, IsoTherming®. CNOOC technology
selection targeted reduced operating costs and improved economic benefits. The IsoTherming®
technology has demonstrated through commercialization that it is a well-proven, reliable and
acceptable refining upgrading technology that is capable of diesel and VGO hydrotreating. CNOOC
states the IsoTherming® hydroprocessing technology is characterized by low investment, minimal plot
space and low energy consumption and therefore it deserves broad application.