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Meeting low sulphur diesel challenges

Liquid stream hydroprocessing technology enabled a refiner to meet fast-


changing diesel sulphur specifications and process a wide variety of feedstocks

Timothy Carmann DuPont Clean Technologies

D
iesel is the predominant fuel used for ship-
20th century, and it has essentially been done
ping goods and moving freight across the the same way since that time – using conven-
country and around the world. Increasing tional, two-phase trickle bed reactor technology.
global demand for cleaner burning transporta- Approximately 10 years ago, a disruptive hydro-
tion fuel (particularly diesel fuel) is driving refin-
processing innovation, IsoTherming technology,
ers to look for ways to increase low sulphur diesel
was finally brought to the marketplace, chal-
production capacity. At the same time, refiners lenging the norms associated with conventional
are looking to process larger amounts of low costtrickle bed technology. The core of IsoTherming
sour and heavy feedstocks to increase profitabil-technology is the ability to provide the hydrogen
ity. With increasingly strict fuel quality regula-
necessary for hydroprocessing reactions using a
tions being rolled out across the world, meeting liquid stream, rather than a recycle gas stream.
this increased demand for cleaner burning diesel To satisfy hydrogen requirements within the
fuel is a significant challenge. reactor, fresh reactor feed is saturated with
To meet increased demand for cleaner burn- hydrogen. Additional hydrogen can be added to
ing fuel while simultaneously maintaining or the feed by means of a saturated product recy-
increasing profitability, refiners need to increase
cle stream (using a reactor recycle pump) and
their hydroprocessing capacity and capabilities by hydrogen injection to resaturate the liquid
to produce more diesel and remove more sul- within or between catalyst beds. These different
phur while minimising capital investment and hydrogen addition options eliminate the need
operating costs. Hydroprocessing involves chem- for a recycle gas compressor. Figure 1 illustrates
ically treating a petroleum stream with hydrogen these different hydrogen delivery options for an
in the presence of a catalyst at elevated tempera-
IsoTherming reactor.
tures and pressures. Hydroprocessing units allow The technology also employs a novel reactor
refiners to improve product system with a single liquid
quality, comply with govern- Make-up phase that uses hydrogen
ment regulations, and increase hydrogen and catalyst more efficiently.
profitability by converting low Feed Regardless of the method
valued streams into high mar- of hydrogen delivery, all of
gin and high quality prod- the hydrogen needed for the
ucts. Refiners can increase hydroprocessing chemical
hydroprocessing capacity reactions is dissolved in a sin-
by constructing new grass- IsoTherming gle liquid phase. Applications
roots hydroprocessing units or reactor in which the technology has
debottlenecking and revamping been commercially deployed
existing units. To include kerosene and die-
Recycle low-pressure sel hydrotreating, fluid
pump separation
IsoTherming technology catalytic cracking (FCC) pre-
Hydroprocessing has been treating, and mild hydroc-
part of the typical refinery Figure 1 Hydrogen delivery options for racking. IsoTherming tech-
configuration since the mid- IsoTherming technology nology has commercially

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processed a wide range of profile and acts as a heat sink
straight run and cracked feed- Conventional hydroprocessing for exothermic chemical reac-
stocks, including 100% light tions. This results in a lower
cycle oil (LCO), at capacities temperature rise across the
ranging from 2000 b/d to 78 reactor and minimises light
500 b/d (13 m3/hr to 520 m3/ ends generation.
hr).
The technology has other IsoTherming hydroprocessing Reduced operating expenses
commercially proven advan- and capital cost savings
tages compared to conven- IsoTherming technology’s
tional trickle bed technology. approach to hydrogen deliv-
They include the following. ery eliminates the need for a
recycle gas compressor (and
Increased catalyst associated high pressure sep-
performance and improved Figure 2 Conventional trickle bed vs aration equipment). Figure 2
yields IsoTherming equipment configurations shows a visual comparison
A conventional trickle bed of the equipment differences
reactor depends on near perfect feedstock dis- between IsoTherming technology and conven-
tribution throughout the catalyst bed to maxim- tional trickle bed technology. IsoTherming com-
ise reaction efficiency and to avoid overheating mercial units have noticeably less equipment and
and coking. In addition, the quench stages in a smaller plot space requirements compared to
trickle bed reactor are meant to manage temper- conventional trickle bed units.
ature rise and require the injection of large vol- Electricity usage is lower for IsoTherming
umes of additional hydrogen into the reactor. technology due to the use of a lower power
With an IsoTherming liquid full reactor, the cat- reactor recycle pump for delivering hydrogen
alyst is completely wetted. This draws the heat instead of a higher power recycle gas compres-
of reaction away from the catalyst surface and sor. In addition, the direct heat transfer result-
eliminates local hot spots that would otherwise ing from the recycle of hot reactor product to
promote coking and catalyst deactivation. All the inlet of the reactor reduces the required
commercially operating IsoTherming gas- fired heater duty needed to achieve the target
oil hydrotreating units have experienced cata- reactor temperature. For units with low hydro-
lyst life in excess of four years, demonstrating gen requirements, the ability to supply hydro-
the technology’s ability to achieve lower cata- gen using only feed saturation (and no saturated
lyst deactivation rates than conventional trickle product recycle) means even fewer pieces of
bed technology. In addition, uniform liquid flow high pressure equipment are required. The tech-
throughout the catalyst bed in an IsoTherming nology has been shown to have 40-60% utility
reactor results in a uniform radial temperature savings and up to 30% capital cost savings com-
pared to conventional trickle
bed technology in evaluated
units.
Reactor bed temperature,

~4 h ~5 h Robustness, reliability, and


Prior to power
outage, WABT
Following power outage, safety
WABT was equal or less for
One unique feature of
ºC

was ~347ºC. the same feed composition;


desulphurization rates were IsoTherming technology is the
Power outage Power the same as before the
occurs. restored. power outage. reactor recycle pump. As men-
tioned previously, the reac-
~308ºC
tor recycle pump recycles a
Time, h portion of the reactor prod-
uct to the inlet of the reactor.
Figure 3 IsoTherming reactor bed temperature during an unplanned power This additional liquid volume
failure is then saturated with hydro-

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gen to ensure that sufficient levels of hydro- and a lack of hot liquid entering the system.
gen are delivered to the reactor for all required With IsoTherming technology, hydrogen con-
hydroprocessing chemical reactions. This par- tent in the liquid full reactor is limited by solu-
ticular service requires low head and high flow bility. While the liquid maintained in the reactor
to pump high pressure and high temperature still contained dissolved hydrogen, hydrogen sol-
liquid. Conventional pumps with mechanical ubility limitations significantly reduced the num-
seals do not offer the necessary safety and reli- ber of hydroprocessing chemical reactions (and
ability, so a canned motor pump is the only via- associated heat release) that could occur. Also,
ble type of pump to use for this service. Canned the liquid full catalyst bed acted as a heat sink for
motor pumps are often an anomaly in the refin- the exothermic chemical reactions, which limited
ing industry, but are very commonplace in the undesired temperature rise and eliminated any
chemical industry. They are used because the potential for runaway in the reactor.
high suction pressure and temperature make Within five hours of regaining power, the
a conventional shaft sealing system unrelia- commercial IsoTherming unit shown in Figure
ble, and the design guarantees there are no 3 returned to stable operation, producing an
leaky seals. DuPont engaged rotating equipment on-spec diesel product at similar operating tem-
experts to develop a complete specification for perature and with no apparent catalyst deacti-
the IsoTherming reactor recycle pump, which has vation. This quick return to original operating
resulted in robust reactor recycle pump designs conditions without any long-term damage (and
well known for their commercial reliability. without having to refill, reheat, and repressur-
The technology is also an inherently safer ise the reactor) demonstrates the technology’s
hydroprocessing technology. Elimination of the robustness and inherently safer operation com-
recycle gas compressor and associated treating pared to conventional trickle bed technology.
equipment not only removes a large amount of
high pressure equipment from the system, but A grassroots IsoTherming DHT unit
also significantly reduces the hydrogen inventory In April 2014, DuPont commissioned and
in the unit. There is also no potential for reactor brought online the world’s largest capacity grass-
runaway (and associated catalyst deactivation) roots IsoTherming diesel hydrotreating (DHT)
in the IsoTherming reactor. This is illustrated in unit (78 500 b/d, 520 m3/hr) at a refinery in Asia.
Figure 3, which shows operating data from a com- The unit utilises DuPont proprietary hydropro-
mercial unit that experienced a four hour power cessing catalyst and was designed to process a
failure. feed blend containing 60% straight run diesel
With a conventional trickle bed unit, a power (SRD) and 40% cracked feedstocks consisting of
failure would cause the unit to lose make-up light coker gas oil (LCGO), light cycle oil (LCO),
hydrogen and would trip the reactor charge desulphurised resid (RDS), and coker naphtha
pump and heater. To eliminate the potential for (CN). Capital cost advantages, decreased energy
reactor temperature runaway and increased cata- consumption, and reduced utilities requirements
lyst deactivation, operators would need to quickly and operating costs were the key drivers for the
depressurise and drain the conventional trickle refiner’s selection of IsoTherming technology
bed reactor to remove excess hydrogen and reac- over conventional trickle bed technology.
tants. Once power was restored, the conven-
tional trickle bed unit would need to be refilled, Unit design
reheated, and repressurised. This process would When the DHT unit was originally licensed in
take multiple hours (if not days), resulting in 2010, it was designed to produce a Euro IV equiv-
additional unit downtime. alent (<50 wppm sulphur) diesel product (‘Phase
For the reactor power failure event shown in 1’) to meet impending government fuel regula-
Figure 3, the reactor vents and pressure con- tions. During the detailed design and construc-
trol valve on the reactor outlet were completely tion phase, however, the government announced
closed so that liquid volume was maintained in plans to implement even more stringent Euro V
the reactor vessel at a pressure close to normal equivalent (<10 wppm sulphur) diesel fuel regu-
operating conditions. The cooling over the four lations to address air quality issues. To address
hour outage period was due to natural heat losses the rapidly changing regulations, DuPont worked

www.digitalrefining.com/article/1001426 PTQ Q4 2017 3


Reactor 1 Reactor 2 Make-up
hydrogen

M
Diesel
product
Blended
feed

Stripper
off-gas

Unstabilised Stabilised
CLPS
BFW Steam naphtha naphtha
off-gas
product product
Steam

Figure 4 Process flow diagram of the IsoTherming DHT unit

with the customer to develop a plan to meet the 2014 and the DHT unit met all Phase 1 perfor-
new product specifications. To minimise the mance requirements. Due to the wide operability
overall project cost and schedule impact, DuPont range afforded by the Phase 1 DHT unit design,
launched a ‘Phase 2’ process design phase in par- the customer was able to produce a wide vari-
allel with the original Phase 1 detailed design ety of products to meet local demand, and chose
and construction activities. During the Phase 2 to continue operation rather than commission
design phase, DuPont designed and integrated the second reactor. In February 2016, the Phase
an additional IsoTherming reactor into the pre- 2 reactor was commissioned and the DHT unit
vious Phase 1 design. The additional catalyst vol- demonstrated continuous production of Euro V
ume within the new reactor would enable the equivalent diesel product in compliance with gov-
customer to produce a Euro V equivalent die- ernment regulations. A complete process flow
sel fuel product compliant with the upcoming diagram of the grassroots DHT unit is shown in
regulations. To expedite fabrication and com- Figure 4.
missioning of the Phase 2 reactor, DuPont and
the refiner agreed to procure a duplicate of the DHT unit operating performance
Phase 1 reactor design. With detailed engineer- Upon initial start-up of the IsoTherming DHT
ing and fabrication already complete on the first unit in April 2014, a wide range of diesel fuel
reactor, design duplication allowed the refiner regulations were being phased in, providing
to reduce the second reactor’s delivery time. By the refiner with multiple outlets and markets
early 2014, however, the refiner had completed for the DHT unit diesel product. As the ‘Initial
construction activities associated with the Phase Operation’ phase in Figure 7 shows, the refiner
1 design and decided to start up the IsoTherming was able to selectively produce diesel products
DHT unit without the second reactor. The Phase ranging from 10-150 wppm sulphur. The key fac-
1 design was successfully commissioned in April tor allowing the customer this operational flexi-

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bility was the design of the DHT
unit reaction zone. Initial operation Full operation
The final DHT unit reaction (one reactor) (two reactors)
200
zone is configured in two sepa- 180

consumption, % of design
rate sections. The first reaction
160

Chemical hydrogen
zone (Phase 1 design) features
140
a single IsoTherming reac-
120
tor (Reactor 1) which utilises a
100
reactor recycle pump to recycle Design value
80
a portion of the reactor prod-
60
uct to the inlet of Reactor 1. The
40
reactor product recycle stream
20
is saturated with additional
hydrogen, which provides suffi- 0
0 100 200 300 400 500 600 700 800 900 1000
cient hydrogen for the required Days on stream
hydroprocessing chemical reac-
tions and provides the DHT unit Figure 5 Chemical hydrogen consumption data during commercial operation
the flexibility to operate with of the IsoTherming DHT unit
large variations in feed flow and
composition. This operating
flexibility is demonstrated in the Initial operation Full operation
DHT unit’s hydrogen consump- (one reactor) (two reactors)
18 000
tion (see Figure 5, days 0-600),
Feed sulphur content, wppm

16 000
which varies from 60% to over
14 000 Design value
160% of the design hydrogen
12 000
consumption. This flexibility
allowed the refiner to process a 10 000
wide variety of feeds in order to 8000
maximise refinery profits. 6000
By 2015, Euro IV equiva- 4000
lent diesel fuel regulations had
2000
been widely implemented and
0
the refiner had shifted oper- 0 100 200 300 400 500 600 700 800 900 1000
ation of the DHT unit almost Days on stream
exclusively to Euro IV equiva-
lent (<50 wppm sulphur) diesel Figure 6 Feed sulphur content data during commercial operation of the
production (see Figure 7, days IsoTherming DHT unit
300-600). With the impend-
ing implementation of Euro V equivalent diesel dilution effect) in Reactor 2 allows the over-
regulations, the refiner decided to commission all DHT unit to produce Euro V equivalent die-
the second (Phase 2) IsoTherming reactor in sel product (see Figure 7, days 650-1000) with
February 2016. The second reaction zone (Phase reduced catalyst volumes.
2 design) features a single reactor (Reactor 2) Since the start-up of Reactor 2, the DHT unit
installed downstream, and in series with the first has continuously produced Euro V equivalent
reactor (Reactor 1). Reactor 2 is a polishing reac- diesel product. The capabilities of IsoTherming
tor designed to convert the Euro IV equivalent technology continue to provide the refiner with
diesel from Reactor 1 into Euro V equivalent die- a wide range of operating flexibility. As Figures
sel product. Unlike Reactor 1, Reactor 2 does not 5, 6 and 7 show, the refiner is able to process a
utilise a saturated product recycle stream, and wide variety of feedstocks with sulphur levels and
instead operates in the plug flow regime (with hydrogenation requirements well in excess of the
once-through liquid). Elimination of the satu- DHT unit design, while still consistently produc-
rated product recycle stream (and its associated ing Euro V equivalent diesel product.

www.digitalrefining.com/article/1001426 PTQ Q4 2017 5


increasingly severe feedstocks
Initial operation Full operation at a lower capital cost. The com-
(one reactor) (two reactors) pany is also actively identifying
150
and evaluating opportunities
for the technology in new and
Diesel product sulphur

120
emerging markets and applica-
content, wppm

tions and licenses the technology


90
and offers products and services
throughout the life of the unit.
60
Design value With 24 licensed commercial
units worldwide, IsoTherming
30
technology is an innovative and
Design value
commercially proven technology
0 that is changing the way refiners
0 100 200 300 400 500 600 700 800 900 1000
Days on stream are looking at hydroprocessing.

Figure 7 Diesel product sulphur content data during commercial operation IsoTherming is a trademark of DuPont Clean
of the IsoTherming DHT unit Technologies.

Conclusion
IsoTherming hydroprocessing technology from Timothy Carmann is a Business Development Manager with
DuPont Clean Technologies. He has 11 years of experience
DuPont has many commercially proven advan-
with development, commercialisation, and licensing of new
tages compared to conventional trickle bed
technologies. He holds BS and MS degrees in chemical
technology. These include increased catalyst
engineering from the University of Nebraska-Lincoln and North
performance, improved product yields, reduced Carolina State University, respectively, and an MBA degree from
operating expenses, capital cost savings, and Washington University in St. Louis.
inherently safer operation. In addition, the suc- Email: timothy.carmann@dupont.com
cessful start-up and ongoing operation of the
world’s largest capacity grassroots IsoTherming
DHT unit using DuPont proprietary catalyst
shows that IsoTherming technology alone can LINKS
consistently produce Euro V equivalent (<10
wppm sulphur) diesel product, even with signif- More articles from: DuPont Clean Technologies
icant variability in feed properties and operating
More articles from the following categories:
performance.
Hydroprocessing
DuPont is continuously optimising its liq- Sulphur Removal and Recovery
uid full IsoTherming reactor design to process

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