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Diesel hydroprocessing
 Optimizing your
diesel production
3 |
2

Optimizing your diesel production

As an increasing number of countries

move towards requirements for low
and ultra-low sulfur diesel with a high
cetane number, the refining industry
faces a double-edged challenge in
terms of meeting the ever stringent
specifications for diesel fuel, while
simultaneously producing more diesel
product from lower quality feedstocks.

The market for clean and ultra-clean fuels continuously calls for
a variety of improved diesel hydrotreating catalysts and
processes. Many of the low-pressure diesel hydrotreaters are
being revamped, and new high-pressure units are built in order
to meet the latest diesel specifications.

Whether it is extracting more diesel product from each barrel of

oil, creating higher quality of the middle distillate product or
meeting the growing demand for processing of renewable feeds,
our global network of industry-leading scientists and catalyst
specialists will meet your requirements.
4 |
Optimizing your diesel production
High-performance catalysts
and technology
Topsoe has been at the forefront of the hydroprocessing catalyst
technology for many years, and today, we are the market leader
within the field of catalysts, licensed technology and reactor
internals for the production of Ultra-Low Sulfur Diesel (ULSD).
Our HydroTech™ solutions for hydroprocessing offer you the
opportunity to meet all legislative requirements when producing
clean fuels.
HydroTech™ includes a broad catalyst portfolio and advanced
innovative hydroprocessing technologies, supported by
consultancy services from our experienced engineers.
More than 50% of all the ultra-low sulfur diesel
units worldwide use catalysts from Topsoe
>50%
Using our extensive knowledge of hydroprocessing, we are able
to optimize operating conditions and catalyst loadings, thereby
minimizing investment costs and utility consumption.
Our HydroTech™ solutions within diesel hydrotreating consist
of the following technologies:
• production of ultra-low sulfur diesel
• dewaxing of diesel
• cetane improvement
• saturation of aromatics
• hydroprocessing of renewable feeds
5 |

Optimizing your diesel production

Up to 40% activity increase when using HyBRIM™

catalysts

up to 40%

BRIM® and HyBRIM™

catalyst technology
Topsoe BRIM® catalysts have proven to be leading for the
production of clean transportation fuels. By virtue of the unique
method of catalyst preparation, they exhibit a high activity and
stability at all pressure levels on straight-run feed, as well as on
cracked feedstocks.

With the invention of our HyBRIM™ catalyst preparation

technology, we have added new products to our portfolio that
can help you reach your targets even more efficiently. HyBRIM™
combines the existing BRIM® technology with an improved
catalyst preparation step, resulting in an increased activity.
The HyBRIM™ catalysts exhibit the same high stability that our
customers have come to expect from all of our BRIM® catalysts. HyBRIM™ catalyst
State-of-the-art
diesel catalysts
7 |

State-of-the-art diesel catalysts

Topsoe offers our cobalt molybdenum (CoMo) catalysts for

low-medium pressure applications and our nickel molybdenum
(NiMo) catalysts for high pressure applications.

Cobalt molybdenum catalysts

Topsoe cobalt molybdenum (CoMo) catalysts are recommended
for low and ultra-low sulfur diesel services, often being operated
in low to medium pressure (20-50 bar/300-750 psi) applications
with high nitrogen feedstocks. Frequently, hydrogen
consumption in these applications is critical. Currently, our CoMo
series consists of the following catalysts listed with increasing
activity:
Figure 1: Active structure, the metal slab, of a working NiMo catalyst
TK-568 BRIM® < TK-570 BRIM® < TK-578 BRIM®

TK-568 BRIM® is our cost-efficient CoMo catalyst, especially

developed for a lower fill cost option. The low density formulation
has been designed for units processing average severity feeds,
while meeting ULSD product specifications and still providing a
stable performance during operation.

For processing cracked stock fractions, and hence more difficult

feeds, TK-570 BRIM® is well suited with its excellent HDS
activity. The enhanced pore structure combines a moderate
density with an activity that has shown to provide an
outstanding performance.

TK-578 BRIM® is the recommended catalyst when high activity

and high stability is required, leading to a cost-effective life cycle
Figure 2: Active structure, the metal slab, of a working CoMo catalyst
for demanding ULSD services with high levels of cracked stock.
Its improved activity can be utilized to increase cycle length to
process tougher feeds or to increase feed rate.
8 |

State-of-the-art diesel catalysts

Case story: Feed properties

Feedstock type
Unit

SR VGO/Kero + 35% LCO

Increased capacity SG/°API 0.85/34.5
with TK-578 BRIM® Final boiling point, (°C/°F) 350/660

Sulfur, wt % 0.25
Aiming for a long cycle length and producing less than 10 ppm
sulfur diesel with the highest possible throughput, this US refiner Operation conditions
operates a 20,000 BPSD diesel hydrotreating unit.
0.8 (TK-578 BRIM®)/
LHSV, hr -1
After two successful cycles with TK-576 BRIM (previous ® 0.7 (TK-576 BRIM®)
generation CoMo catalyst) and TK-578 BRIM® over a six-year H2 inlet pressure, (barg/psig) 42/610
period, the client decided to continue with TK-578 BRIM® due to
its proven success. This catalyst made it possible to increase the Product properties
annual throughput from 14,000 to 20,000 BPSD, corresponding
Sulfur, wt ppm <10
to an annual profit gain of approx. €18/$24 mil.

390 734
TK-578 BRIM®
TK-576 BRIM®
380 716

370 698
Temperature, °C

Temperature, °F
360 680

350 662

340 644

330 626

0 200 400 600 800 1000

Run days

Figure 3: The result of the upgrade to TK-578 BRIM® is clearly observed on the normalized WABT.
The start-of-run (SOR) temperature is more than 5°C (9°F) lower than the cycle loading with TK-576 BRIM®.

The customer says: “It was essential for us to find a catalyst capable of producing
ultra-low sulfur diesel with minimum catalyst deactivation throughout the cycle.
We found that Topsoe came out the strongest on quality, with impressive scientific
research behind their catalyst, and the performance of TK-578 BRIM® exceeded
our expectations with respect to cycle length and capacity.”
9 |
State-of-the-art diesel catalysts
Nickel molybdenum catalyst 
Topsoe NiMo catalysts are recommended for the production of
ULSD at high operating pressures (> 50 bar/750 psi), especially
when sufficient hydrogen is available. NiMo catalysts are the
optimal solution when targeting high activity and volume swell.
NiMo catalysts are preferable to CoMo catalysts at:
• high-pressure operations
• lower content of feed nitrogen
• lower feed rate.
Currently, our NiMo series consists of the following catalysts
listed with increasing activity:
TK-563 BRIM® < TK-569 HyBRIM™ < TK-609 HyBRIM™
Topsoe cost-efficient solution developed for removing nitrogen
and sulfur at a higher pressure operation are TK-563 BRIM® and
the TK-569 HyBRIM™. The formulation has been designed for
units processing lower severity feed, while meeting low sulfur
product specifications and stable hydrodenitrogenation (HDN)
during operation.
Our highest activity catalyst, ideally suited for treatment of very
difficult feedstocks including all cracked material, is the TK-609
HyBRIM™. It is designed to maximize nitrogen removal, increase
volume swell and hydrogenation of the aromatic compounds,
while minimizing the deactivation rate to provide a long cycle.
The higher activity can be utilized to obtain longer cycles to
process tougher feeds or to improve the yield structure.
10 |

State-of-the-art diesel catalysts

Case story:
Comparison of
TK-609 HyBRIM™
and TK-607 BRIM® Feed properties Unit

Pilot plant results in Figure 4 demonstrate that TK-609 Feedstock type LG/LCO 75/25
HyBRIM™ provides on average 0.4 % additional increase in SG/°API 0.88/29
volume swell compared to previous generation NiMo catalyst
TK-607 BRIM®. This corresponds to 160 additional barrels of Sulfur, wt % 1.35
ULSD per day for a 40,000 BPSD unit, improving the Nitrogen, wt ppm 385
annual revenue.
Operation conditions
The result of the upgrade to TK-609 HyBRIM™ in a commercial
unit is also clearly observed on the normalized weighted average Reactor inlet Pressure, (bar/psi) 80/1,160
bed temperature (WABT) as shown in Figure 5. TK-609 LHSV, hr -1
1.0
HyBRIM™ provides a significant increase in the activity
Temperature, (°C/°F) 336/637
compared to our previous generation NiMo catalysts.

6.0
TK-609 HyBRIM™
TK-607 BRIM®
5.5

5.0
Volume swell, vol%

4.5

4.0

3.5

3.0

0 100 200 300 400 500

Run hours

Figure 4: Obtained volume swell with TK-607 BRIM® and TK-609 HyBRIM™ at equal conditions, pilot plant data.
11 |

State-of-the-art diesel catalysts

720

375 TK-609 HyBRIM™ Summer TK-609 HyBRIM™ Winter

TK-607 BRIM® Summer TK-607 BRIM® Winter

700
365
Normalized WABT ( ºC )

Normalized WABT ( ºF )
680
355

660
345

640
335

325 620

315 600

0 5 10 15 20 25 30 35

Cumulative feed processed across catalyst ( BBLS/LB )

Figure 5: Performance of TK-607 BRIM® versus TK-609 HyBRIM™ at same conditions, commercial data.
 Topsoe diesel
hydroprocessing
technologies
13 |

Topsoe diesel hydroprocessing technologies

The importance of
good distribution
Efficient distribution of the reactants is mandatory in order to
achieve ultra-low sulfur levels. Poor liquid distribution will
contribute to channeling through the catalyst bed, resulting in
inefficient utilization of the catalyst, development of hot spots
and catalytic deactivation due to coke formation.

The advantages of installing a Topsoe designed distributor

tray are:
• custom-made design for the feedstock and
operating conditions
• significantly more drip points than conventional trays
• uniform coverage of the entire cross-section area in the bed
• very low sensitivity to degree of tray levelness
• good distribution over wide range of conditions (high
turndown ratios and higher than design throughputs)
• low vulnerability to plugging.

Dewaxing for improved Dewaxed USLD

cold flow properties Diesel

Hydrogen
HDS/HDN Dewaxing
With the incentive of processing higher end-point feeds, tight
oils or processing renewable feeds in the diesel hydrotreater,
meeting cold flow properties is often a concern, especially in
colder climates with strict winter specifications.

The freezing point of the paraffins in the upper ULSD boiling

range will mainly determine the cold flow properties and can
cause the ULSD to become off-spec due to wax crystallization.
Cold flow properties of diesel fuels can be improved by catalytic
dewaxing. Fractionation

We have developed an isomerization dewaxing technology to

be utilized in grassroots and revamp scenarios of a diesel
hydrotreating unit. The yield loss of the diesel fraction is reduced
by up to 30% compared to conventional dewaxing technology. Our patent-pending technology within isomerization dewaxing
14 |

Topsoe diesel hydroprocessing technologies

Full feedstock flexibility

Our renewable fuels licensed technology – HydroFlex™– provides
solutions for converting renewable feedstocks into ULSD that
can be blended with conventional diesel.

With our catalysts, it is possible to process a wide range of

renewable feedstocks. Our catalyst portfolio for renewable feeds
includes a selection of specialty catalysts for biofuels
hydroconversion, which make it possible to control the heat
release and potential associated pressure drop build-up. We
also have isomerization catalysts for the improvement of the cold
flow properties and pour point where needed.

TK-335, TK-337 and TK-339: Are all used in top of the reactor to
control the highly exothermal reactions. Grading products are
well suited for processing feed with high levels of phosphor
lipids, as they need low HDS and HDN activity in order not to
polymerize the phosphor lipids.

TK-340: High selectivity toward the hydrogenation route

compared to other catalysts, thus eliminating the formation of
CO2 from the process. This selective conversion functionality
provides a number of advantages as opposed to normal
hydrotreating catalyst, utilizing both the hydrogenation and the
decarboxylation route:
• Very small amount of CO2 is formed and thus little risk for the
byproducts formation of CO and methane
• 6% higher liquid yield of diesel, which significantly improves
the economics of the renewable fuels unit
• No need for additional amine scrubbing capacity for removing
the CO2 in a co-processing unit and the possibility of
completely eliminating the amine scrubber in a grass roots
facility, thus reducing the installed cost for the unit.

TK-341 and TK-351: Are both NiMo catalysts developed for HDO
services, with TK-351 being most active. The catalysts are
typically applied as second-stage catalyst in diesel hydrotreating
units, processing mixtures of diesel and renewable fuels. The
catalysts are characterized by high HDO activity and, at the
same time, moderate activities of HDS, HDN and saturation.

The high quality of renewable diesel produced with our

technology allows you to blend green diesel with conventional
diesel. Due to the very low sulfur content of renewable diesel, it
may be blended with low quality fossil diesel and still meet
product requirements.

Any renewable oil can be hydrotreated in a stand-alone unit or

co-processed with diesel in a refinery. The optimal solution
depends on cold-flow properties, existing refinery capacity and
location of the unit.
15 |

Topsoe diesel hydroprocessing technologies

R Aromatics saturation
In case significant reduction in aromatics is required, i.e. to
increase the cetane number, our high-pressure two-stage
process for combined deep desulphurization and de-
aromatization, HDA, is available. Both stages in the process may
be used separately, which makes the process ideal for
upgrading of existing diesel units. The first stage uses a
high-activity NiMo catalyst, whilst a sulfur tolerant noble metal

+ 2 H2 catalyst is used in the second stage.

Depending on the severity of the operation, three HDA catalysts

are available: TK-907 < TK-911 < TK-915. These catalysts can
R tolerate several hundred ppm sulfur; however, as the activity
strongly depends on the sulfur and nitrogen content in the feed,
we normally recommend pretreating the feed to low levels (less
than 20 wt ppm sulfur and nitrogen) in order to minimize the
required HDA catalyst volume, thereby reducing costs.

This two-stage HDS/HDA process has demonstrated attractive

product properties including color removal and stable
performance on both straight-run and cracked gas oil
Reactivity of aromatics: Mono-aromatics << Di-aromatics ≤ Triaromatics feedstocks.

Your partner in business

For refineries all around the world, meeting future demands and
legislation for ULSD will require continuous plant investments
and improvements, as well as optimized operational excellence.

For optimum design, in which the cost of new units is kept to a

minimum and the best use is made of existing equipment, it is
necessary to have a thorough understanding of the factors
governing the removal of the most refractive sulfur compounds in
diesel. We have identified the specific basic nitrogen
compounds, which inhibit removal of the most refractive sulfur
compounds, and this knowledge is used to define the optimum
choice of catalyst for you. The choice of catalyst also affects
other key diesel properties such as density, aromatic content
and cetane number, as well as hydrogen consumption and the
required treat gas/oil ratio. In addition, properly designed reactor
internals are necessary in meeting ultra-low sulfur fuel
requirements.

With us, you will have a highly competent and reliable partner for
today and for the future. We are known for our commitment to
catalysis – a commitment we share with you. To find out more
about our diesel hydroprocessing technologies and catalysts,
please visit www.topsoe.com or contact your local Topsoe
representative.
The information and recommendations have been prepared by Topsoe specialists having
a thorough knowledge of the catalysts. However, any operation instructions should be
considered to be of a general nature and we cannot assume any liability for upsets or damage
of the customer’s plants or personnel. Nothing herein is to be construed as recommending
any practice or any product in violation of any patent, law or regulation.

Haldor Topsoe A/S

Nymollevej 55
2800 Kongens Lyngby
Denmark
Tel +45 4527 2000
topsoe.com

Corporate Communications & Marketing 07.2014