Haldor Topsoe’s

BRIM® & HyBRIM™

Technology

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CoMoS Structure

• In the late 1970's Topsoe researchers discovered that the activity of the HDS catalysts
correlates with the presence of CoMoS active sites
• In the 1980's, Topsoe researchers identified the existence of two types of CoMoS: Type I and
Type II
• Recently, Topsoe has been involved in research that has provided greater insight into the
hydrogenation function of the catalysts with CoMoS active sites. Topsoe researchers named
these sites:

BRIM® sites

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New Catalysts have been Introduced Based on Fundamental Insight

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BRIMTM Technology
- advances in catalyst preparation

C & EN 2 (2001)
Topsøe
researchers with
Besenbacher’s
group (2001)

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Edge Terminations of CoMoS

Cobalt S edge

Mo edge

BRIM™ sites
The near
metallic BRIM™
sites of high
electron density
are located close
to the edge of
the CoMoS

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CoMoS Model

Reaction sites for hydrogenation

(brim sites)

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CoMoS Model

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CoMoS Model

Reaction sites for direct desulfurization

(Type I and II)

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BRIM® and Vacancy Sites in Type I and Type II Structures
Type I and II Co-Mo-S and MoS2

• Mo-O-Al linkages result in low active Type I

Type I Type II
High activity Type II can
be formed by high
temperature sulfiding
(Candia, Topsoe) using
supports like carbon
with weak surface
interaction (Topsoe) or
by using complexing
agents and stacking of
the CoMoS slabs (van
Veen, Prins,…)

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The Direct Route in ULSD Occurs at Edge Vacancies

S vacancies

Topsøe
researchers with
Besenbacher’s
group (2001)

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Interaction of Sulfur Containing Molecule with Edge Vacancy
STM image after quenching to 250K

Topsøe
researchers with
Besenbacher’s
group (2001)

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Mobility of Thiolate Species on One-dimensional Metallic Brim States

Time-lapse STM images

#1 #2

J.V. Lauritsen et al.

Nanotechnology 14,
#3 #4 385 (2003);

J. Catal. 224(2004)94

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Mobility of Thiolate Species on One-dimensional Metallic Brim States

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NiMoS nanocluster – Type A
Type A NiMoS very similar to CoMoS

• Hexagonally truncated triangle

• Single-layer
• Effect of Nickel : Two different edge
terminations
• Similar to CoMoS

Ni S-edge
Bright brim (~ 0.7Å)
Protrusions in registry

Mo-Edge (100% S)

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NiMoS nanocluster – Type B

• ”Dodecagonal” shape
• Single-layer
• Effect of Nickel : different
edge terminations

Mo edge
high index (50% S coverage)
S-edge Ni edge?
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Reaction sites on Co-Mo-S

Reaction sites for hydrogenation

(Brim sites)

Reaction sites for direct HDS (Type I and II sites)

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Movie of BRIM Functionality

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Summary: BRIM™ Technology

• The hydrogenation activity of the BRIM™ sites is enhanced

• Single slab structures are preferred since BRIM™ sites are on top of slabs allowing for better
metals utilization

• The frequency of BRIM™ sites is increased

• Bonding of CoMoS to the carrier is optimized giving more Type II for direct desulfurization
sites and BRIM™ sites for HDA and HDN on the basal planes for single CoMoS slabs

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 Next generation BRIM® catalysts
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Goals for the next generation:

• Higher activity
• Unmatched stability
• Improved cost effectiveness

• Improved metal dispersion

• Increased number of reaction sites

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In-situ characterisation of TK-578 BRIM®

• Improved metal dispersion is achieved through:

• Less stacking and clustering of metal slabs

• Stacking and and

Less stacking clustering can
clustering of be
the measured using Transmission
metal slabs increases the number ofElectron Microscopy (TEM)
images
reaction sites

Unstack Uncluster

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Sintering of Active Sites

Area of interest

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CoMoS clusters
Large-scale STM image (630 x 644 Å2, )

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Titan ETEM

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Metal stacking (TEM)

0.6 TK-576 BRIM

TK-578 BRIM®
Frequency

0.4

0.2

0
1 2 3 4 5 6
Stack height

Results indicate improved metal dispersion!

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Metal clustering (TEM)

0.40 TK-576 BRIM

TK-578 BRIM®
0.30
Frequency

0.20 27% of the metal slabs are 8 nm or longer

19%

0.10

0
2 4 6 8 10 12 14 16 18 20
Length (nm)

Results indicate improved metal dispersion!

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HyBRIMTM developments

The HyBRIMTM technology

• Improved catalyst preparation
• Combines the BRIMTM technology with an improved preparation step
• Optimized interaction between active metals and the catalyst carrier
• Essential for the Type II sites and in the BRIMTM technology
Resulting in
• Step change in activity of both the direct sites and the BRIM™ sites
• Same high stability as our BRIM™ catalysts HyBRIMTM technology
• As our clients have come to expect
The high activity can be used to
• Achieve longer cycles at the same feed rate
• Process tougher feeds
• Increase conversion – e.g. to achieve lower product sulfur
• Increase throughput

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Features of the BRIM® and HyBRIM™ products

• Highest activity catalysts

• All BRIM® and HyBRIM™ products are delivered in oxidic state
• No use of chelating agents
• Easy loading at ambient conditions
• No special requirements during start-up/activation
• Can be regenerated using conventional regeneration technologies
• Good physical integrity
• Minimal loss during unloading and regeneration

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BRIM® catalysts for ULSD

• Low to medium pressure operation (CoMo):

− TK-568 BRIM® - best of the low-cost, low-density (also in QL)
− TK-570 BRIM® - standard-bearer amongst competitors
− TK-578 BRIM® - unbeaten activity amongst competitors
− TK-580 BRIM® - maximum activity

• High pressure operation (NiMo):

− TK-563 BRIM® - best of the low-cost, low-density
− TK-607 BRIM® - maximum activity
− TK-609 HyBRIM™ - (13 °F more active than TK-607 BRIM® in diesel service)
− TK-611 HyBRIM™ - (11 °F more active than TK-609 HyBRIM™ in diesel service)
− Isomerizing and Dewaxing - TK-928, TK-932, TK-935, TK-930 and TK-920
• Improves cold flow properties by n-paraffin isomerization/cracking
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New Products for ULSD - Activity and Density

Service Catalyst Activity Density

TK-576 BRIM® Base Base

TK-570 BRIM® Base Base – 9%
TK-578 BRIM® Base + 20% Base – 5%
TK-568 BRIM® Base – 20% Base – 14%
TK-580 BRIM® Base + 38% Base
ULSD
TK-575 BRIM® Base Base
TK-607 BRIM® Base + 10% Base – 9%
TK-609 HyBRIM™ Base + 50% Base – 9%
TK-569 HyBRIM™ Base – 12% Base – 13%
TK-611 HyBRIM™ Base + 85 % Base + 7%
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New Products for FCC P/T - Activity and Density

Service Catalyst Activity Density

TK-558 BRIM® Base Base
CoMo TK-562 BRIM® Base + 10% Base – 6%
TK-560 BRIM® Base Base – 11%
TK-559 BRIM® Base Base
TK-561 BRIM® Base Base – 3%

Base – 10% (HDS)

NiMo TK-565 HyBRIM™ Base – 8%
Base + 25%(HDN)

Base + 10%(HDS)
TK-569 HyBRIM™ Base + 5%
Base + 65%(HDN)

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 TK-569 HyBRIM™ vs. BRIM®
80% VGO + 20% CGO

H2 partial pressure 1160 psi (80 bar)

500 WABT 689°F (365°C)
TK-569 HyBRIM™ gives a remarkable drop in product LHSV 1 hr-1
nitrogen H2/Oil 4450 SCF/BBL (750 Nm3/m3)

400 Product S
Product N
Product S/N, wtppm

300

200

100

0
TK-569 HyBRIM™ TK-567 BRIM® TK-563 BRIM® TK-561 BRIM®

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TK-569 HyBRIM™
What to expect

Achieve the same product N at a

Catalyst Volume Volume 13°C/23°F lower
Relative bulktemperature
density Relative Mo amount
activity activity compared to per volumen
HDS HDN
TK-561 BRIM®
TK-559 BRIM® 100 100 Base Base
TK-561 BRIM® 100 100 Base -3% Base -3%
TK-563 BRIM® 100 115 Base -12% Base -10%
TK-567 BRIM® 110 125 Base -3% Base -3%
TK-569 HyBRIM™ 110 165 Base +5% Base +2%

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Increased volume swell with TK-569 HyBRIM™

• Increased nitrogen removal and higher poly-aromatics saturation in the gas oil HDT unit
results in increased gasoline and propylene yield from the FCCU
80/20 VGO/CGO
5.0 S 2.4 wt %
N 1400 wt ppm
TK-567 BRIM® 20°API (0.932 SG)

4.5 TK-569 HyBRIM™ LHSV 1 hr-1

P 1160 psi (80 bar)
Volume swell, vol%

T 690°F (365°C)
4.0 H2/HC 4450 SCF/bbl (750 Nm3/m3)

3.5

3.0

2.5

2.0
20 120 220 320 420 520
34 Run hour (h)
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TK-569 HyBRIM™
HDS stability
80/20 VGO/CGO
S 2.4 wt %
N 1400 wt ppm
20°API (0.932 SG)

30 LHSV 1 hr-1
P 1160 psi (80 bar)
T 690°F (365°C)
25 H2/HC 4450 SCF/bbl (750 Nm3/m3)

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K (HDS)

15

10
TK-567 BRIM®
5 TK-569 HyBRIM™

0
20 120 220 320 420 520
Run hour (h)
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TK-569 HyBRIM™
HDN stability
80/20 VGO/CGO
S 2.4 wt %
N 1400 wt ppm
20°API (0.932 SG)
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LHSV 1 hr-1
P 1160 psi (80 bar)
T 690°F (365°C)
H2/HC 4450 SCF/bbl (750 Nm3/m3)
6
K (HDN)

2 TK-567 BRIM®
TK-569 HyBRIM™

0
20 120 220 320 420 520
Run hour (h)
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Next generation of pretreatment catalyst to be commercialized, TK-609 HyBRIM
TK-609 HyBRIM™ vs. TK-607 BRIM®

RVA RVA
Density (sock/dense)
HDS HDN
TK-605 BRIM® 100 100 Base
TK-607 BRIM® 110 110 Base – 9%
TK-609 HyBRIM 150 150 Base – 9%
TK-611 HyBRIM™ 200 200 Base + 7%
Improved preparation technology
Step-change in performance

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 Performance differences in HC PTR

Feed, Ural VGO: Test conditions:

wt % Sulfur 1.8 Temperature 700° F
ppm Nitrogen 1261 Pressure 1470 psi
Sp. Gr. 0.915 LHSV 1.0

°C
390 °F
WABT to obtain 15 ppm

TK-607 BRIM®

Product N/S for WABT

80
TK-609 HyBRIM
product nitrogen

720
380 60

at 700°F
40
700
370
20

360 680 0
TK-607 BRIM® TK-609 HyBRIM Product nitrogen Product sulfur

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Performance test in HC PTR service

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Test conditions:

25 VGO Russian SR export blend

Pressure 1838 psi
LHSV 1.64
Product N (wt ppm)

20

15

10

TK-607 BRIM® - 723°F

5
TK-609 HyBRIM - 710°F

0
500 550 600 650 700 750
Run hour
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 Performance differences in ULSD

Feed, 75/25 SR/LCO: Test conditions:

wt% Sulfur 1.4 Temperature 640° F
ppm Nitrogen 361 Pressure 882 psi
Sp. Gr. 0.877 LHSV 1.27

°C
370 °F 40
WABT to obtain 10 ppm

Product sulfur at WABT

366 690 30
product sulfur

362

640°F
680 20
358

670 10
354

350 0
TK-607 BRIM® TK-609 HyBRIM TK-607 BRIM® TK-609 HyBRIM

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Performance test in ULSD service

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The first 1300 hours in HC PTR service
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Product S (wt ppm)

12

10

4 TK-607 BRIM® - 685°F

TK-609 HyBRIM - 671°F
2

0
1300 1400 1500 1600 1700
Run hour
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Performance benchmark
Ultra-Low Sulfur Diesel

Diesel feed Test conditions

Sulfur wt % 0.6 Temperature 622°F (328°C)
Nitrogen wt ppm 700 Pressure 1,020 psi (70 bar)
Density API (SG) 32.3 (0.864) LHSV 1.0
°C

Product sulfur in wt ppm

340 40
10 ppm product sulfur

640
336

at WABT 622 °F
WABT to obtain

30 32 ppm
332 633°F 630
(334°C) 20
328
622 °F 620
(328°C) 10
324 10 ppm
610 0
320
TK-611 HyBRIM TK-609 HyBRIM TK-611 HyBRIM TK-609 HyBRIM

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Performance benchmark
Hydrocracking pretreatment

VGO feed Test conditions

Sulfur wt % 1.9 Temperature 678°F (359°C)
Nitrogen wt ppm 1,400 Pressure 2,030 psi (140 bar)
Density API (SG) 22.3 (0.920) LHSV 1.15

80 400
Product nitrogen

Product sulfur
60 62 ppm 300 322 ppm

in wt ppm
in wt ppm

40 200
193 ppm
20 26 ppm 100

0 0
TK-611 HyBRIM TK-609 HyBRIM TK-611 HyBRIM TK-609 HyBRIM

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Stability data
Hydrocracking pretreatment

On-stream stability of TK-611 HyBRIM™ equal to TK-609 HyBRIM™

TK-611 HyBRIM™ TK-609 HyBRIM™
140
Test conditions
Temperature 710°F (375°C) 130
Pressure 1,800 psig (125 barg)

Relative activity
120
LHSV 1.6
6°C (11°F)
110

VGO feed Product 100

Sulfur wt ppm 19,000 100
90
Nitrogen wt ppm 1,400 20
Density API (SG) 22.3 (0.92) 29.3 (0.88) 80
600 700 800 900 1000 1100
Run hours
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 Volume Swell
TK-609HyBRM™ versus TK-611HyBRIM™

Our pilot plant data show that at the same operating conditions TK-
611HyBRIM™ will provide 0.4 vol% higher volume swell compared to TK-
609HyBRIM™

Example: 40,000 BPD ULSD unit

Additional swell barrels with TK-609HyBRIM™: 160 per day or 58,400 per year
Cost of the swell barrel with NG price of $3/MMBTU: $18-20
Value of swell barrel to the refiner when sold as ULSD: ~$50
Total value per year: ~$1.9 MM
Please note that the above value only represents the delta swell between the
two catalysts – not the total swell, which may be 5-20 time higher depending
on the feed composition and unit pressure.

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