HALDOR TOPSØE A/S
Hydrocracking
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RED series Maximizes hydrogenation
HALDOR TOPSØE A/S | Hydrocracking | 3
Hydrocracking
Topsoe is a true Topsoe true singlesource supplier of proprietary hydrocracking catalystss and licensed catalyst technologies.. Through technologies industrial experience and strong fundamental understanding, we master both disciplines and bring about complete synergy between the catalyst and the process design to maximize your hydrocracker perfomance.
D-sel™ series –
maximizes diesel yields Blue series – optimizes cold flow properties Red series – maximizes hydrogenation y t i v i t c e l e s e t a l l i t s i d e l d d i M
TK-939 D-sel TK-926 TK-921 TK-925
TK-931
TK-943
TK-947 TK-941 TK-951 TK-961
Activity Figure 1 shows the Topsoe hydrocracking catalyst portfolio.
Topsoe’ss hydrocrackin Topsoe’ hydrocracking g catalysts improve the middle distillate yield, product properties and maximize the overall performance of your hydrocracker. A hydrocracker is one of the most profitable units in a refinery, partly due to the volume swell, and partly because it converts heavy feedstocks to lighter and more valuable products such as naphtha, kerosene and diesel. The unconverted oil (UCO) may be used as feedstock for fluid catalytic cracking (FCC) units, lube oil plants and ethylene plants. Any improvement in the hydrocracking unit operation significantly improves the overall refinery economics. For optimum performance of a hydrocracking catalyst, it is important to have a high-activity hydrotreating catalyst in front of it in order to convert organic nitrogen and heavy aromatic compounds to low levels.
As a result of our extensi ve R&D efforts, ef forts, we have developed and commercialized three series of maximum middle distillate hydrocracking catalyst series: our Red series which offers maximum hydrogenation, our Blue series which offers maximum cold flow properties of the diesel and our D-sel™ series which provides maximum diesel yield. In combination with our pretreatment catalyst from the BRIM® or the HyBRIM™ series, they have shown to provide an outstanding performance compared to existing hydrocracking catalysts in the market. We offer a complete hydrocracking solution, comprising hydrocracker pretreatment catalysts, hydrocracking catalysts, grading catalysts and hydrocracking processes including heavy polynuclear aromatics (HPNA) management and high-performance reactor internals.
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Maximum middle distillate hydrocracking catalysts
RED hydrocracking catalyst series Our Red hydrocracking catalyst series provides exceptional performance with: • • •
very high hydrogenation activity high VI of UCO for lube production high cetane number of diesel.
Case: Obtaining high yields and high VI
Aiming for high yi elds and high VI of the UCO, a European refinery uses our pretreatment catalyst TK-607 BRIM ® and one of our Red series catalysts to achieve maximum performance. 160
Currently, our Red series consists of the following catalysts listed with increasing activity: TK-921 < TK-925 < TK-931 < TK-947 < TK-941 < TK-951 < TK-961
150
O 140 C U f 130 o I V 120
These reflect a wid e range of catalysts with di fferent activity activ ity and selectivity. TK-921 is an amorphous catalyst developed for optimized properties of the UCO, maximizing the VI barrels being produced. This catalyst is i s specifically designed d esigned for lube lub e oil hydrocracking units. uni ts.
110
100 0
100
200
300
400
500
600
700
800
Run day
TK-947 is optimized for units operating at high sp ace velocity and low unit pressure. TK-947 has shown excellent performance for the typical mild hydrocrackers. TK-961 is the recommended catalys t when a very high acti vity is important, typically in high nitrogen feeds and high space velocity applications. Furthermore, TK-961 is our recommended catalyst for flexible operations.
Figure 2 illustrates how an extraordinary VI is obtained by combining TK-607 BRIM ® and TK-941 in a hydrocracker being operated at 80% conversion.
Operating conditions LHSV, hr -1
0.65
Reactor inlet pressure (bar/psi)
170/2,500
High VI of UCO for lubes
When the UCO is used for production of lube oil base stock, properties such as viscosity, VI and pour point, are all crucial product parameters for the lube plant. Using catalysts from our Red series in combination with the pretreatment catalyst TK-609 HyBRIM™ ensures not only a high yield of middle distillates, but also a high VI of UCO. A very high hydrod enitrogenatio enitrogenation n (HDN), (HDN) , aromatic saturation acti vity and ring opening in combination with end-point reduction ensure the highest possible VI.
Type T ype of molecu molecules les
Influence Influen ce on VI
The compositio n of UCO has a significant impact on the VI with normal paraffins being the most favorable and aromatics and poly-naphthenics being the least favorable
Feed properties Feed type
Blends of SR VGO
SG/°API
0.932/20.3
Sulfur, wt %
1.7
Nitrogen, wt ppm
1,700
CCR, wt %
0.9
Distillation 95% (°C/°F)
560/1,040
Product properties Diesel SG/°API
0.855/34.0
UCO sulfur/nitrogen (wt ppm)
4/3
UCO VI
135-145
HALDOR TOPSØE A/S | Hydrocracking | 5
BLUE hydrocracking catalyst series Our Blue hydrocracking catalyst series provides: • • •
Operating conditions
higher yield of middle distillates very good cold flow proper ties of the diesel product reduced H2 consumption.
LHSV, hr -1
0.95
Rea Re acto torr inle inlett pres pressu surre (bar (bar//ps psi) i)
130/ 13 0/1, 1,89 890 0
A special acid fun ction modification is u sed to improve the isomerization activity and the middle distillate selectivity. The diesel cloud point is typically 10-20°C (18-36°F) lower than that obtained with catalysts from the Red series.
Feed properties Feed type
SR Russian export blend
SG/°API
0.915/23.1
Currently, our Blue series consists of the following catalysts listed with increasing activity:
Sulfur wt %
1.7
Nitrogen, wt ppm
1,500
TK-926 < TK-943
CCR (wt%)
0.1-0.5
Distillation 95 (°C/°F)
550/1,022
Cold flow properties
Cold flow properties are strongly related to the content of normal and near normal paraffins present in the diesel. The more highly branched paraffins that are present in the diesel, the better the cold flow properties. Catalysts from our Blue series provide a very high yield of middle distillates, with a high ratio between iso- and normal paraffins, resulting in excellent cold flow properties.
Product properties
Case: Obtaining high yields and good cold flow properties
SG/°API
0.855/34.0
Diesel sulfur (wt ppm)
<3
Diesel cl cloud po point (° (°C/°F)
(-5)-(-10)/23-14
UCO sulfur/nitrogen (wt ppm)
10/10
Aiming for high yi elds of diesel, wit h good cold flow proper ties and a moderate hydrogen consumption, a European refinery uses our pretreatment catalyst TK-607 BRIM® and one of our Blue series catalyst to achieve optimal performance of their hydrocracker.
420/788
140
Rx1
Conversion
410/770
120
F 400/752 ° / C ° e r 390/734 u t a r e p m 380/716 e T
100 % n o i s r e v 60 n o C 80
370/698
40
360/680
20
350/662
0 0
200
400
600
Run day Figure 3 illustrates the stable performance of TK-607 BRIM ® combined with TK-943 in a hydrocracker aiming for 60% conversion.
800
1000
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Maximum middle distillate hydrocracking catalysts
D-sel™ hydrocracking catalyst series Our D-sel™ hydrocracking catalyst series is our latest development, especially created for those hydrocrackers where the primary objective is middle distillate yield. They provide: • •
an outstanding yield of diesel typicall y 4+ vol % higher yield than the Red series catalysts.
Currently, our D-sel™ series consists of the following catalyst: TK-939 D-sel™
present in the same reactor. Having cracking and dewaxing catalysts in the same reactor provides a high selectivity and a very high degree of flexibility. From our vast experience in the refinery industry, we have in-depth knowledge of all feeds ranging from distillate to deasphalted oil (DAO), including difficult feeds such as heavy coker and extra heavy coker gasoils.
Flexible designs and catalysts
No two hydrocrackers are identical – and no two requirements are the same. In order to meet all requirements, such as cold flow properties of diesel during the winter season, increased gasoline production during the summer and even production of high VI of the UCO if required, we often recommend that the different catalyst series are
D-sel
™
series
HALDOR TOPSØE A/S | Hydrocracking | 7
Mild hydrocracking applications
For mild hydrocrackers (MHC), the main objectives are to obtain a certain minimum conversion as well as meeting specific product properties, such as sulfur content, density, cloud point and cetane number. Typical pressure s are in the 60-110 60-110 bar (850(850 -1,600 psi) range, achieving conversions between 15% and 50%. Meeting the product objectives under such conditions can be challenging. Very often, the cycle length is not determined by conversion, but by failure to meet a product property, such as sulfur content in the diesel fraction or in the UCO. Our catalysts exhibit an excellent nitrogen tolerance, resulting in very stable hydrodesulfurization (HDS) and HDN activities throughout the cycle. The optimal catalyst, or combination of catalysts, depends on feed quality and the available hydrogen.
Case: Producing ULSD with stable HDS and HDN activities
A European mild hydrocracker pr oduces ULSD using usin g our nitrogen tolerant hydrocracking catalysts. Operating conditions LHSV, hr -1
0.8
Reac Re acto torr inle inlett pres pressu sure re (ba (bar/ r/ps psi)i)
110/ 11 0/1, 1,60 600 0
Feed properties Feed type
Blends of SR VGO
SG/°API
0.925/21.5
Sulfur, wt %
1.6
Nitrogen, wt ppm
1,100
Distillation 95% (°C/°F)
595/1,104
Diesel properties SG/°API
0.867/31.7
Sulfur, ppm
<10
430/806 420/788 e r u t a r 410/770 e p m e F 400/752 t o d / e C o b ) 390/734 e T g B a r A 380/716 e W v ( a d 370/698 e t h g i 360/680 e W 350/662 340/644 0
50
100
150
200
250
300
Run day
Figure 4 displays the stable performance of TK-567 BRIM ® and TK-943 in a mild hydrocracking application aiming for production of ULSD.
350
400
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BLUE series
Optimizes cold flow properties
HALDOR TOPSØE A/S | Hydrocracking | 9
Hydrocracker pretreatment
The pretreatment stag e in a hydrocracker has the primary objective of removing organic nitrogen, particularly basic nitrogen compounds, and to saturate aromatics in the feed. Nitrogen compounds have a significantly negative impact on the activity of the hydrocracking catalyst and, consequently, on the performance of the hydrocracker. The growing interest i n processing heavy he avy oils with high nitrogen content has created a need for pretreatment catalysts with an even higher HDN activity. Depending on the specific needs, we have developed various catalysts for this service. These catalysts are produced with our proprietary BRIM® or HyBRIM™ technologies, resulting in high activity for both HDS and in particular HDN. In addition, due to the better utilization of the active metals and modified carriers, the high activity catalysts have lower densities, resulting in a reduced fill cost.
Role of nitrogen compounds
Organic nitrogen compounds have a significantly negative effect on the hydrotreating reactions. Nitrogen poisoning of the acidic catalysts employed in a hydrocracker is even more severe. An increase in nitrogen slip into the cracking catalyst, from e.g. 20 wt ppm to 80 wt ppm, has a strong impact on the conversion selectivity (as seen in the table below). Using N-speciation techniques and methods, our researchers have gained in-depth knowledge of the most refractive nitrogen species in vacuum gasoil (VGO) Figure 5 (right) shows an example of an extremely refractive N-compound found in VGO. Low N-slip
High N-slip
N-slip, wt ppm
20
80
Pressure, bar (psi)
150 (2,175)
150 (2,175)
HyBRIM™
HC temperature, ºC (ºF)
395 (743)
395 (743)
HyBRIM™ is the latest generation catalyst production technology derived from our proven and successful BRIM® technology.
H2 consumption, wt % FF
2.9
2.5
Conversion, %
Base
-17
C3 + C4 yields, wt %
Base
-2
C5 yields, wt %
Base
-9
Kero yields, wt %
Base
-7.6
Diesel yields, wt %
Base
+0.5
TK-609 HyBRIM™ is designed for hydrocracker pretreatment and highpressure ultra-low sulfur diesel services. TK-569 HyBRIM is designed for FCC pretreatment pretreat ment services. ™
Catalysts with our HyBRIM™ formulation exhibit the highest activity, counting up to 40% higher activity for both sulfur and nitrogen removal, when compared to the BRIM® catalysts. In addition, they provide higher aromatic saturation, resulting in an increased volume swell. This means achievement of longer cycles at the same feed rate, or the ability to process tougher feeds or higher feed rates at the same cycle length.
Due to the poisoning of acidic sites, the impact of N-slip on the performance of the hydrocracker is very large. Not only conversion and yield structure, but also cycle length and product properties are impacted.
N H
Figure 5: The most refractive nitrogen compounds found in VGO are a family of ca rbazol e derive d compounds c alled 4, 8, 9, 10 – Tetrahydrocyclohepta[def] carbazole. They have been isolated and characterized.
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Hydrocracking processes
Topsoe’ T opsoe’ss HPNA Trim Trim™ process Off-gas
Naphtha
Fractionator
Hydrocracker product
Stripper
Steam
Kero/Jet
Diesel
Recycle oil
Steam
UCO
HUCO bleed
HPNA Trim™
Topsoe’ss mild Topsoe’ hydrocracking licensed technology portfolio includes unique partial conversion hydrocracking processes, such as staged partial conversi conversion on (SPC), mild hydrocracking hydrocracking with integral posttreatment treat ment (MHC-IPT) and back-end back -end shift (BES). ( BES).
HPNA management Heavy polynuclear aromatics (HPNA) are formed in the reactor due to condensation of aromatics and dehydrogenation of poly-naphthenes. These compounds cause fouling in the heat exchangers and additional coking of the catalyst. In general, high end-point feed, low pressure and high operating temperature are the factors that promote formation of HPNA. The HPNA compounds in the UCO have a significant impact on the color as shown in figure 6.
the hydrocracker UCO into a light and heavy portion, with the HPNAs concentrated in the heavy liquid product. The HPNA Trim™ process consists of very few equipment elements only. This allows for a low-cost modular approach which also makes it very suitable for easy retrofit to existing hydrocracking units.
The HPNA Trim Trim™ ™ solution
For full conversion hydrocrackers, we have developed a new HPNA Trim™ solution (patent pending) for HPNA management. Our solution reduces the required UCO bleed rate to an absolute minimum and maximizes distillate product yield. Our unique, yet simple HPNA Trim™ process takes advantage of the extremely high boiling points of the heaviest and most problematic HPNA compounds. The HPNA Trim™ Trim ™ process separates, separ ates, by distillation,
Figure 6: Display of the structure of typical heavy polynuclear aromatics. These species are found in concentrations, varying from 25 to 2000 wt ppm.
HALDOR TOPSØE A/S | Hydrocracking | 11
Hydrocracking basics
High-performance reactor internals We are a leading supplier of state-of-the-art reactor internals in the refining industry. Our vapor-lift trays (VLT), with its unparalleled features, is currently used in 300 + hydrotreating and hydrocracking
units worldwide. Using detailed mathematical modeling and extensive experimental measurements, we have improved the vaporassisted principles to obtain unbeaten performance and exceptional benefits in operation. The most impor tant benefit of our reactor i nternals in hydrocracki ng and hydrotreating units, is the self-adjusting principle which ensures
that the liquid level of the tray stays constant over a very wide range of operating conditions. This ensures the same outstanding performance throughout the operating cycle. Furthermore, our trays are self-cleaning and have a very high capacity for in-organic feed contaminants which are collected on the tray plate, thus minimizing pressure drop build-up in the catalyst bed. To reduce downtime during turnarounds, we have incorporated a Quick-Release™ system which enables man-way access in minutes, without the use of any tools.
Our technical service program Our technical service is available 24/7 to all customers using Topsoe’s technology or catalysts, either on an ad-hoc or contractual basis. As no two two hydrocrack hydrocracker er units ts are identic identical al – and and no two two support support requirements are the same – we provide customized solutions, along with detailed guidelines to meet your specific requirements. Furthermore, our experienced engineers will be on site to provide valuable advice and feedback, ensuring optimum conditions throughout the key stages of start-up, operation and turnaround.
Our specialist hydrocracker team of dedicated engineers has more than 800 man-years of combined experience within hydrocracking technology development and catalysis. They have designed and upgraded more than 54 different hydrocracking units worldwide. Our experts supply you with troubleshooting assistance at day-to-day response, thus enabling you fast access to our expertise in all urgent matters, including site visits if required.
Quick response - 24/7
Optimizing and troubleshooting
y n a p m o c l a b o l G
Loading and start-up L o c a l p r e s e n c e
Customer
Performance evaluations
Operator training on-site
Just-in-time delivery
The information and recommendations have been 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 Topsøe A/S Nymøllevej 55 2800 Kongens Lyngby Denmark Tel +45 4527 2000 2000
topsoe.com
Corporate Communications & Marketing 05.2014.D
