Title of Invention

HYDROTREATING AND HYDROCRACKING PROCESS AND APPARATUS

Abstract Partial conversion hydrocracking process comprising the steps of (a) hydrotreating a liydrocarbon feedstock with a hydrogen rich gas to produce a hydrotreated effluent stream comprising a liquid/vapour mixture and separating the liquid/vapour mixture into a liquid phase and a vapour phase, and (b) separating the liquid phase into a controlled liquid portion and an excess liquid portion, and (c) combining the vapour phase with the excess liquid portion to form a vapour plus liquid portion, and (d) separating an FCC feed-containing fraction from the controlled liquid portion and simultaneously hydrocracking the vapour plus liquid portion to produce a diesel containing fraction, or hydrocracking the controlled liquid portion to produce a diesel-containing fraction and simultaneously separating a FCC feed-containing fraction from the vapour plus liquid portion. The invention also includes an apparatus for carrying out the partial conversion hydrocracking process.
Full Text

HYPROTREATING AND HYDROCRACKING PROCESS AND APPARATUS
The invention relates to a partial conversion hydrocracking process and apparatus whereby heavy petroleum feed is hy-drotreated and partially converted to produce feed for a fluid catalytic cracking (FCC) unit. The invention is particularly useful in the production of ultra low sulfur die-sell (ULSD) and high quality FCC feed, which can be used to produce ultra low sulfur gasoline (USLG) in the FCC unit without post treating the FCC gasoline to meet sulfur specifications,
BACKGROUND OF THE INVENTION
Partial conversion or "Mild" hydrocracking has been utilized by refiners for many years to produce incremental middle distillate yields while upgrading feedstock for fluid catalytic cracking (FCC). Initially, specialized catalysts were adapted to the low or moderate pressure conditions in FCC feed desulfurizers to achieve 20 to 30 percent conversion of heavy gas oils to diesel and lighter products. The combination of low pressure and high temperatures used to achieve hydro-conversion conditions typically resulted in heavy, high aromatic products with low cetin quality. The promulgation of new specifications for both gasoline and diesel products has put pressure on such processes to make lighter, lower sulfur products that can fit into the refinery ultra low sulfur diesel and gasoline (ULSD and ULSG) pools. The continued growth in middle distillate fuel demand compared to gasoline has re-focused attention on drocracking and particularly on partial conversion hydro-

cracking as a key process option for adapting to the modern clean fuels environment.
New specifications in both the U.S. and E.U. have mandated dramatic reductions in both diesel and gasoline sulfur levels. It is now clear that lower sulfur levels in these products provide substantial benefits in terms of decreased tail pipe emissions from automobiles and trucks. Pipeline transportation of both low sulfur and high sulfur distillate grades is still a work in progress. Recent studies in the U.S. indicate that as much as 10% of ultra low sulfur diesel (ULSD) will be downgraded by common pipeline transportation, and some carriers are requiring that ULSD be no more than 5 wppm sulfur at the refinery boundary. The environmental benefits and product transportation logistics make it certain that there will be continued pressure to force all fuels into the ultra low sulfur category-Conventional partial conversion units utilised in many refineries around the world have been designed for pressure levels in the 50 to 100 brag range depending on feed quality and cycle life objectives. They have been designed to achieve 20% to 30% net conversion of heavy vacuum gas oil and total sulfur removal of about 95% to yield FCC feed suitable for making low sulfur gasoline. The process configuration has evolved to include hot high pressure separators for better heat integration and amine absorbers to mitigate the effects of very high recycle gas hydrogen sulfide content.
One significant shortcoming of this technology has been the inability to have independent control of hydro-conversion

and hydro-desulfurization reaction severity. While the die-sel product sulfur can be decreased to a large extent by applying more hydrotreating catalyst and achieving deeper HDS severity, the only real option for improving density and cetane quality is to increase reactor operating pressure or to increase hydrocracking severity.
Large increases in reactor pressure can raise chemical hydrogen consumption by 70% to 100%, The high capital and operating cost associated with such large increases in hydrogen consumption is a significant disadvantage for utilizing high pressure designs to achieve product uplift•
WO patent application No. 99/47626 discloses an integrated hydroconversion process comprising hydrocracking a combined refinery and hydrogen stream to form liquid and gaseous components, Unheated hydrogen from the hydrocracking step is combined with a second refinery stream and hydro treated. The product is separated into a hydrogen stream and a portion of this stream is recycled to the hydrocracking step-Higher yields of naphtha and diesel and lower yields of fuel oil were obtained. However, this process has the disadvantage of requiring a feedstock with relatively low nitrogen, sulfur and aromatics content. This implies, in many cases, that the feedstock needs to be pre-treated prior to the disclosed process.
U.S. patent No, 6294079 discloses an integrated low conversion process comprising separating the effluent from a hydrotreating step into three fractions: a light fraction, an intermediate fraction and a heavy fraction. The light fraction and a portion of the intermediate and heavy fractions

are bypassed the hydrocracking zone and sent to a separator, A series of high pressure separators are used. The remaining intermediate and heavy fractions are hydrocracked, FCC feedstock is produced. An augmented separator and other separators are used to separate the hydrotreater effluent into a vapour stream and two liquid streams. Parts of each liquid stream are flow controlled and remixed with the cooled, compressed vapour stream, reheated and hydrocracked at high severity to produce the higher quality middle distillate products. The complex arrangement of multiple separators and the cooling of the vapour stream lead to the use of extra equipment and added cost.
Increasing overall hydrocracking severity is at times not a viable option. When the process objective is to make a required amount of FCC feed, a high conversion leads to the formation of good quality diesel. However, high conversion also results in production of insufficient FCC feed since more diesel is produced.
The objective of this invention is to provide a process and apparatus in which FCC feed is treated to produce ultra low sulfur FCC feed suitable for production of ultra low sulfur gasoline (USLG) not requiring gasoline post treatment.
Another objective of this invention is to provide a process and apparatus for producing diesel with an ultra low sulfur content and substantially improved ignition quality as measured by cetane number, cetane index, aromatics content and density.

A further objective of this invention is to provide a simple apparatus for carrying out the process of the invention.
SUMMARY OF THE IKVENTION
The process of the invention comprises hydrotreating and partially converting a heavy petroleum feed stream which boils above 260*’0 while being low in aspartames ( The process of the invention comprises*a partial conversion hydrocracking process comprising the steps of
(a) hydrotreating a hydrocarbon feedstock with a hydrogen-rich gas to produce a hydrotreated effluent stream comprising a liquid/vapour mixture and separating the liquid/vapour mixture into a liquid phase and a vapour phase, and
(b) separating the liquid phase into a controlled liquid portion and an excess liquid portion, and
(c) combining the vapour phase with the excess liquid portion to form a vapour plus liquid portion, and
(d) separating an FCC feed-containing fraction from the controlled liquid portion and simultaneously hydrocracking

the vapour plus liquid portion to produce a diesel-containing fraction, or
hydrocracking the controlled liquid portion to produce a diesel-containing fraction and simultaneously separating a FCC feed-containing fraction from the vapour plus liquid portion.
The apparatus of the invention comprises an apparatus for the partial conversion hydrocracking process comprising a hydrotreating reactor having one or more catalytic beds and in series with a hydrocracking reactor, and having an liquid/vapour separation system downstream the one or more catalytic beds of the hydrotreating reactor, the liquid/vapour separation system comprising an outlet device and an outlet pipe in a separator vessel, the outlet device comprising a pipe extension above the bottom of the separation vessel, the pipe extension being provided with an anti-swirl baffle at the top open end of the pipe extension, the separator vessel being provided with an outlet pipe at the separator vessel bottom, the outlet pipe being provided with an anti-swirl baffle.
SUMMARY OF THE FIGURES
Fig* 1 shows a partial conversion hydrocracking process of the invention.
Fig, 2 shows an alternative partial conversion hydrocracking process of the invention.
Fig. 3 shows a section through the bottom of the hydro-treatment reactor,

Fig, 4 shows the process of the invention where the liquid/vapour separation system is located between the hydrotreating reactor and the hydrocracking reactor.
DETAILED DESCRIPTION OF THE I13VENTI0N
The process of the invention is a medium pressure partial conversion hydrocracking process comprising a hydrotreating step and a hydrocracking step. The process and apparatus of the invention provides a solution that meets current and expected product specifications for both gasoline and die-sel fuel without the need for further processing or blending with other lighter, higher quality components. An advantage of the process is that both hydrogen partial pressure and hydrocracking conversion can be utilized for die-sel quality improvement, while maintaining the relatively low overall conversion and HDS (hydrodesulfurization) severity requirements dictated by FCC pretreatment applications.
By the term 'hydrotreating' (HDT) is meant a process carried out in the presence of hydrogen whereby heteroatoms such as sulfur and nitrogen are removed from hydrocarbon feedstock and the aromatic content of the hydrocarbon feedstock is reduced. Hydrotreating covers hydrodesulfurization and hydrodenitrogenation.
By the term "hydrodesulfurization" (HDS) is meant the process, whereby sulfur is removed from the hydrocarbon feedstock.

By the term "hydrodenitrogenation" (HDN) is meant the process, whereby nitrogen is removed from the hydrocarbon feedstock.
By the term "hydrocracking" (HC) is meant a process, whereby a hydrocarbon containing feedstock is catalytically decomposed into a chemical species of smaller molecular weight in the presence of hydrogen.
In the process of the invention the main reactor loop of the process has two reactors in series, a hydrotreating reactor for pretreatment of the feedstock and a hydrocracking reactor for hydrocracking a part of the effluent from the hydrotreating reactor. By the term "in series" is meant the hydrocracking reactor is located downstream the hydrotreating reactor.
There is a liquid/vapour separation system integrated in the bottom of the hydrotreating reactor or contained in a separator vessel located between the two reactors for separating the effluent, a mixture of liquid and vapour, emerging from the catalytic beds of the hydrotreating reactor.
In the liquid/vapour separation system a flash is carried out using an outlet device and an outlet pipe- The liquid/vapour mixture separates into a liquid phase and a vapour phase in the separator vessel. The outlet device is an internal overflow standpipe for dividing the liquid phase into a controlled liquid portion and an excess liquid portion. The vapour phase is combined with the excess liquid portion and this vapour plus liquid portion can be fed to the hydrocracking reactor. In this case the controlled lid-

aid portion is withdrawn, bypassing the hydrocracking reactor and is routed to a stripper to produce FCC feed and naphtha and lighter products. It is also possible to send the controlled liquid portion to the hydrocracking reactor and simultaneously separating a FCC feed-containing fraction from the vapour plus liquid portion.
By the term "flash' is meant a single stage distillation in which the hydrotreated effluent stream comprising a liquid/vapour mixture is separated into a liquid portion and a vapour plus liquid portion, A change in pressure is not required.
An advantage of the process of the invention is that a simple flash step is used instead of a complex augmented and multi-separator scheme to split the effluent from the catalytic beds of the hydrotreating reactor into the two portions. The vapour plus liquid portion is sent to the hydrocracking reactor without substantially cooling the vapour, other than the cooling required for temperature control to the inlet of the hydrocracking reactor-Part of the liquid phase in the hydrotreater effluent is routed to an FCC feed stripper. A low pressure flash drum can optionally be added. Only naphtha and lighter hydrocarbons are recovered. The diesel contained in this portion is of lower quality since it has a higher density, higher aromatic content and lower cetane value than the diesel produced in the hydrocracking reactor, so it is better suited as an FCC feed. The entire diesel produced by the inventive process is produced in the hydrocracking step and have a much improved quality•

An unconverted oil that has a boiling range higher than the diesel product (>370°C+) is recovered from the hydrocracked effluent in a fractionator column. This is unconverted and can be used as FCC feed or as feedstock for an ethylene plant or a lube plant because it has higher hydrogen content and lower aromatic content than the FCC feed produced in the FCC feed stripper.
Suitable feedstock for the process of the invention is vacuum gas oil (VGO), heavy coker gas oil (HCGO), thermally cracked or visbroken gas oil (TCGO or VBGO) and deasphalted oil (DAQ) derived from crude petroleum or other synthetically produced hydrocarbon oil. The boiling range of such feeds are in the range of 300°C to 700°C with sulfur content of 0,5 to 4 wt% and nitrogen content of 500 to 10,000 wppm.
The objective of the hydrotreating reactor is mainly to desulfurize the feed down to a level of 200 to 1000 wept sulfur, which will result in an FCC gasoline with ultra-low sulfur content suitable for blending to meet both European and U. S. specifications (10 and 30 wept, respectively), obviating the need for gasoline post-hydrotreating. The low sulfur content in the feed also has the benefit of dramatically reducing emissions of sulfur oxides (SOx) from the FCC regenerator. Secondly, the hydrotreating reactor reduces the nitrogen content in the feed to the hydrocracking reactor. Thirdly, the aromatic content of the FCC feed is also reduced, which will result in higher conversion and higher gasoline yields.

The hydrotreating reactor comprises a hydrotreating zone followed by a separation zone. The hydrotreating zone contains one or more catalyst beds for hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) of the feedstock. The products from the hydrotreating zone comprise a mixture of liquid and vapour. In a conventional hydrotreating reactor, the catalyst beds are supported by bed support beams and the head space in the bottom reactor head is filled with inert balls that support the last catalyst bed. The mixture of vapour and liquid leaves the reactor via an outlet collector which sits on the bottom reactor head.
In an embodiment of the inventive process, the last catalyst bed in the hydrotreating reactor is supported by bed support beams just like the upper beds. However, instead of holding a large volume of inert balls, the head space in the bottom reactor head is used to separate the liquid/vapour mixture. The liquid/vapour separation system is used in the bottom head to split the mixture of liquid and vapour from the catalytic beds of the hydrotreating reactor into a liquid portion and a vapour portion containing a fraction of liquid, i.e. a vapour plus liquid portion.
The vapour plus liquid portion can be directed to the hy-drocracking reactor and converted under suitable conditions to produce ULSD. The feed to the FCC is mainly composed of the liquid portion.
The liquid/vapour separation system is integrated in the hydrotreating reactor and located in the head space at the bottom of this reactor. It comprises an outlet device for transfer of the vapour plus liquid portion to the hydro-

cracking reactor. The liquid portion is contained in the reactor bottom outside the outlet device and leaves the hydrotreating reactor separately through the outlet pipe for transfer to, for instance, a stripper. The level of the liquid portion in the reactor bottom and hence the amount of liquid transferred to the stripper is controlled by conventional flow control valves, Excess liquid not required for transfer to the stripper thereby enters the outlet device with all the vapour and leaves the reactor as the vapour plus liquid portion.
The amount of liquid, i.e. the controlled liquid portion, withdrawn by the outlet pipe is set by the desired HVGO conversion. The controlled liquid portion comprises 30-100 wt% of the liquid phase, and the excess liquid portion comprises 0-70 wt% of the liquid phase. Preferably the controlled liquid portion comprises 60-95 wt% of the liquid phase, and the excess liquid portion comprises 5-40 wt% of the liquid phase.
The integration of the liquid/vapour separation system in the hydrotreating reactor has the advantage of reducing the amount of processing equipment when compared to conventional separation outside the reactor. Conventional separation outside the reactor would require addition of a high pressure separator vessel with the accompanying disadvantage of increased capital cost.
The controlled liquid portion is sent to a stripper in which a stream of steam removes the light hydrocarbons in the naphtha boiling range and hydrogen sulfide (H2S) and ammonia (NH3) dissolved in the liquid. The stripped product

is used as feed for the FCC unit. The light overhead products from the stripper are comprised predominantly of naphtha boiling range light hydrocarbons together with ammonia and hydrogen sulfide.
All the vapour plus liquid portion leaves the separation zone of the hydrotreating reactor and is transferred to the hydrocracking reactor. The hydrocracking reactor also contains one or more catalytic beds. This reactor may contain some hydrotreating catalyst to further lower the nitrogen to an optimum level ( Alternatively, in another embodiment of the invention, after leaving the separation zone where the products from the hydrotreating zone are split into a liquid portion and a vapour plus liquid portion, the vapour plus liquid portion is directed to a separator for removal of a hydrogen-rich stream. The hydrogen-rich stream can be further purified from hydrogen sulfide and ammonia by amine scrubbing and water washing- The liquid product from the separators (a high pressure hot separator in series with a high pressure cold separator) is mainly FCC feed and it is sent to stripping for removal of the light hydrocarbons, H2S and NH3 dissolved in the liquid. The stripped product is used as feed for the FCC unit.

The liquid portion from the separation zone is sent to the hydrocracking reactor operating with a cracking severity sufficient to produce a diesel fraction with product properties in accordance with EN 590 ULSD specifications. Operating conditions in the hydrocracking reactor can be adjusted to provide a product satisfying U.S. market requirements. This embodiment provides a lower ammonia and hydrogen sulfide environment in the hydrocracking reactor which increases the hydrocracking catalyst activity.
In another embodiment of the invention, a second feed can be added as feed to the hydrocracking reactor. In this embodiment, the second feed can be hydrotreated and hydro-cracked in the hydrocracking reactor and bypasses the hy-drotreating reactor. One example of a second feed is a light cycle oil (LCD) from the FCC, which needs further hy-drotreating and hydrocracking to convert it into high quality diesel, jet and naphtha.
Fig, 1 illustrates an embodiment of the invention in which the vapour plus liquid portion from the separation zone is cracked in the hydrocracking reactor and the controlled liquid portion is sent to a stripper.
A feed 1 is combined with hydrogen, for instance a hydrogen-rich recycle gas 2, and sent to a hydrotreating reactor 3 for hydrodesulfurization and hydrodenitrogenation in one or more catalytic beds. The effluent from the one or more catalytic beds is a mixture of vapour and liquid which separates into a liquid phase and a vapour phase. In the separation zone 4 downstream the last catalytic bed separate-

ton into a vapour plus liquid portion 5 and a liquid portion 6 takes place using a liquid/vapour separation system integrated in the hydrotreating reactor.
The liquid/vapour separation system comprises the outlet device and the outlet pipe (shown in Fig. 3). The liquid portion 6 consists of only liquid and the vapour plus liquid portion 5 includes all the vapour. The flow rate of the liquid portion 6 is controlled by conventional flow control valve If and excess liquid not required leaves the separation zone 4 as overflow through the outlet device together with all the vapour and thus forms the vapour plus liquid portion 5.
Controlled liquid portion 6 is comprised of heavy liquid hydrocarbons with substantially reduced sulfur and nitrogen content relative to the feed 1. It leaves the hydrotreating reactor 3 and bypasses the hydrocracking reactor 8 to enter a stripping column 9. Light hydrocarbons together with ammonia and hydrogen sulfide are separated into the overhead stream 10 from stripping column 9 and the resulting liquid stream from the bottom of the stripping column 9 is suitable as low sulfur FCC feed 11.
The vapour plus liquid portion 5 leaves the hydrotreating reactor 3, It may optionally be combined with a second hydrocarbon feedstock 22. It then enters the hydrocracking reactor 8 where it is catalytically cracked to form a hydrocrack effluent 12 having properties suitable for die-sel fuel preparation. One or more catalyst beds are present in this reactor. The hydrocracked effluent 12 is sent to a separator vessel 13 and a hydrogen-rich gas stream 14 is

recycled from the separator 13 to the hydrotreating reactor 3 via a recycle gas compressor 15, Make-up hydrogen 16 can be added to the hydrogen-rich stream 14 either upstream or downstream of the compressor 15 to maintain the required pressure. The liquid product 17 from the separator vessel 13 comprising light and heavy hydrocarbons together with dissolved ammonia and hydrogen sulfide is then sent to the fractionator column 18, where a naphtha stream 19 with ammonia and hydrogen sulfide are removed overhead. The heavy hydrocarbon components comprising a diesel stream 20 and an unconverted oil stream 21 are separated and recovered lower in the fractionator column 18, The naphtha stream 19 can be subjected to additional separation steps. The diesel stream 20 can also be further separated by boiling points into other valuable products such as aviation jet fuel.
Streams 11 (low sulfur FCC feed) and 21 (unconverted oil stream) are typically combined as a single feed for the FCC unit. However, stream 21 can also be kept segregated for use as a valuable intermediate product for making lubricating oils or as feed for making ethylene.
Separating the liquid phase into a controlled liquid portion and an excess liquid portion makes it possible to bypass the controlled liquid portion around the hydrocracking reactor* This allows a high conversion in the hydrocracking reactor and this improves the diesel quality while main tainting a low overall conversion so the desired amount of FCC feed is produced-
Fig. 2 illustrates an embodiment of the invention in which the liquid portion from the separation zone is cracked in

the hydrocracking reactor and the vapour plus liquid portion is sent to the stripper column.
A feed 1 is combined with hydrogen, for instance hydrogen rich recycle gas 2’ and sent to a hydrotreating reactor 3 for hydrodesulfurization and hydrodenitrogenation in the one or more catalytic beds. The hydrotreated effluent stream comprising a liquid/vapour mixture enters the separation zone 4 downstream the last catalytic bed and is separated into a vapour plus liquid portion 5 and a controlled liquid portion 6 using the outlet device as de’ scribed in Fig, 1. The flow rate of controlled liquid portion 6 is controlled by conventional flow control valve 1, and excess liquid not required leaves the separation zone 4 as overflow through the outlet device (shown in Fig. 3) together with all the vapour and thus forms the vapour plus liquid portion 5,
The vapour plus liquid portion 5 leaves the hydrotreating reactor 3 and flow to a separator vessel 8, A hydrogen-rich vapour stream 9 is produced from the separator overhead and a hydrocarbon liquid stream 10 is produced from the bottom of separator vessel 8. The hydrocarbon liquid stream 10 also contains dissolved ammonia and hydrogen sulfide and flows to the stripper column 11. A light hydrocarbons stream 12 together with ammonia and hydrogen sulfide are separated from stripper column 11 and the resulting liquid stream from the bottom of stripper column 11 is suitable as low sulfur FCC feed 13.
Controlled liquid portion 6 is comprised of heavy liquid hydrocarbons with substantially reduced sulfur and nitrogen

content relative to the feed 1. It leaves the hydrotreating reactor through the flow control valve 7 and combines with hydrogen*-rich vapour stream 9 from separator vessel 8 to make the mixed vapour-liquid stream 14. A second hydrocarbon feedstock 26 can optionally be added to the mixed vapour-liquid stream 14 if required* The mixed vapour-liquid stream 14, optionally combined with the second feed’ enters the hydrocracking reactor 8, where it is catalytically cracked into the components of stream 16 having properties suitable for diesel fuel preparation. One or more catalyst beds are present in reactor 15. Stream 16 flows to separator vessel 17 where a hydrogen rich vapour stream 18 is separated overhead and recycled to the hydrotreating reactor via a recycle compressor 19. Make-up hydrogen 20 can be added to the hydrogen-rich stream 18 either upstream or downstream of the compressor 19 to maintain the required pressure,
The liquid product 21 from the separator 17 comprising light and heavy hydrocarbons together with dissolved ammonia and hydrogen sulfide is then sent to the fractionator column 22, where naphtha with ammonia and hydrogen sulfide are removed overhead in naphtha stream 23. The heavy hydrocarbon components comprising a diesel stream 24 and an unconverted oil stream 25 are separated and recovered lower in the fractionator column 22. Naphtha stream 23 can be subjected to additional separation steps- Diesel stream 24 can also be further separated by boiling points into other valuable products such as aviation jet fuel.
Fig. 3 shows an embodiment of the invention in which the bottom section of the hydrotreating reactor is adapted to

include the liquid/vapour separation system. The separator vessel is therefore integrated in the bottom section of the hydrotreating reactor. The outlet device is located below the support of the last catalyst bed 1 and the support can typically be provided by beams and grids 2. A disengagement space 3 is created in the bottom of the reactor vessel to allow separation of vapour and liquid phases.
In this embodiment of the invention the outlet device is in the form of a standpipe 4 provided with an ant swirl baffle 5 at the top open end of the standpipe 4- A liquid interface level 6 is created at the height of the baffle 5 which allows all the reactor vapour and a portion of the liquid phase to overflow as a vapour plus liquid portion and exit the reactor through transfer pipe 7 to the downstream hydrocracking reactor (not shown)•
An outlet pipe 8 is provided for removing a controlled portion of the liquid phase from the center low point of the bottom head of the reactor also covered by an ant swirl baffle 5, The flow of the liquid portion through outlet pipe 8 is regulated by the flow control element 9 through a standard flow control valve 10 through the transfer pipe 11 to a downstream stripper (not shown)-
Fig. 4 illustrates another embodiment of the invention where a separator vessel 13 containing the outlet device and the outlet pipe is added downstream of the hydrotreating reactor. The separator vessel 13 is connected by pipe 12 transferring all of the vapour and liquid contents from the bottom catalyst bed 1 of the hydrotreating reactor to the separator vessel 13. In this embodiment the outlet de-

vice is in the form of a standpipe 4 provided with an anti-swirl baffle 5 at the top open end of the pipe. A liquid interface level 6 is created at the height of the baffle 5 which allows all the reactor vapour and a portion of the liquid phase, i.e. the vapour plus liquid portion, to overflow and exit the hydrotreating reactor through transfer pipe 7 to the downstream hydrocracking reactor (not shown). An outlet pipe 8 is provided for removing a portion of the liquid phase, i.e. the controlled liquid portion, from the centre low point of the bottom head of the reactor also covered by an anti-swirl baffle 5, The flow through this pipe is regulated by the flow control element 9 through a standard flow control valve 10 through the transfer pipe 11 to a downstream stripper (not shown).
This embodiment of the invention is especially advantageous when existing plants have to be revamped. In such cases it may not be possible to install the liquid/vapour separation system in an already existing hydrotreating reactor. Installing the liquid/vapour separation system outside the hydrotreating reactor in the form of a separator vessel containing the outlet device and the outlet pipe directly downstream the hydrotreating reactor allows a separation of the mixture of vapour and liquid effluent from the hydrotreating reactor into a liquid stream and a vapour plus liquid stream suitable for further processing.
The effluent from the one or more catalytic beds in the hydrotreating reactor is a mixture of vapour and liquid which separates into a liquid phase and a vapour phase. The boiling range of the liquid phase is slightly lower than the

boiling range of the feed entering the hydrotreating reactor. The liquid phase has a boiling range of 200-580*'.
Partial conversion hydrocracking catalysts useful in the process of the invention need to fulfil the following key functional requirements:
- Size and activity grading to minimize fouling and pressure drop
- Demoralization and carbon residue reduction
- Hydrodesulfurization for FCC feed pre-treatment to sulfur levels of typically 100 to 1000 wppm
- Hydrodenitrogentation for hydrocracker feed pre-treatment to nitrogen levels of typically 50 to 100 wppm
- Hydrocracking with high conversion activity and high selectivity to diesel-
In order to maximize performance in each of these functional categories, stacked (multiple) catalyst systems are useful and provide better overall performance and lower cost compared with single multi-function catalyst systems. The process described here is useful in facilitating the independent control of reaction severity for multiple catalysts leading to optimized performance and longer useful life.
Hydrotreating catalysts are individually specified to optimize sulfur removal for FCC feed pretreatment and for nitrogen removal for hydrocracking feed pretreatment, Zola-tic and amorphous silica-alumna hydrocracking catalysts are also useful in the process of the invention to convert heavy feed to lighter products with high diesel yield.

The hydrotreating catalysts can for instance be based on cobalt, molybdenum, nickel and wolfram (tungsten) combinations such as CoMo, NiMo, NiCoMo and NiW and supported on suitable carriers. Examples of such catalysts are TK-558, TK*559 and TK-565 from Haldor Tops0e A/S. Suitable carrier materials are silica, alumina, silica-alumina, titania and other support materials known in the art. Other components may be included in the catalyst for instance phosphorous.
Hydrocracking catalysts may include an amorphous cracking component and/or a zeolite such as zeolite Y, ultrastable zeolite Y, dealuminated zealots etc. Included can also be nickel and/or cobalt and molybdenum and/or wolfram combinations. Examples are TK-931, TK-941 and TK-951 from Haldor Tops0e A/S, The hydrocracking catalysts are also supported by suitable carriers such as silica, alumina, silica-alumina, titania and other conventional carriers known in the art. Other components may be included such as phosphorus may be included as reactivity promoters.
Reaction conditions in the hydrotreating reactor include a reactor temperature between 325'C-425°C, a liquid hourly space velocity (LHSV) in the range 0.3 hr"‘ to 3,0 hr"‘, a gas/oil ratio of 500-1,000 Nm’/m’ and a reactor pressure of 80-140 bars.
Reaction conditions in the hydrocracking reactor include a reactor temperature between 325**C-425*C, a liquid hourly space velocity (LHSV) in the range 0.3hr*’ to 3,0hr"\ a gas/oil ratio of 500-1,500 a reactor pressure of 80-140 bars.

The controlled liquid portion can comprise 30-100 wt% of the liquid phase’ and the excess liquid portion can comprise 0-70 wt% of the liquid phase. Preferably the controlled liquid portion comprises 60-95 wt% of the liquid phase, and the excess liquid portion comprises 5-40 wt% of the liquid phase.
The current European standard EN 590 EU ULSD specifications for diesel are:
Sulfur: 10 - 50 wppm
Density: T95 (D-86): Cetane No. D-630: >51
Cetane Index D-4737; >46
Poly-Aromatics: The current U.S. standard specifications are less restrictive than the European Standard specifications mentioned above.
Yield terms are defined with respect to true boiling point (TBP) cuts and the following definitions are used in the examples:
Component: TBP Cut
Naphtha: Kerosene: 150"260'C
Heavy diesel: 260-390’C
Full range diesel: 150-390'C
Unconverted: >390'*C

Conversion terms are defined are defined in the following, Feed and product values are in %:
390°C+ net conversion = Feed390oc+ - Product39ooc+
390*’0-*- true conversion = (Feed390oc+ - Product390oc+)/Feed 3900C+
390°C4- gross conversion = 100 - Product39ooc+
EXAMPLES
Example 1:
In this example the liquid/vapour separation system is integrated in the hydrotreating reactor. This example shows how the different boiling ranges of the hydrotreating reactor effluent split in the flash at the outlet device and the outlet pipe in the liquid/vapour separation system.
Temperature and pressure of the hydrotreating reactor is shown at start-of-run conditions in Table 1 and end-of-run conditions in Table 2.



The results show that the liquid phase contains mainly gas oil boiling range material with some diesel material, but only a small portion of jet and naphtha* The diesel boiling range material from the hydrotreating reactor has a relatively high sulfur content and high density, and it con-taints a high content of mono-aromatics so it is more suitable as an FCC feed rather than as high quality ULSD.
The process of the invention leads to substantial economic benefits as illustrated in Table 2.
Example 2: (Comparative)
This example shows how the 260-390*'C diesel quality improves with additional hydrocracking when compared to only hydrotreating a HVGO. The results are shown in Table 3. The 260-390°C diesel is produced at 80 bar hydrogen pressure.


The results in Table 3 show that the qualities of an HVGO improve with conversion, as the specific gravity decreases and the cetane index increases.
Example 3 (Comparative):
This example illustrates a simplified comparison of both a conventional medium pressure hydrocracking process and a high pressure hydrocracking process using a conventional hydrocracker as compared with the process of the invention, i.e. a medium pressure partial conversion hydrocracking process. The same pressure level was used in both the MHC and the process of the invention. Sufficient catalyst was used to achieve ULSD sulfur level (10 wppm). Table 4 shows the performance that can be achieved by the process of the invention.


The results shown in Table 4 indicate that it is not possible for a MHC process to make the equivalent diesel density and cetane quality as compared to the process of the invention. Increasing hydrogen pressure to achieve sufficient aromatic saturation to match the diesel density achieved with the invention requires about 60% higher operating pressure for the conventional hydrocracker unit as shown by the results in Table 4.
For a unit processing 5000 tones per day of total charge, it is estimated that the process of the invention can save 10 to 20 million Euro capital cost compared to a high pressure conventional once-through partial conversion hydro-cracker making the same product quality. Hydrogen is also used more efficiently using the apparatus of the invention

Resulting in a savings of 250,000 normal cubic meters of hydrogen per day. The annual operating cost savings based hydrogen demand would be 2 to 3 million euro. Utility costs are lowered relative to the high-pressure hydrocracker option, mainly as a result of decreased hydrogen makeup and recycle compression requirements•











NEW CLAIMS
1. Hydro cracking process for partially converting a hydrocarbon feedstock comprising the steps of
(a) hydrotreating a hydrocarbon feedstock with a hydrogen-rich gas to produce a hydro treated effluent stream comprising a liquid/vapour mixture that separates into a liquid phase and a vapour phase, and
(b) in a separation step, separating the liquid phase into a controlled liquid portion set by the conversion and an excess liquid portion by means of regulating the flow of controlled liquid from the separation step with a flow control element and combining the vapour phase with the excess liquid portion to form a vapour plus liquid portion, and
(c) subsequently separating a fraction containing feed for fluid catalytic cracking from the controlled liquid portion and simultaneously hydrocracking the vapour plus liquid portion to produce a diesel-containing fraction, or
hydrocracking the controlled liquid portion to produce a diesel-containing fraction and simultaneously separating a fraction containing feed for fluid catalytic cracking from the vapour plus liquid portion.

2. Process according to claim 1 wherein either the van
pour plus liquid portion or the controlled liquid portion
is combined with a second hydrocarbon feedstock to provide
a feed for the hydrocracking step,
3, Process according to claim 1, wherein the controlled
liquid portion is hydro cracked to produce a diesel-
containing fraction and the fraction containing feed for
fluid catalytic cracking is separated from the vapour plus
liquid portion by cooling washing and phase separation
into a hydrogen-rich vapour stream low in ammonia and hy
drogen sulfide and a hydrocarbon liquid stream comprising
the FCC feed-containing fraction,
4* Process according to claim 3, wherein the hydrogen-rich vapour stream low in ammonia and hydrogen sulfide is combined with the controlled liquid portion and hydro-cracked to produce a diesel-containing fraction.
5. Process according to claim 1 wherein the fraction containing feed for fluid catalytic cracking is separated from the controlled liquid portion by stripping,
6. Process according to claim 3, wherein the fraction containing feed for fluid catalytic cracking is separated from the hydrocarbon liquid stream comprising the fraction containing feed for fluid catalytic cracking by stripping

7. Apparatus for carrying out a hydrocracking process,
comprising a hydrotreating reactor having one or more
lyric beds and in series with a hydrocracking reactor, having a liquid/vapour separation system downstream the or more catalytic beds of the hydrotreating reactor, liquid/vapour separation system comprising an outlet dev
and an outlet pipe in a separator vessel, the outlet
comprising a pipe extension above the bottom of the spear’s-
tion vessel, the pipe extension being provided with an
anti-swirl baffle at the top open end of the pipe extend
sion, the separator vessel being provided with an outlet
pipe at the separator vessel bottom, the outlet pipe ;
provided with an ant i-swirl baffle and with a flow contra element through a flow control valve.
8. Apparatus according to claim 7, wherein the separate.:. vessel is integrated in the hydrotreating reactor downstream the last catalytic bed of the one or more cattily beds.
9. Apparatus according to claim 1, wherein the separate vessel is located downstream the hydrotreating reactor.


Documents:

1454-CHENP-2008 EXAMINATION REPORT REPLY RECEIVED 17-02-2014.pdf

1454-CHENP-2008 OTHERS 03-01-2014.pdf

1454-CHENP-2008 OTHERS 17-02-2014.pdf

1454-CHENP-2008 AMENDED PAGES OF SPECIFICATION 03-01-2014.pdf

1454-CHENP-2008 AMENDED CLAIMS 03-01-2014.pdf

1454-CHENP-2008 AMENDED CLAIMS 28-03-2014.pdf

1454-CHENP-2008 AMENDED PAGES OF SPECIFICATION 28-03-2014.pdf

1454-CHENP-2008 CORRESPONDENCE OTHERS 10-02-2014.pdf

1454-CHENP-2008 CORRESPONDENCE OTHERS 16-04-2013.pdf

1454-CHENP-2008 CORRESPONDENCE OTHERS 06-03-2014.pdf

1454-CHENP-2008 EXAMINATION REPORT REPLY RECEIVED 03-01-2014.pdf

1454-CHENP-2008 EXAMINATION REPORT REPLY RECEIVED 28-03-2014.pdf

1454-CHENP-2008 FORM-1 03-01-2014.pdf

1454-CHENP-2008 FORM-1 28-03-2014.pdf

1454-CHENP-2008 FORM-3 03-01-2014.pdf

1454-CHENP-2008 FORM-3 28-03-2014.pdf

1454-CHENP-2008 OTHER PATENT DOCUMENT 03-01-2014.pdf

1454-CHENP-2008 POWER OF ATTORNEY 28-03-2014.pdf

1454-chenp-2008-abstract.pdf

1454-chenp-2008-claims.pdf

1454-chenp-2008-correspondnece-others.pdf

1454-chenp-2008-description(complete).pdf

1454-chenp-2008-drawings.pdf

1454-chenp-2008-form 1.pdf

1454-chenp-2008-form 26.pdf

1454-chenp-2008-form 3.pdf

1454-chenp-2008-form 5.pdf

1454-chenp-2008-pct.pdf

Petition for POR.pdf


Patent Number 260200
Indian Patent Application Number 1454/CHENP/2008
PG Journal Number 15/2014
Publication Date 11-Apr-2014
Grant Date 04-Apr-2014
Date of Filing 25-Mar-2008
Name of Patentee HALDOR TOPSOE A/S
Applicant Address NYMOLLEVEJ 55 DK-2800 KGS. LYNGBY
Inventors:
# Inventor's Name Inventor's Address
1 HUNTER, MICHAEL, GLENN 7543 EAST CROWN PARTWAY ORANGE, CA 92867
2 VIVAS, ANGELICA, HIDALGO ENTEDALEN 60 DK-2730 HERLEV
3 JENSEN, LARS, SKOV SANDBANKEN 25 DK-4320 LEJRE
4 LOW, GORDON, GONGNGAI 14722 PLAZA DRIVE APT. D, TUSTIN, CA 92780
PCT International Classification Number C10G 65/02
PCT International Application Number PCT/EP06/08868
PCT International Filing date 2006-09-12
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 PA200501334 2005-09-26 Denmark