Title of Invention	"AN IMPROVED PROCESS FOR THE UPGRADATION OF PETROLEUM HEAVY FEED STOCK"
Abstract	There is disclosed an improved process for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stripping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of stem and oxygen for the stripping reaction, allowing hydro-cracking to take place above the stripping reaction zone characterized in that. (a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst. <b) the catalyst bed in the stripping zone is kept in an unsettled and agitated condition with the catalyst parties physically having limited movement. (c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling. There is also disclosed a reactor therefor.

Title of Invention

"AN IMPROVED PROCESS FOR THE UPGRADATION OF PETROLEUM HEAVY FEED STOCK"

Abstract

There is disclosed an improved process for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stripping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of stem and oxygen for the stripping reaction, allowing hydro-cracking to take place above the stripping reaction zone characterized in that. (a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst. <b) the catalyst bed in the stripping zone is kept in an unsettled and agitated condition with the catalyst parties physically having limited movement. (c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling. There is also disclosed a reactor therefor.

Full Text	Introduction in the field of invention. This invention, in one aspect, relates to an improved process for the upgradation of petroleum heavy feed stock. In another aspect, this invention relates to an improved reactor for the upgradation of petroleum heavy feed stock. Prior Art. It is well known to subject the heavy feed stock to reaction in a cracking zone of conventional reactors This is a packed bed of inert material. In this zone, the comer material containing residual oil and coke moves downward into the gasification zone, oil is stripped by the rising gas and coke is gasified in the bottom of the gasification zone. The drawback of this design is as follows. Comer material will fill up the void space and may not move downward due to blockage of the channel. Also, this will cause the hot gas to bypass through the central tube and not move through the packed bed. The above problem can be eliminated by vibrating the reactor and choosing proper shape of the packing material. By vibrating the reactor the packing material will be allowed to move laterally and this helps in free flow of comer material downwards since the channels get opened up. Also, the void space can be increased by choosing cubical (square cross section) shape packing material More the void space more is the free flowing of comer material and the rising gas cubes give more and more void space due to multiple contact points on it (8 comers for each cube). 2 Another drawback of the reactor design is the manner in which the residuum is spread on the comer material. The previous design shows a tube with holes installed in the cracking zone. This is not a good design as because only the comer material close to the tube will receive the oil on it with a thick layer of it and the comer material in the lower portion of the cracking zone will run dry. A thick oil layer means more diffusional resistance for hydrogen to reach the layer close to comer material leading to excessive coke formation It is, therefore, an object of this invention to propose an improved method for the upgradation of petroleum heavy feed stock. It is another object to propose an improved reactor for the above method. It is a further object to propose such a method and reactor which are easy to control and operate A still further object is to propose such a method and reactor by which it is possible to effectively gasify the coke. It is still further object to propose such a method and reactor by which the top gases obtained can be liquefied by condensation and to effect separation of different liquid products. These and other objects will be apparent from the following description. In the process of invention, the petroleum crude is fed from the top of the reactor at around 975° F into the cracking zone. The cracking zone has a bed of inert materials like dolomite, magnetite with large external surface. These are maintained at around 1000° F by the hot gases coming from below. The crude oil is fed through a set of nozzles arranged around the inner wall of the cracking zone of the reactor. These nozzles can be arranged at one or more horizontal plane/s and many arrangements are possible. The oil is sprayed with desired pressure and feed rate throughout the cracking zone. 3 The inert materials are supported on suitable support member like a wire mesh. Below the cracking zone is a stripping zone having a packed bed made of ceramic material. These are preferably made of special shapes like hollow cubes circular rings. The shape and size are judiciously selected taking into consideration the density of the material so that necessary voids are created in the bed encouraging less channeling in the bed. In the process, the liquid feed is subjected to thermal cum hydro-cracking by means of hydrogen gas coming from the gasification zone, which is below the stripping zone. The hydrogen is fed to the cracking zone through a co-axial tube, preferably disposed centrally, in the stripping zone connecting gasification zone and hydro-cracking zone. The product of reaction is mainly gasoline, gaseous hydro-carbons and coke. The coke gets deposited around the inert magnetite /dolomite refractory shapes. These cokes deposited material flow downwardly due to increased density through the voids of channels in the stripping zone into the gasification zone. The coke is stripped off the surfaces of the magnetite by the following hot gases and the magnetite/dolomite becomes lighter after shedding the coke and hence is lifted back to the hydro-cracking zone preferably through central tube in the stripping zone by the gases of the reaction which are pnncipally C02, H2 and CO. A temperature gradient of 1000° F to 1400° F is maintained between the top and bottom of the packed zone. The coke is gasified to produce H2 and C02 in presence of steam and oxygen. The CO2 and H2 join the product gases leaving the top of the cracking zone and the gases are condensed and separated into desired fractions. The process and the reactor described above are only illustrative of the invention and are not restricted thereto. 4 The other features are the following (a) the nozzles are connected to the feed supply by a tubular means secured to the inner surface of the reactor wall. (b) the angle of the nozzles is adjustable and is directed towards in the interior central portion of the hydro-cracking zone. (c) the nozzles are provided in one or more horizontal layers (d) each horizontal layer is formed of a single or more tubes connected to the inner wall of the reactor carrying the nozzle and (e) the vibrating or rocking means is an eccentric cam. Thus according to this invention there is provided an improved for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stripping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of steam and Oxygen for the stripping reaction, allowing hydro-cracking to take place above the stripping zone characterized in that. (a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst. (b) the catalyst bed in the stripping zone is kept in an unsettled and agitated condition with the catalyst parties physically having limited movement. (c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling. There is also provided according to this invention an improved hydro-cracking reactor for petroleum feed stock comprising. i) a first top hydro-cracking zoned having one or more levels of nozzles on the inner circumstances for spraying the feed stock. ii) the nozzles being connected to the feed stock supply by tubular means. iii) a second intermediate stripping zone having the hydro-cracking catalysts of different shapes and sizes. iv) a third gaisification zone at the bottom below the stripping zone and v) a vibrating mechanism connected to the external lower end of the reactor. This invention will now be described with reference to the accompanying drawings wherein File 1 shows a conventional reactor. File 2 shows the reactor of the invention File 3 shows a few shapes of the packing materials. It will be seen that in the conventional reactor (A) the oil is fed through one or more tubes perforated at the top surface (7) extending across the section of the reactor and in the Hydro-cracking zone (2) above the stripping zone (3). The stripping zone below has conventional packing materials like Raschig Rings (8) and as stated earlier these are stationary beds and the top layers get the oil layer There is the problem of channeling and coke is formed on the surface of the packing material. In the reactor (B) shown in Fig. 2 the feed in sprayed through nozzles (7A) from one or more circular tubes arranged along the inner surface of the reactor in the Hydro-cracking zone (2). This covers the entire surface area of the stripping zone (3) below when oil is sprayed. The reactor is vibrated on suitable supports due to which the particles of the packed bed/stripping zone is continuously dislocated thereby dislodging the coke formed on the surface. This increases the chances for fresh oil to go through the gasification process. Moreover, the bed is in a state of expanded condition and channeling is eliminated. As in the conventional reactor there is a feed zone 1, a hydro-cracking zone 2 improved stripping zone 3 and gasification zone 4. Steam/02 is admitted through feed pipe 5 at the bottom. There is an outlet 6 at the top. Recycle is possible (5A), (8). (9). I have found that using solids of irregular shape increases the contact area of the unit materials, viz. Manganese dolomite supported on wire mesh plate as against shapes like raschig rings etc. The material can be also of doughnut shapes and some such shapes are shown in fig. 3. The oil feed is sprayed towards the interior and there is uniform wetting and coverage of the entire top surface of the catalyst bed. 6 Due to the novel shapes and also due to the vibration imparted to the reactor at the lower end, say for example by eccentric cam arrangement, the bed is not behaving like a stationary block but is in agitated or disturbed condition and channeling is avoided. Moreover, due to the rising gases (steam + 02) from below, the bed is further expanded and the catalyst particles are more in a free condition not possible in the known reactor. Due to this physical movement of the catalyst particles the coke formed on the surface is dislodged opening the surface of the catalyst for further reaction not possible in the known reactor. Further, the oil flows down through the entire bed without channeling witnessed in the known art. Furthermore, any oil coming down carrying away catalyst particles is recycled to the top of the bed through a central tube by another stream of steam or gas. The circular rings along the inner surface can be arranged in one or more horizontal planes, can be continuous rings or a plurality of interrupted rings and many variations are possible. Though in the known art reactors, it is expected that during hydro-cracking coke is formed and the coke with any metals from the feedstock is deposited on the carrier and falls through the stripping zone, this does not happen satisfactorily. There may be some vertical expansion of the catalyst bed due to flow of oil gas and steam in the upward direction, but channeling is witnessed. 7 claim (1) An improved process for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stnpping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of stem and oxygen for the stnpping reaction, allowing hydro-cracking to take place above the stnpping reaction zone characterized in that. (a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst (b) the catalyst bed in the stripping zone is kept in an unsettled and agitated condition with the catalyst parties physically having limited movement (c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling. 2. A process as claimed in claim 1 wherein the petroleum feed stock is sprayed from spraying nozzles arranged around the inner surface of the hydro-cracking zone of the reactor. 3. A process as claimed in claims 1 and 2 wherein the catalysts are of shapes like doughnut cubes, triangles, cylinders, squares and rectangles 4. An improved hydro-cracking reactor for petroleum feed stock comprising. i) a first top hydro-cracking zoned having one or more levels of nozzles on the inner circumstances for spraying the feed stock ii) the nozzles being connected to the feed stock supply by tubular means. in) a second intermediate stripping zone having the hydro-cracking catalysts of different shapes and sizes iv) a third gasification zone at the bottom below the stripping zone and v) a vibrating mechanism connected to the external lower end of the reactor 5 A reactor as claimed in claim 4 wherein the nozzles are connected to the feed supply by a tubular means secured to the inner surface of the reactor wall 6. A reactor as claimed in claim 5 wherein the angle of the nozzles are adjustable and are directed towards the interior central portion of the hydro-cracking zone. 7. A reactor as claimed in claim 4 and 5 wherein the nozzles are provided in one or more horizontal layers 8. A reactor as claimed in Claim 7 wherein each horizontal layer is formed of a single or more tubes connected to the inner wall of the reactor carrying the nozzles. 9. A reactor as claimed in claims 4 to 8 wherein the vibrating or rocking means is an eccentric cam. 10. An improved hydro-cracking process substantiating as herein described 11. An improved hydro-cracking reactor substantiating as herein described with reference to the accompanying drawing. 9 There is disclosed an improved process for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stripping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of stem and oxygen for the stripping reaction, allowing hydro-cracking to take place above the stripping reaction zone characterized in that. (a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst. (c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling. There is also disclosed a reactor therefor.

Full Text

Introduction in the field of invention.
This invention, in one aspect, relates to an improved process for the upgradation of petroleum heavy feed stock.
In another aspect, this invention relates to an improved reactor for the upgradation of petroleum heavy feed stock.
Prior Art.
It is well known to subject the heavy feed stock to reaction in a cracking zone of conventional reactors
This is a packed bed of inert material.
In this zone, the comer material containing residual oil and coke moves downward into the gasification zone, oil is stripped by the rising gas and coke is gasified in the bottom of the gasification zone.
The drawback of this design is as follows.
Comer material will fill up the void space and may not move downward due to blockage of the channel.
Also, this will cause the hot gas to bypass through the central tube and not move through the packed bed.
The above problem can be eliminated by vibrating the reactor and choosing proper shape of the packing material.
By vibrating the reactor the packing material will be allowed to move laterally and this helps in free flow of comer material downwards since the channels get opened up.
Also, the void space can be increased by choosing cubical (square cross section) shape packing material More the void space more is the free flowing of comer material and the rising gas cubes give more and more void space due to multiple contact points on it (8 comers for each cube).
2

Another drawback of the reactor design is the manner in which the residuum is spread on the comer material. The previous design shows a tube with holes installed in the cracking zone. This is not a good design as because only the comer material close to the tube will receive the oil on it with a thick layer of it and the comer material in the lower portion of the cracking zone will run dry. A thick oil layer means more diffusional resistance for hydrogen to reach the layer close to comer material leading to excessive coke formation
It is, therefore, an object of this invention to propose an improved method for the upgradation of petroleum heavy feed stock.
It is another object to propose an improved reactor for the above method.
It is a further object to propose such a method and reactor which are easy to control and operate
A still further object is to propose such a method and reactor by which it is possible to effectively gasify the coke.
It is still further object to propose such a method and reactor by which the top gases obtained can be liquefied by condensation and to effect separation of different liquid products.
These and other objects will be apparent from the following description.
In the process of invention, the petroleum crude is fed from the top of the reactor at around 975° F into the cracking zone.
The cracking zone has a bed of inert materials like dolomite, magnetite with large external surface.
These are maintained at around 1000° F by the hot gases coming from below.
The crude oil is fed through a set of nozzles arranged around the inner wall of the cracking zone of the reactor.
These nozzles can be arranged at one or more horizontal plane/s and many arrangements are possible.
The oil is sprayed with desired pressure and feed rate throughout the cracking zone.
3

The inert materials are supported on suitable support member like a wire mesh.
Below the cracking zone is a stripping zone having a packed bed made of ceramic material.
These are preferably made of special shapes like hollow cubes circular rings. The shape and size are judiciously selected taking into consideration the density of the material so that necessary voids are created in the bed encouraging less channeling in the bed.
In the process, the liquid feed is subjected to thermal cum hydro-cracking by means of hydrogen gas coming from the gasification zone, which is below the stripping zone.
The hydrogen is fed to the cracking zone through a co-axial tube, preferably disposed centrally, in the stripping zone connecting gasification zone and hydro-cracking zone.
The product of reaction is mainly gasoline, gaseous hydro-carbons and coke.
The coke gets deposited around the inert magnetite /dolomite refractory shapes. These cokes deposited material flow downwardly due to increased density through the voids of channels in the stripping zone into the gasification zone.
The coke is stripped off the surfaces of the magnetite by the following hot gases and the magnetite/dolomite becomes lighter after shedding the coke and hence is lifted back to the hydro-cracking zone preferably through central tube in the stripping zone by the gases of the reaction which are pnncipally C02, H2 and CO.
A temperature gradient of 1000° F to 1400° F is maintained between the top and bottom of the packed zone.
The coke is gasified to produce H2 and C02 in presence of steam and oxygen.
The CO2 and H2 join the product gases leaving the top of the cracking zone and the gases are condensed and separated into desired fractions.
The process and the reactor described above are only illustrative of the invention and are not restricted thereto.
4

The other features are the following
(a) the nozzles are connected to the feed supply by a tubular means secured to the inner surface of the reactor wall.
(b) the angle of the nozzles is adjustable and is directed towards in the interior central portion of the hydro-cracking zone.
(c) the nozzles are provided in one or more horizontal layers
(d) each horizontal layer is formed of a single or more tubes connected to the inner wall of the reactor carrying the nozzle and
(e) the vibrating or rocking means is an eccentric cam.
Thus according to this invention there is provided an improved for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stripping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of steam and Oxygen for the stripping reaction, allowing hydro-cracking to take place above the stripping zone characterized in that.
(a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst.
(b) the catalyst bed in the stripping zone is kept in an unsettled and agitated condition with the catalyst parties physically having limited movement.
(c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling.
There is also provided according to this invention an improved hydro-cracking reactor for petroleum feed stock comprising.
i) a first top hydro-cracking zoned having one or more levels of nozzles on the inner
circumstances for spraying the feed stock.
ii) the nozzles being connected to the feed stock supply by tubular means.
iii) a second intermediate stripping zone having the hydro-cracking catalysts of different
shapes and sizes.
iv) a third gaisification zone at the bottom below the stripping zone and
v) a vibrating mechanism connected to the external lower end of the reactor.

This invention will now be described with reference to the accompanying drawings wherein
File 1 shows a conventional reactor.
File 2 shows the reactor of the invention
File 3 shows a few shapes of the packing materials.
It will be seen that in the conventional reactor (A) the oil is fed through one or more tubes perforated at the top surface (7) extending across the section of the reactor and in the Hydro-cracking zone (2) above the stripping zone (3).
The stripping zone below has conventional packing materials like Raschig Rings (8) and as stated earlier these are stationary beds and the top layers get the oil layer There is the problem of channeling and coke is formed on the surface of the packing material.
In the reactor (B) shown in Fig. 2 the feed in sprayed through nozzles (7A) from one or more circular tubes arranged along the inner surface of the reactor in the Hydro-cracking zone (2).
This covers the entire surface area of the stripping zone (3) below when oil is sprayed. The reactor is vibrated on suitable supports due to which the particles of the packed bed/stripping zone is continuously dislocated thereby dislodging the coke formed on the surface. This increases the chances for fresh oil to go through the gasification process.
Moreover, the bed is in a state of expanded condition and channeling is eliminated.
As in the conventional reactor there is a feed zone 1, a hydro-cracking zone 2 improved stripping zone 3 and gasification zone 4.
Steam/02 is admitted through feed pipe 5 at the bottom. There is an outlet 6 at the top. Recycle is possible (5A), (8). (9).
I have found that using solids of irregular shape increases the contact area of the unit materials, viz. Manganese dolomite supported on wire mesh plate as against shapes like raschig rings etc.
The material can be also of doughnut shapes and some such shapes are shown in fig. 3.
The oil feed is sprayed towards the interior and there is uniform wetting and coverage of the entire top surface of the catalyst bed.
6

Due to the novel shapes and also due to the vibration imparted to the reactor at the lower end, say for example by eccentric cam arrangement, the bed is not behaving like a stationary block but is in agitated or disturbed condition and channeling is avoided.
Moreover, due to the rising gases (steam + 02) from below, the bed is further expanded and the catalyst particles are more in a free condition not possible in the known reactor.
Due to this physical movement of the catalyst particles the coke formed on the surface is dislodged opening the surface of the catalyst for further reaction not possible in the known reactor.
Further, the oil flows down through the entire bed without channeling witnessed in the known art.
Furthermore, any oil coming down carrying away catalyst particles is recycled to the top of the bed through a central tube by another stream of steam or gas.
The circular rings along the inner surface can be arranged in one or more horizontal planes, can be continuous rings or a plurality of interrupted rings and many variations are possible.
Though in the known art reactors, it is expected that during hydro-cracking coke is formed and the coke with any metals from the feedstock is deposited on the carrier and falls through the stripping zone, this does not happen satisfactorily. There may be some vertical expansion of the catalyst bed due to flow of oil gas and steam in the upward direction, but channeling is witnessed.
7

claim
(1) An improved process for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stnpping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of stem and oxygen for the stnpping reaction, allowing hydro-cracking to take place above the stnpping reaction zone characterized in that.
(a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst
(b) the catalyst bed in the stripping zone is kept in an unsettled and agitated condition with the catalyst parties physically having limited movement
(c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling.

2. A process as claimed in claim 1 wherein the petroleum feed stock is sprayed from spraying nozzles arranged around the inner surface of the hydro-cracking zone of the reactor.
3. A process as claimed in claims 1 and 2 wherein the catalysts are of shapes like doughnut cubes, triangles, cylinders, squares and rectangles
4. An improved hydro-cracking reactor for petroleum feed stock comprising.
i) a first top hydro-cracking zoned having one or more levels of nozzles on the inner
circumstances for spraying the feed stock
ii) the nozzles being connected to the feed stock supply by tubular means.
in) a second intermediate stripping zone having the hydro-cracking catalysts of different
shapes and sizes
iv) a third gasification zone at the bottom below the stripping zone and
v) a vibrating mechanism connected to the external lower end of the reactor
5 A reactor as claimed in claim 4 wherein the nozzles are connected to the feed supply by a
tubular means secured to the inner surface of the reactor wall

6. A reactor as claimed in claim 5 wherein the angle of the nozzles are adjustable and are directed towards the interior central portion of the hydro-cracking zone.
7. A reactor as claimed in claim 4 and 5 wherein the nozzles are provided in one or more horizontal layers
8. A reactor as claimed in Claim 7 wherein each horizontal layer is formed of a single or more tubes connected to the inner wall of the reactor carrying the nozzles.
9. A reactor as claimed in claims 4 to 8 wherein the vibrating or rocking means is an eccentric cam.
10. An improved hydro-cracking process substantiating as herein described
11. An improved hydro-cracking reactor substantiating as herein described with reference to the accompanying drawing.
9
There is disclosed an improved process for hydro-cracking of petroleum feed stock comprising the steps of feeding the feed stock on to a catalyst bed, for stripping reaction to take place, recycling the oil and carrying over material through recycle zone through and out of contact with the catalyst bed, passing a stream of stem and oxygen for the stripping reaction, allowing hydro-cracking to take place above the stripping reaction zone characterized in that.
(a) the petroleum feed stock is fed in the form of sprays in the hydro-cracking zone and directed towards the centre from the external regions thereof, above the stripping reaction zone containing the catalyst.
(c) The catalyst particles being of different shapes, thereby creating more free spaces and avoiding channeling.
There is also disclosed a reactor therefor.

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Patent Number

200688

Indian Patent Application Number

04/CAL/2002

PG Journal Number

N/A

Publication Date

26-Jan-2007

Grant Date

25-Jan-2007

Date of Filing

01-Jan-2002

Name of Patentee

DR. AMALESH SIRKAR

Applicant Address

76/A, BONDEL ROAD, CALCUTTA-700 019, WEST BENGAL, INDIA,

Inventors:

#	Inventor's Name	Inventor's Address
1	DR. AMALESH SIRKAR	76/A, BONDEL ROAD, CALCUTTA-700 019,

PCT International Classification Number

C 10 G 47/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA