Two stage thermal cracking process with multistage separation system
10865349 · 2020-12-15
Assignee
Inventors
- Satyen Kumar Das (Faridabad, IN)
- Terapalli Hari Venkata Devi Prasad (Faridabad, IN)
- Ponoly Ramachandran Pradeep (Faridabad, IN)
- Arjun Kumar Kottakuna (Faridabad, IN)
- Debasis Bhattacharyya (Faridabad, IN)
- Sanjiv Kumar Mazumdar (Faridabad, IN)
- Sankara Sri Venkata Ramakumar (Faridabad, IN)
Cpc classification
C10G9/14
CHEMISTRY; METALLURGY
C10G69/06
CHEMISTRY; METALLURGY
C10G55/04
CHEMISTRY; METALLURGY
C10G47/00
CHEMISTRY; METALLURGY
C10G45/00
CHEMISTRY; METALLURGY
C10G2300/107
CHEMISTRY; METALLURGY
C10G2300/1044
CHEMISTRY; METALLURGY
C10G9/005
CHEMISTRY; METALLURGY
International classification
C10G47/00
CHEMISTRY; METALLURGY
C10G69/06
CHEMISTRY; METALLURGY
C10G45/00
CHEMISTRY; METALLURGY
C10G55/04
CHEMISTRY; METALLURGY
C10G9/00
CHEMISTRY; METALLURGY
Abstract
The present invention relates to Delayed Coking of heavy petroleum residue producing petroleum coke and lighter hydrocarbon products. The invented process utilizes a pre-cracking reactor for mild thermal cracking of the feedstock and intermediate multistage separation system before being subjected to higher severity thermal cracking in delayed coking process, resulting in reduction in overall coke yield.
Claims
1. A method of reducing overall coke yield in a delayed coking process, said method comprising the steps of: a) passing a fresh hydrocarbon feed to a bottom of a main fractionator and mixing with internal recycle to make a secondary hydrocarbon feedstock; b) heating the secondary hydrocarbon feedstock in a furnace to obtain hot feed at a desired inlet temperature of a pre-cracking reactor; c) passing the hot feed at the desired inlet temperature and a pressure to the pre-cracking reactor, wherein the hot feed undergoes mild thermal cracking reactions to obtain an outlet product material stream; d) introducing the outlet product material stream to a first intermediate separator to split hydrocarbons in the outlet material stream into a first top product and bottom fractions, wherein the first top product comprises lighter products and gases and the bottom fractions is split into a first portion and a second portion; e) routing the first top product to the main fractionator; f) separating a first portion of the bottom fractions in a second intermediate separator column operating at vacuum conditions to obtain a second top product and a heavier bottom product; g) passing the second top product obtained in step (f) to the main fractionator; h) withdrawing the heavier bottom product from the second intermediate separator column of step (f) and passing to the main fractionator, wherein the heavier bottom product comprises Light Vacuum Gas Oil (LVGO) and Heavy Vacuum Gas Oil (HVGO); i) mixing the second portion from the first intermediate separator of step (d) and the heavier bottom product from the second intermediate separator column of step (f) and heating in a furnace to a desired coking temperature to obtain a hot hydrocarbon stream; j) passing the hot hydrocarbon stream from the furnace to a preheated coke drum; and k) passing product vapors exiting the coke drum to the main fractionator column to obtain product fractions.
2. The method as claimed in claim 1, wherein in step (a) the fresh hydrocarbon feedstock is heated directly in the furnace.
3. The method as claimed in claim 1, wherein a vacuum gasoil range cut is withdrawn from the second intermediate separator column and passed to secondary processing units, wherein the secondary processing units are selected from fluid catalytic cracking, hydrocracker and/or hydrotreater units.
4. The method as claimed in claim 1, wherein the second top product from the second intermediate separator column is routed to at least one of product treatments units and the secondary processing unit.
5. The method as claimed in claim 1, wherein the heavier bottom product are passed to secondary processing units.
6. The method as claimed in claim 5, wherein a single stream is withdrawn from the second intermediate separator column and passed to the secondary processing units.
7. The method as claimed in claim 1, wherein the product fractions comprise off-gas with LPG and naphtha, Kerosene, Light Coker Gas Oil (LCGO), Heavy Coker Gas Oil (HCGO), and heavy bottom product.
8. The method as claimed in claim 1, wherein the heavy bottom product from the main fractionator is routed to the second intermediate separator.
9. The method as claimed in claim 1, wherein the heavier bottom product are withdrawn from the second intermediate separator and passed to secondary processing units, wherein the secondary processing units comprises at least one of fluid catalytic cracking, hydrocracker, and/or hydrotreater units.
10. The method as claimed in claim 1, wherein the pre-cracking reactor operates at the desired temperature in the range of 350 to 470 C. and the pressure in the range of 1 to 15 Kg/cm.sup.2 (g).
11. The method as claimed in claim 1, wherein feedstock within the pre-cracking reactor has a residence time in the range of 1 to 40 minutes.
12. The method as claimed in claim 1, wherein the first intermediate separator is operated at a pressure in the range of 1 to 6 Kg/cm.sup.2 (g).
13. The method as claimed in claim 1, wherein the first intermediate separator is operated at a bottom temperature in the range of 300 to 400 C.
14. The method as claimed in claim 1, wherein the second intermediate separator column is operated at a pressure in the range of pressure of 10 to 200 mmHg.
15. The method as claimed in claim 1, wherein the second intermediate separator column is operated at a bottom temperature in the range of 200 to 350 C.
16. The method as claimed in claim 1, wherein the coke drum is operated at a temperature in the range of 470 to 520 C. and a pressure in the range of 0.5 to 5 Kg/cm.sup.2 (g).
17. The method as claimed in claim 1, wherein feedstock within the coke drum is provided with a residence time of more than 10 hours for thermal cracking reactions.
18. The method as claimed in claim 7, wherein the heavy bottom product is Coker Fuel Oil (CFO).
19. A method of reducing overall coke yield in a delayed coking process, said method comprising the steps of: a) heating a hydrocarbon feedstock in a furnace to obtain a hot feed at a desired inlet temperature of a pre-cracking reactor; b) passing the hot feed at the desired inlet temperature and a pressure to the pre-cracking reactor, wherein the hot feed undergoes mild thermal cracking reactions to obtain an outlet product material stream; c) introducing the outlet product material stream to a first intermediate separator to split hydrocarbons in the outlet material stream into a first top product and bottom fractions; d) routing the first top product to a main fractionator; e) separating the bottom fractions in a second intermediate separator column operating at vacuum conditions to obtain a second top product, a heavier bottom product and a heavy bottom material, wherein the heavy bottom product comprises of Coker Fuel Oil (CFO); f) passing the second top product obtained in step (e) to the main fractionator; g) withdrawing the heavier bottom product from the second intermediate separator of step (e) and passing to the main fractionator, wherein the heavier bottom product comprises Light Vacuum Gas Oil (LVGO) and Heavy Vacuum Gas Oil (HVGO); h) heating the heavy bottom material in a furnace to a desired coking temperature to obtain a hot hydrocarbon stream; i) passing the hot hydrocarbon stream from the furnace to a preheated coke drum; and j) passing product vapors exiting the coke drum to the main fractionator column to obtain product fractions.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE INVENTION
(9) While the invention is susceptible to various modifications and/or alternative processes and/or compositions, specific embodiment thereof has been shown by way of example in tables and will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular processes and/or compositions disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the spirit and the scope of the invention as defined by the appended claims.
(10) The tables and protocols have been represented where appropriate by conventional representations, showing only those specific details that are pertinent to understanding the embodiments of the present invention so as not to obscure the disclosure with details that will be readily apparent to those of ordinary skill in the art having benefit of the description herein.
(11) The following description is of exemplary embodiments only and is NOT intended to limit the scope, applicability or configuration of the invention in any way. Rather, the following description provides a convenient illustration for implementing exemplary embodiments of the invention. Various changes to the described embodiments may be made in the function and arrangement of the elements described without departing from the scope of the invention.
(12) Any particular and all details set forth herein are used in the context of some embodiments and therefore should NOT be necessarily taken as limiting factors to the attached claims. The attached claims and their legal equivalents can be realized in the context of embodiments other than the ones used as illustrative examples in the description below.
(13) The present invention relates to a method of reducing overall coke yield in a delayed coking process, wherein the process employs multistage intermediate separator system with the second stage operating in vacuum conditions to prevent the coke formation.
(14) According to one embodiment of the present invention, a method of reducing overall coke yield in delayed coking process, said method comprising the steps of: a) passing fresh hydrocarbon feed to the bottom of a main fractionator and mixing with internal recycle to make secondary hydrocarbon feedstock; b) heating secondary hydrocarbon feedstock in a furnace to obtain hot feed at a desired inlet temperature of a pre-cracking reactor; c) passing the hot feed at desired temperature and pressure to the pre-cracking reactor, wherein the hot feed undergoes mild thermal cracking reactions to obtain outlet product material stream; d) introducing the outlet product material stream to a first intermediate separator to split hydrocarbons in the outlet material stream into top and bottom fractions, wherein the top fraction comprises of lighter products and gases and the bottom fraction is split into first portion and second portion; e) routing the top fraction to the main fractionator; f) separating first portion of the bottom fraction in a second separator column operating in vacuum conditions to obtain top product, heavier product, and bottom product; g) passing the top product obtained in step (f) to the main fractionator; h) withdrawing the heavier product cuts from the second separator column of step (f) and passing to the main fractionator, wherein the heavier cuts comprises of Light Vacuum Gas Oil (LVGO) and Heavy Vacuum Gas Oil (HVGO); i) mixing the second portion from the first intermediate separator of step (d) and the bottom product from the second separator column of step (f) and heating in a furnace to a desired coking temperature to obtain hot hydrocarbon stream; j) passing the hot hydrocarbon stream from the furnace to a preheated coke drum; and k) passing the product vapors exiting the coke drum to the main fractionator column to obtain product fractions.
(15) According to another embodiment of the present invention, a method of reducing overall coke yield in delayed coking process, said method comprising the steps of: a) heating hydrocarbon feedstock in a furnace to obtain hot feed at a desired inlet temperature of a pre-cracking reactor; b) passing the hot feed at desired temperature and pressure to the pre-cracking reactor, wherein the hot feed undergoes mild thermal cracking reactions to obtain outlet product material stream; c) introducing the outlet product material stream to a first intermediate separator to split hydrocarbons in the outlet material stream into top and bottom fractions; d) routing the top fraction to a main fractionator; e) separating first portion of the bottom fraction in a second separator column operating in vacuum conditions to obtain top product, heavier product cuts, and heavy bottom material; f) passing the top product obtained in step (e) to the main fractionator; g) withdrawing the heavier product cuts from the second separator of step (e) and passing to the main fractionator, wherein the heavier cuts comprises of Light Vacuum Gas Oil (LVGO) and Heavy Vacuum Gas Oil (HVGO); h) heating the heavy bottom material in a furnace to the desired coking temperature to obtain the hot hydrocarbon stream. i) passing the hot hydrocarbon stream from the furnace to a preheated coke drum; and j) passing the product vapors exiting the coke drum to the main fractionator column to obtain product fractions.
(16) According to an embodiment of the present invention, in step (a) the fresh hydrocarbon feedstock is heated directly in the furnace.
(17) According to a preferred embodiment of the present invention, the product fraction comprises of off-gas with LPG and naphtha, Kerosene, Light Coker Gas Oil (LCGO), Heavy Coker Gas Oil (HCGO), and heavy bottom product, wherein the heavy bottom product comprises of Coker Fuel Oil (CFO). According to another embodiment of the present invention, the heavy bottom product from the main fractionator may be routed to the second separator.
(18) According to another embodiment of the present invention, vacuum gasoil range cut may be withdrawn from the second separator and passed to secondary processing units. In another embodiment of the present invention, the heavier cuts may be withdrawn from the second separator and passed to secondary processing units. The secondary processing unit comprises of fluid catalytic cracking, hydrocracker and/or hydrotreater units.
(19) According to yet another embodiment of the present invention, the heavier product cuts may be passed to secondary processing units.
(20) According to another embodiment of the present invention, the top product from the second separator may be routed to at least one of product treatments units and the secondary processing unit.
(21) According to yet another embodiment of the present invention, a single stream is withdrawn from the second separator and passed to the secondary processing units.
(22) Feedstock
(23) Liquid hydrocarbon feedstock used in the process may be selected from heavy hydrocarbon feedstock comprising of vacuum residue, atmospheric residue, deasphalted pitch, shale oil, coal tar, clarified oil, residual oils, heavy waxy distillates, foots oil, slop oil, crude oil or blends of such hydrocarbons. The Conradson carbon residue content of the feedstock may be above 4 wt % and density can be minimum of 0.95 g/cc.
(24) Reaction Conditions
(25) According to an embodiment of the present invention, the pre-cracking reactor may be operated in the desired operating temperature ranging from 350 to 470 C., preferably between 420 C. to 470 C.
(26) In another embodiment of the present invention, the desired operating pressure inside pre-cracking reactor ranging from 1 to 15 Kg/cm.sup.2 (g) preferably between 5 to 12 Kg/cm.sup.2 (g).
(27) In another embodiment of the present invention, the residence time inside the pre-cracking reactor range from 1 to 40 minutes, preferably operated in the range of 5 to 30 minutes.
(28) According to an embodiment of the present invention, the multistage intermediate separation system comprising of minimum two separator columns, wherein the first separator may be operated at a pressure ranging from 1 to 6 Kg/cm.sup.2 (g), preferably in the range of 1.5 to 5 Kg/cm.sup.2 (g).
(29) In another embodiment of the present invention, the first separator may be operated at a bottom temperature of 300 to 400 C., preferably in the range of 350 to 390 C.
(30) In another embodiment of the present invention, the second separator column can be operated at a pressure of 10 to 200 mmHg, preferably in the range of 20 to 75 mmHg.
(31) In yet another embodiment of the present invention, the second separator may be operated at a bottom temperature of 200 to 350 C., preferably in the range of 270 to 330 C.
(32) According to an embodiment of the present invention, the second stage coke drums may be operated at a higher severity with desired operating temperature ranging from 470 to 520 C., preferably between 480 C. to 500 C.
(33) In another embodiment of the present invention, the desired operating pressure ranging from 0.5 to 5 Kg/cm.sup.2 (g) preferably between 0.6 to 3 Kg/cm.sup.2 (g).
(34) In yet another embodiment of the present invention, the residence time provided in coke drums is more than 10 hours.
(35) Process Description
(36) In accordance to
(37) According to an embodiment of the present invention, the term second separation column can be used interchangeably with the term second intermediate separator.
(38) Further, removal of lighter material is achieved in the second separator column and the top product (88) is sent to the main fractionator (76). Two heavier product cuts namely, Light Vacuum Gas Oil (LVGO) (97) and Heavy Vacuum Gas Oil (HVGO) (98) are also withdrawn from the second intermediate separator and are sent to the main fractionator. The second portion of heavy bottom material (85) from the first separator and bottom product (89) from the second separator column are mixed and then subjected to heating in furnace (78) to the desired coking temperature to obtain hot hydrocarbon stream. The hot hydrocarbon stream (90) exiting the furnace is then sent to the preheated coke drum (91), where it is provided with a longer residence time for thermal cracking reactions to obtain product vapors. The product vapors exiting the coke drum (92) are routed to the main fractionator (76) column for further separation into desired product fractions comprising of off-gas with LPG and naphtha (93), Kerosene (94), Light Coker Gas Oil (LCGO) (95), and Heavy Coker Gas Oil (HCGO) (96). The entry points of products from the intermediate separator and the coke drum to the main fractionator may be suitably selected based on good engineering practices.
(39) Another embodiment of the invention is provided in accordance to
(40) In an embodiment of the present invention, a single stream is withdrawn from the intermediate separator and sent to the other secondary processing units comprising of fluid catalytic cracking, hydrocracker and/or hydrotreater units.
(41) Another embodiment of the invention is provided in accordance to
(42) In an embodiment of the present invention, the top product (188) from second intermediate separator (187) is routed to other product treatment units or secondary processing units.
(43) Another embodiment of the present invention is provided in accordance with
(44) Another embodiment of the present invention is provided in accordance with
(45) Another embodiment of the present invention is provided in accordance with
(46) Another embodiment of the present invention is provided in accordance with
(47) Another embodiment of the present invention is provided in accordance with
(48) In an embodiment of the present invention, Light Vacuum Gas Oil (LVGO) and Heavy Vacuum Gas Oil (HVGO) are also withdrawn from the second intermediate separator and are sent to other secondary processing units comprising of fluid catalytic cracking, hydrocracker and/or hydrotreater units.
(49) According to an embodiment of the present invention, incorporation of Pre-cracker reactor in the first thermal cracking section is an advantage of the present invention, as this enables control of thermal cracking reaction rate by means of reaction time control. The process of the present invention, avoids the use of hydrogen, catalysts, and/or additives and thus enables the process to be cost effective. The present invention employs multistage separation system, in which the second separator works in vacuum conditions. Operation under vacuum conditions cause increase in relative volatility of the molecules, enabling separation of further heavier molecules. Since these molecules are separated out in the multistage separator system, they are not sent to the second thermal cracking reactor section, thereby the molecules do not participate in further coke formation reactions. This effectively reduces coke to a further extend.
EXAMPLES
(50) Pilot scale experimental study is carried out for validating the merits of the invented process schemes. Experiments are carried out with a resid feedstock of characteristics provided in Table-1.
(51) TABLE-US-00001 TABLE 1 Properties of resid feedstock Value Feed characteristics Density, g/cc 1.042 CCR, wt % 23.39 Asphaltene content, wt % 7.8 Sulfur, wt % 5.73 Liquid analysis (D2887/D6352) wt % C. 0 409 10 506 30 562 50 600 70 639 80 659 90 684 95 698 Metal, ppm Fe 6 Ca 3 Cr 1 Si 1
(52) A base case experiment is carried out in the delayed coker pilot plant using the resid feedstock at delayed coking conditions. The operating conditions for all the experiments are 495 C., feed furnace outlet line temperature, 1.05 Kg/cm2 (g) coke drum pressure, 1 wt % steam addition to the coker feed and a feed rate maintained at about 8 kg/h. The operation is carried out in semi batch mode. The vapors from the coking drums are recovered as liquid and gas products and no coker product is recycled to the coker drum. Major operating parameters and the corresponding discrete product yield pattern are provided in Table-2.
(53) TABLE-US-00002 TABLE 2 Base case pilot plant experimental data with resid feedstock at delayed coker conditions. Unit Value Feed characteristics Feed rate Kg/hr 8 Run duration Hr 12 Coil Outlet Temperature C. 495 Drum pressure kg/cm.sup.2 1.05 Yield (Basis: fresh feed) Fuel gas wt % 6.82 LPG wt % 5.66 C.sub.5-140 C. wt % 9.38 140-370 C. wt % 26.80 370 C.+ wt % 24.40 Coke wt % 26.94
(54) The yields obtained from the base case experiment as provided in Table-2 form the conventional Delayed coker unit (DCU) process yields for the resid feedstock taken.
(55) In order to find the yields from invented process, a first experiment is carried out with the resid feedstock of Table-1 at mild thermal cracking conditions envisaged for the pre-cracker reactor. Total products from the pre-cracker reactor are sent to the single intermediate separator, where heavy bottom material (370 C.+) is separated in the bottom and this material is subjected to coking, in the delayed coker section.
(56) After the first experiment, a second experiment was conducted with the resid feedstock of Table-1 at mild thermal cracking conditions envisaged for the pre-cracker reactor. In this second experiment, 2 nos. of intermediate separators were employed. Total products from the pre-cracker reactor are sent to the single intermediate separator, where heavy bottom material (370 C.+) is separated in the bottom and this material is routed to the second intermediate separator operating in vacuum conditions for further separation. The heavy product material separated in the bottom (540 C.+) and this material is subjected to coking, in the delayed coker section.
(57) The major operating parameters for these experiments are provided in Table-3.
(58) TABLE-US-00003 TABLE 3 Pilot plant experimental conditions maintained for the scheme of current invention is compared with that of the scheme with single intermediate separator. Experi- Experi- Process conditions Unit ment 1 ment 2 Run duration hrs 12 12 Feed rate Kg/hr 8 8 Pre-cracker inlet temp C. 440 440 Pre-cracker outlet temp C. 411 411 Pre-cracker inlet pressure Kg/cm.sup.2(g) 12.3 12.3 Pre-cracker outlet pressure Kg/cm.sup.2(g) 11.9 11.9 First Intermediate separator top Kg/cm.sup.2(g) 4 1 pressure Second Intermediate separator top mmHg 50 pressure Coil Outlet Temperature (for heavy C. 495 495 bottom material from intermediate separator) Drum pressure Kg/cm.sup.2(g) 1.05 1.05
(59) From the experimental data the yields for the invented process scheme is estimated and is compared with the base case delayed coker yields, in Table-4.
(60) TABLE-US-00004 TABLE 4 Comparison of yields obtained in invented process and the base case DCU yields Base case Yield Yield DCU Experi- improve- Experi- improve- yields ment-1 ment ment-2 ment Yields Wt % Wt % Wt % Wt % Wt % Fuel gas 6.82 6.92 +0.10 6.23 0.59 LPG 5.66 5.81 +0.15 5.23 0.43 C.sub.5-140 C. 9.38 9.40 +0.02 8.46 0.92 140-370 C. 26.80 34.60 +7.80 31.14 +4.34 370 C.+ 24.40 21.82 2.58 29.06 +4.66 Coke 26.94 21.45 5.49 19.88 7.06
(61) The experimental data reported in Table-4 shows that while there is an improvement in diesel range products (140-370 C. and 370 C.+) of about 5.22 wt %, use of an additional intermediate separator operating in vacuum conditions improves yields of these products by 9 wt %. Also, the coke yield is further improved in the second experiment with additional intermediate separator to 7.06 wt % compared to the conventional delayed coking process.
(62) The products after being separated in the first intermediate separator used in the present invention comprises of hydrocarbon mixture boiling ranges in the close range. In the second intermediate separator, the pressure is employed below atmospheric/vacuum condition which facilitates increase in relative volatility between the constituent hydrocarbons. Also, the material separated in the second intermediate separator top is in the boiling range of 370-540 C., which may form a part of the Heavy Coker Gasoil stream withdrawn from the common fractionator and is usually routed to Hydrocracker unit, the major product of which is diesel. From the data given in the tables above, it can be seen that in the present invention, the major objectives are to maximize the 370-540 C. yields and reduce coke yields from the residue feedstock, so that the overall diesel production can be maximized.
(63) Those of ordinary skill in the art will appreciate upon reading this specification, including the examples contained herein, that modifications and alterations to the composition and methodology for making the composition may be made within the scope of the invention and it is intended that the scope of the invention disclosed herein be limited only by the broadest interpretation of the appended claims to which the inventor is legally entitled.