An Integrated Process For Converting Crude Oil To High Value Petrochemicals
20230227738 · 2023-07-20
Inventors
- Ponoly Ramachandran Pradeep (Faridabad, IN)
- Shahil SIDDIQUI (Faridabad, IN)
- Vineeth Venu Nath (Faridabad, IN)
- Darshankumar Manubhai DAVE (Faridabad, IN)
- Mainak Sarkar (Faridabad, IN)
- Satyen Kumar Das (Faridabad, IN)
- Madhusudan SAU (Faridabad, IN)
- Sankara Sri Venkata Ramakumar (Faridabad, IN)
Cpc classification
International classification
C10G9/00
CHEMISTRY; METALLURGY
C10J3/64
CHEMISTRY; METALLURGY
Abstract
The present invention relates to a process and system for complete conversion of crude oils by integrating Desalter unit, Atmospheric and vacuum column, high severity FCC process, Naphtha cracking process, residue slurry hydrocracking process, Delayed coking process, Selective mild hydrocracking aromatic production unit, Dehydrogenation units, Aromatic/olefin recovery section, gasifier unit along with syngas to olefins conversion section.
Claims
1. A process for converting a crude oil to high value petrochemicals products, the process comprising: i. charging the crude oil to a Desalter unit to obtain a desalted crude oil; ii. fractionating the desalted crude oil in a primary fractionation section to obtain straight run fractions, wherein the straight run fractions comprise an upper Light cut having a boiling point below 350° C., a Middle cut having a boiling point in a range of 350-560° C. and a Lower heavy cut having a boiling point above 560° C.; iii. routing the Lower heavy cut to a first Resid upgradation unit to obtain Fuel gas (FG) and LPG, Naphtha having a boiling point in a range of C5 to 140° C., Light Gasoil (LGO) having a boiling point in a range of 140-370° C., Heavy Gasoil (HGO) having a boiling point in a range of 370-560° C. and unconverted Pitch having a boiling point above 560° C. by Residue Slurry Hydrocracking; iv. routing the Middle cut from Primary fractionation section r, HGO from the first Resid upgradation unit and Heavy Coker Gas oil (HCGO) from a second Resid upgradation unit to a Hydrotreater Unit to obtain a combined Hydrotreated Gasoil stream; v. routing the combined Hydrotreated Gasoil stream to a High severity Fluid Catalytic Cracking Unit (FCCU), to obtain FG, LPG, Naphtha having a boiling point in a range of C.sub.5 to 210° C., Light Cycle Oil (LCO) having a boiling point in a range of 210 to 340° C., and Clarified oil (CLO) with a boiling point above 340° C.; vi. routing the unconverted Pitch from the first Resid upgradation unit and CLO from the FCCU to the second Resid upgradation unit for Delayed Coking reactions to obtain FG, LPG, Coker Naphtha with a boiling point in a range of C.sub.5 to 140° C., Light Coker Gas oil (LCGO) having a boiling point in a range of 140 to 370° C., Heavy Coker Gas oil (HCGO) having a boiling point in a range of 370 to 540° C. and Coke; vii. withdrawing a part of the Coke as high value Coke product and routing the remaining Coke to a Coke Gasifier unit where it is converted to syngas, and syngas is converted to olefins using Syngas to Methanol (STM) and Methanol to Olefins (MTO) processes; viii. splitting the LCGO stream from the second Resid upgradation unit into two parts on a mass ratio without altering boiling range (140-370° C.) and routing a first part along with the Light Cycle Oil from the high severity FCC unit and Light Cycle Oil having a boiling point in a range of 210 to 340° C. recycled from a Catalytic Naphtha Cracker unit, to a Selective Mild Hydrocracking unit (SMHC) to obtain Fuel Gas, LPG, a Light cut having a boiling point in a range of C.sub.5 to 90° C., a Middle cut having a boiling point in a range of 90 to 180° C. and a Bottom cut having a boiling point above 180° C.; ix. routing the upper Light cut having the boiling point below 350° C. from Primary fractionation section, the Naphtha having the boiling point in the range of C.sub.5 to 140° C. from the first and the second Resid upgradation units, the Light cut having the boiling point in the range of C.sub.5 to 90° C. from the SMHC unit, the LGO from the first Resid upgradation unit, the Naphtha having the boiling point in the range of C.sub.5 to 210° C. from the FCCU and a second part of the LCGO stream from the second Resid upgradation unit to a Catalytic Naphtha cracker unit to obtain FG, LPG and Gasoline having a boiling point in a range of C.sub.5 to 210° C., Light Cycle Oil having a boiling point in a range of 210 to 340° C. and Clarified oil (CLO) having a boiling point above 340° C.; x. routing the FG and LPG from the first Resid upgradation unit, the High severity Fluid Catalytic Cracking Unit (FCCU), the second Resid upgradation unit, the Selective Mild Hydrocracking unit, the Catalytic Naphtha cracker unit, and a Methanol to Olefin conversion unit to Olefin recovery section having a C.sub.2 splitter, a Propylene Recovery Unit (PRU) and a C.sub.4 splitter, to obtain ethane, ethylene, propylene, butylenes and C.sub.3/C.sub.4 paraffins; xi. routing the C.sub.3 praffins stream to a propane dehydrogenation unit to obtain propylene; xii. routing the C.sub.4 paraffins back to Catalytic Naphtha cracker unit for complete conversion; xiii. routing the Middle cut having the boiling point in the range of 90 to 180° C. from the Selective mild hydrocracking unit and the gasoline having the boiling point in the range of C5 to 210° C. from the Catalytic naphtha cracker unit to an Aromatic recovery unit to obtain an extract stream containing Benzene, Toluene, Xylene and a raffinate stream containing paraffins; xiv. routing the raffinate stream containing paraffins to the Catalytic Naphtha cracker unit as a recycle stream.
2. The process as claimed in claim 1, wherein the desalted crude oil is fractionated in an atmospheric distillation unit, a vacuum distillation unit or a combination thereof.
3. The process as claimed in claim 1, wherein the Primary fractionation section comprises an Atmospheric distillation unit operating at a pressure in a range of 1-2 Kg/cm.sup.2(g) and at a top temperature in a range of 150 to 250° C.; and a Vacuum distillation unit operating at a pressure in a range of 0.01 to 0.05 Kg/cm.sup.2(g).
4. The process as claimed in claim 1, wherein the processing of the Light Coker Gas Oil from the first resid upgradation unit, the light cycle from the Catalytic Naphtha cracker unit and the Light Cycle Oil from the Selective Mild Hydrocracking increases yield of aromatics and light olefins.
5. The process as claimed in claim 1, wherein the mass ratio at which the LCGO stream from the second Resid upgradation unit is split, is in a range of 10:90 to 90:10 for routing to the SMHC and the Catalytic Naphtha Cracker Units.
6. The process as claimed in claim 1, wherein the upper light cut with the boiling point below 350° C. from the primary fractionation section is routed to a Thermal Naphtha cracker unit via a Naphtha hydrotreater unit to remove Sulfur and Nitrogen impurities.
7. The process as claimed in claim 1, wherein the upper light cut with the boiling point below 350° C. from the primary fractionation section comprises Straight Run Naphtha, Kerosene, Light Gas Oil, Heavy Gas Oil and the middle cut comprises Vacuum diesel and Vacuum Gas Oil (VGO) and the Lower heavy cut comprises Vacuum Residue (VR).
8. The process as claimed in claim 1, wherein the high value coke has Sulfur in a range of 1-3 wt % and has a sponge structure, and wherein the high value coke is a graphite grade coke.
9. The process as claimed in claim 1, wherein the first Resid Upgradation Unit is a Residue Hydrocracking Unit, wherein a catalyst in the first Resid Upgradation Unit comprises an oil soluble liquid catalyst, and wherein the oil soluble catalyst comprises 1-5 wt % of Ni and 95-99 wt % of Mo.
10. The process as claimed in claim 6, wherein the Naphtha Hydrotreater Unit is operated at a temperature in a range of 300-360° C. and at a pressure in a range of 10-20 bar.
11. The process as claimed in claim 1, wherein the selective mild hydrocracking unit has two reactors for hydrotreating and for selective mild hydrocracking.
12. The process as claimed in claim 1, wherein the Second Resid upgradation unit is a Delayed Coker Unit having coke drums, wherein the coke drums are operated at a temperature in a range of 470 to 520° C. and at an operating pressure ranging from 0.5 to 5 Kg/cm.sup.2 (g) and a residence time in a range of 10 to 32 hours.
13. The process as claimed in claim 1, wherein the High severity FCC unit operates at a temperature of 550 to 650° C., at a pressure in a range of 0.7 to 2.5 Kg/cm.sup.2 (g), and a catalyst to oil ratio is in a range of 10 to 25.
14. The process as claimed in claim 1, wherein the Catalytic Naphtha Cracker Unit operates at a reactor outlet temperature of 580 to 670° C., at a reactor pressure in a range of 0.7 to 2.5 Kg/cm.sup.2 (g), and a catalyst to oil ratio in the range of 15 to 30.
15. The process as claimed in claim 1, wherein the first Resid upgradation unit is a Residue Slurry Hydrocracker Unit and operates at a pressure in a range of 45 to 80 Kg/cm.sup.2 (g), and at a temperature in a range of 360 to 450 C.
16. The process as claimed in claim 1, wherein the coke Gasifier operates with a 1.sup.st stage as a Low temperature fluidized gasifier and a 2.sup.nd stage as a high temperature entrained Gasifier, wherein the Pt stage has a temperature in a range of 750 to 825° C., a residence time is in a range of 50 to 100 seconds, and wherein the 2.sup.nd stage has a temperature in a range of 1400 to 1500° C. and a residence time in a range of 2 to 5 seconds.
17. A system for converting a crude oil to high value petrochemicals products, the system comprising: a. a desalter unit to obtain a desalted crude oil from the crude oil; b. a primary fractionation section comprising an atmospheric distillation unit and a vacuum distillation unit to receive the desalted crude oil from the desalter unit and to separate the desalted crude oil into an upper cut having a boiling point below 350° C., a middle cut having a boiling point in a range of 350-560° C. and a lower heavy cut having a boiling point above 560° C.; c. a Slurry hydrocracker unit as a first resid upgradation unit to receive the lower heavy cut and to hydrocrack the lower heavy cut to generate FG, LPG, Naphtha, LGO, HGO and an unconverted Pitch; d. a Delayed Coker Unit as a second upgradation unit to receive and to upgrade the unconverted Pitch and the FCC Clarified Oil by Delayed Coking to generate FG, LPG, Coker Naphtha, LCGO, HCGO and a solid petroleum coke; e. a Coke Gasifier Unit to receive the solid petroleum coke produced in the second upgradation unit for converting it to Syngas; f. a Syngas to Methanol conversion unit to convert the Syngas from the Coke Gasifier Unit to Methanol; g. a Methanol to olefin unit to convert the methanol to light olefins; h. a Hydrotreater Unit to receive the Middle cut from the primary fractionation section, HGO from the Slurry hydrocracking unit and the Heavy Coker Gas Oil from the Delayed Coker Unit to generate a combined Hydrotreated gasoil stream; i. a High Severity Catalytic Cracker Unit to receive a combined Hydrotreated gasoil stream from Hydrotreater Unit to generate a Clarified Oil stream, gaseous products, wherein the gaseous products comprise FG and LPG, Light Cycle Oil and Naphtha; j. a Selective mild hydrocracking unit (SMHC) comprising hydrotreating and selective mild hydrocracking reactors, to receive the Light Cycle Oils from the High Severity FCC unit and the Catalytic Naphtha Cracker Unit and a part of the Light Coker Gas Oil from the Delayed Coker unit to generate FG and LPG, a Light cut, a Middle cut and a Bottom cut; k. a Catalytic Naphtha Cracker Unit to receive the upper cut from the primary fractionation section, a Paraffinic Raffinate from the Aromatic recovery unit, a Light cut from the SMHC unit, Naphtha and LGO from the Slurry Hydrocracker Unit, Naphtha from the FCC unit, Naphtha and a part of LCGO from the Delayed Coker Unit and a recycle of C4 paraffins, and to subject them to catalytic cracking to generate lighter olefins and aromatics;
1. a C.sub.2 splitter and a Propylene Recovery Unit (PRU) to receive the FG and LPG from the first resid upgradation unit, the second resid upgradation unit, the High Severity FCC Unit, the Catalytic Naphtha cracker Unit, the Methanol to Olefin conversion unit and the selective mild hydrocracking unit to generate ethane, ethylene, propylene, butylenes and C.sub.3, C.sub.4 paraffinic stream; and m. a propane dehydrogenation unit to receive the C.sub.3 paraffin stream and generate propylene; and n. an aromatic recovery unit to receive the Middle cut having a boiling point in a range of 90 to 180° C. from the SMHC unit and the gasoline from the Catalytic naphtha cracker unit to obtain an Extract stream comprising Benzene, Toluene, Xylene and a Raffinate stream comprising paraffins.
18. The system as claimed in claim 17, wherein the system is provided with a Naphtha Hydrotreater unit for receiving fully or a part of the upper cut and naphtha streams for removing Sulfur and Nitrogen and a Steam cracker unit to receive a treated naphtha stream to generate lighter olefins, pyrolyzed gasoline, and ethylene tar (Pyrolytic Fuel oil) by thermal cracking.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0066]
[0067]
[0068]
[0069]
DESCRIPTION OF THE INVENTION
[0070] While the invention is susceptible to various modifications and alternative forms, specific embodiment thereof will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the scope of the invention as defined by the appended claims.
[0071] 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.
[0072] Feedstock
[0073] The liquid hydrocarbon feedstock that can be used in the process is crude oil or crude oil blends and/or crude oil fractions thereof and/or synthetic crude oils and/or oil sand bitumens and/or oils derived from same having Conradson Carbon Residue (CCR) content less than 15 wt % and in particular ranging from 1 to 15 wt %. The feed blend may also comprise of waste plastic pyrolysis oil and/or biomass pyrolysis oil as part of the blend within a limit of up to 50 wt %.
[0074] Process Conditions
[0075] In the process of present invention, atmospheric distillation unit operates at pressure in the range of 1-2 Kg/cm.sup.2(g) and top temperature in the range of 150 to 250° C. preferably in the range of 190 to 210° C. while vacuum distillation unit operates at pressure in the range of 0.01 to 0.05 Kg/cm.sup.2(g). These process conditions are to be fine-tuned to enable separation of lighter boiling (<200° C.) naphtha range compounds from the crude.
[0076] Coke drums in the delayed coking section of the process may be operated at a higher severity with desired operating temperature ranging from 470 to 520° C., preferably between 480° C. to 500° C. and 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). The residence time provided in coke drums is kept in the range of 10 to 32 hours.
[0077] High severity FCC unit is operated at a high reactor outlet temperature of 550 to 650° C., preferably between 580 to 620° C. Reactor pressure shall vary in the range of 0.7 to 2.5 Kg/cm.sup.2 (g), preferably in the range of 0.8 to 1.5 Kg/cm.sup.2 (g). The catalyst to oil ratio is selected from the range of 10 to 25, preferably in the range of 15 to 20.
[0078] The catalytic naphtha cracker unit as mentioned in the present invention is a circulating fluidized bed unit for continuous catalyst regeneration and operates at a reactor outlet temperature of 580 to 670° C., preferably between 590 to 630° C. Reactor pressure shall vary in the range of 0.7 to 2.5 Kg/cm.sup.2 (g), preferably in the range of 0.8 to 1.5 Kg/cm.sup.2 (g). The catalyst to oil ratio is selected from the range of 15 to 30, preferably in the range of 15 to 25.
[0079] Thermal Naphtha cracking unit is operated in presence of steam in the ratio of 0.4 to 1 with feedstock and carried at a higher reactor temperature of 800 to 900° C. at a residence time in the range of 0.1 to 0.5 seconds.
[0080] Naphtha hydrotreater unit for obtaining hydrotreated naphtha, feed for Thermal naphtha cracker is operated at temperature in the range of 300-360° C. at a pressure of 10-20 bar in presence of hydrogen.
[0081] Selective Mild Hydrocracking Aromatic production unit involves hydrotreating and selective mild hydrocracking steps being carried out in two reactors. The reactors operate at a pressure in the range of 45 to 80 Bar, preferably in the range of 50 to 70 bars and temperature in the range of 360 to 450° C., preferably in the range of 390 to 420° C. in presence of hydrogen.
[0082] The residue slurry hydrocracker unit is operated in the temperature range of 250-550° C. and pressure in the range of 40-250 bar in presence of hydrogen.
[0083] Gasifier unit for conversion of coke into syngas is operated at and Syngas to Methanol & Methanol to olefins is operated with 1St stage as a Low temperature fluidized gasifier and 2′ stage as high temp entrained gasifier. The temperature of both stages in the range of 750-825° C. and 1400-1500° C. respectively and residence time in the range of 50-100 and 2-5 sec respectively.
[0084] Catalyst
[0085] In the process scheme of present invention, no catalysts are employed in Atmospheric/vacuum distillation units, delayed coker units and thermal naphtha cracker units. High severity FCC unit employs a circulating fluidized bed reactor configuration and a catalyst mixture containing ‘large pore bottoms selective active material’ of pore size more than 50 Å, Y/REY/USY/RE-USY zeolites of medium pore size of 7 to 11 Å and shape selective pentasil zeolite components. The catalytic naphtha cracker unit also employs a circulating fluidized bed reactor configuration and uses a catalyst composition, with predominantly shape selective pentasil zeolite. Naphtha Hydrotreater uses CoMo/NiMo Catalyst while Residue Hydrocracking unit employs oil soluble liquid catalyst comprises a Ni (1-5 wt %) and Mo (95-99 wt %) organometallic compound in a suitable solvent such as toluene. Selective Mild Hydrocracking Aromatic production unit employs a bifunctional catalyst based on Nickel and Molybdenum.
[0086] Process and System Flow Scheme
[0087] In the process and system of present invention as depicted in
[0088] In another feature of the present invention as depicted in
[0089] In another feature of the present invention as depicted in
[0090] In another preferred feature of the present invention as depicted in
EXAMPLES
[0091] Two crude blends from an Indian refinery and the properties were analyzed and provided in Table-1.
TABLE-US-00001 TABLE 1 Properties of crude blends Properties Crude-1 Crude-2 Density, Kg/m.sup.3 742.4 849.7 CCR, wt % 5.49 0.96 Sulfur, wt % 1.83 0.2 Asphaltenes, wt % <0.01 <0.01 ASTM D2887 distillation, deg C. vs wt % 5 70 73 10 105 94 30 215 208 50 308 275 70 420 352 90 487 465 95 514 524 100 542 636 Paraffins + Naphthenes, wt % 65.1 72.8 Olefins, wt % Nd Nd Aromatics, wt % 34.9 27.2 Ca, ppmw <1 9 Fe, ppmw 2 6 Mg, ppmw <1 <2 Na, ppmw 8 <2 Ni, ppmw 24 <2 V, ppmw 42 <2 Ti, ppmw <1 <2
[0092] In a preferred feature of the present invention, crude oils with properties provided in Table-1 were subjected to multiple steps of processing as per the process scheme described above in
TABLE-US-00002 TABLE 2 Product yield pattern obtained by crude to chemical conversion Product yield, wt % of crude Crude-1 Crude-2 Ethylene 5.7 6.2 Propylene 19.0 20.7 Butenes 7.4 8.1 BTX 18.6 19.2 MS 10.5 10.0 HSD 1.4 1.3 Sulfur 1.1 0.4 Naphtha 0.0 0.0 Total 88.4 78.9 % Chemical conversion 50.7 54.2
[0093] Comparison of process as disclosed in the present invention with the process known in the art, particularly, with US2019/0256786A1.
[0094] In one feature of the present invention, the Resid is processed in resid slurry hydrocracker, to produces gas oils with low sulfur, nitrogen content and is beneficial for FCC catalyst in terms of increased catalyst life and reduced operating cost as compared to process of US2019/0256786A1 where resid is processed in DCU.
TABLE-US-00003 TABLE 3 Comparison of Resid processing with US2019/0256786A1 Present Scheme US2019/0256786A1 resid slurry hydrocracker Properties DCU Gas oils gas oils Sulfur, wt % 4.33 3.31 Nitrogen, wt % 0.24 0.15
[0095] Value extraction from Pitch containing saturates with low sulfur, nitrogen, metals, less production of unwanted product, making the present process more profitable.
TABLE-US-00004 TABLE 4 Comparison of Value extraction from Pitch Present Scheme US2019/0256786A1 Properties DCU feed quality DCU feed quality Sulfur, wt % 3.8 4.74 Ni/V, ppmw 32/97 87/149 Nitrogen wt % 0.4 0.52
[0096] The process scheme of present invention produces higher quality coke meeting anode grade specifications compared to scheme of US2019/0256786A1 where coke is of fuel grade quality.
TABLE-US-00005 TABLE 5 Comparison of Coke Quality US2019/0256786A1 Present Scheme Scheme Anode grade Properties Coke Quality Coke quality coke specs Sulfur, wt % 1.28 7.1 3.5 Ni/V, ppmw 170/100 182/731 <200/<350 HGI <100 150 <100 VCM wt % 5-9 12 12 Structure Sponge Shot Sponge
TABLE-US-00006 TABLE 6 Comparison of Coke Quality US2019/0256786A1 Present Scheme Scheme Coke Anode grade Properties Coke Quality quality coke specs Sulfur, wt % 1.12 7.1 3.5 Ni/V, ppmw 170/100 182/731 <200/<350 HGI <100 150 <100 VCM wt % 0.1 12 12 Structure Sponge Shot Sponge