WO2022270700A1 - 합성가스 및 방향족 탄화수소의 제조방법 - Google Patents
합성가스 및 방향족 탄화수소의 제조방법 Download PDFInfo
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- WO2022270700A1 WO2022270700A1 PCT/KR2021/018818 KR2021018818W WO2022270700A1 WO 2022270700 A1 WO2022270700 A1 WO 2022270700A1 KR 2021018818 W KR2021018818 W KR 2021018818W WO 2022270700 A1 WO2022270700 A1 WO 2022270700A1
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- stream
- discharge stream
- distillation column
- aromatic hydrocarbons
- pgo
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
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- C10J3/62—Processes with separate withdrawal of the distillation products
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
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- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- B01D3/38—Steam distillation
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C15/02—Monocyclic hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/08—Azeotropic or extractive distillation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1247—Higher hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1258—Pre-treatment of the feed
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/1603—Integration of gasification processes with another plant or parts within the plant with gas treatment
- C10J2300/1606—Combustion processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1656—Conversion of synthesis gas to chemicals
- C10J2300/1659—Conversion of synthesis gas to chemicals to liquid hydrocarbons
Definitions
- the present invention relates to a method for producing syngas and aromatic hydrocarbons, and more particularly, to replace pyrolysis fuel oil discharged from a gasoline rectifier of a naphtha cracking center (NCC) as a raw material for a gasification process, It relates to a method for recovering aromatic hydrocarbons in pyrolysis fuel oil.
- NCC naphtha cracking center
- the Naphtha Cracking Center (hereinafter referred to as 'NCC') thermally cracks naphtha, which is a gasoline fraction, at a temperature of about 950 ° C to 1,050 ° C to produce ethylene, propylene, butylene and It is a process to produce BTX (Benzene, Toluene, Xylene), etc.
- benzene, toluene, xylene, styrene, etc. are produced using pyrolysis gasoline (Raw Pyrolysis Gasoline, RPG), a by-product of the process of producing ethylene and propylene, using naphtha as a raw material, and pyrolysis fuel oil , PFO) was used as fuel.
- RPG Raw Pyrolysis Gasoline
- PFO pyrolysis fuel oil
- CO 2 carbon dioxide
- synthesis gas is an artificially produced gas, unlike natural gas such as natural gas, methane gas, and ethane gas emitted from the ground in oil fields and coal mines, through a gasification process. are manufactured
- the gasification process is a process in which hydrocarbons such as coal, petroleum, and biomass are converted into syngas mainly composed of hydrogen and carbon monoxide by thermal decomposition or chemical reaction with gasifiers such as oxygen, air, and water vapor.
- a gasifier and raw materials are supplied to the combustion chamber located at the forefront of the gasification process to generate syngas through a combustion process at a temperature of 700 ° C. or higher. Since atomizing is not performed smoothly, combustion performance is reduced or the risk of explosion due to excess oxygen is increased.
- raw materials for the gasification process for producing syngas using liquid hydrocarbon raw materials include vacuum residue (VR) and bunker-C oil discharged from refineries that refine crude oil.
- Refinery residues such as bunker-c oil were mainly used.
- these refinery residues are high in kinematic viscosity and require pretreatment such as heat treatment for viscosity mitigation and addition of diluents or water to be used as a raw material for the gasification process. Since the amount of acid gas such as hydrogen sulfide and ammonia is increased, the need to replace the refining residue with a raw material having low sulfur and nitrogen content is emerging in order to cope with the strengthened environmental regulations.
- the present inventors can replace the pyrolysis fuel oil (PFO) of the naphtha cracking process (NCC) as a raw material for the gasification process, greenhouse gas emissions can be reduced compared to the case of using conventional oil residue as a raw material,
- PFO pyrolysis fuel oil
- NCC naphtha cracking process
- the problem to be solved by the present invention is to replace the pyrolysis fuel oil (PFO) discharged from the naphtha cracking process (NCC) as a raw material for the gasification process in order to solve the problems mentioned in the background technology of the above invention, Provides a method for producing syngas that can reduce greenhouse gas emissions, reduce the operating cost of a gasification process, and improve process efficiency compared to the case of using refined oil residue as a raw material, and included in the pyrolysis fuel oil It is intended to recover aromatic hydrocarbons.
- PFO pyrolysis fuel oil
- NCC naphtha cracking process
- PFO pyrolysis fuel oil
- PGO pyrolysis gas oil
- pyrolysis fuel oil (PFO) and pyrolysis gas oil (PGO) of the naphtha cracking process (NCC) are pretreated and replaced with raw materials for the gasification process, thereby reducing greenhouse gas emissions compared to the case of using conventional oil residues as raw materials. Emissions can be reduced, operating costs of the gasification process can be reduced, and process efficiency can be improved.
- 1 is a process flow chart for a method for producing syngas and aromatic hydrocarbons according to an embodiment of the present invention.
- Figure 2 is a process flow chart for a method for producing syngas and aromatic hydrocarbons according to Comparison 1 of the present invention.
- Figure 3 is a process flow chart for a method for producing syngas and aromatic hydrocarbons according to Comparison 2 of the present invention.
- the term "stream" may refer to a flow of a fluid in a process, and may also refer to a fluid itself flowing in a pipe.
- the stream may mean a fluid itself and a flow of the fluid flowing in a pipe connecting each device at the same time.
- the fluid may mean a gas or a liquid, and a case in which a solid component is included in the fluid is not excluded.
- C# in which "#" is a positive integer denotes all hydrocarbons having # carbon atoms. Accordingly, the term “C8” denotes a hydrocarbon compound having 8 carbon atoms. Also, the term “C#-” denotes all hydrocarbon molecules having # or less carbon atoms. Accordingly, the term “C8-” denotes a mixture of hydrocarbons having up to 8 carbon atoms. Also, the term “C#+” refers to any hydrocarbon molecule having # or more carbon atoms. Accordingly, the term 'C10+' denotes a mixture of hydrocarbons having 10 or more carbon atoms.
- the method for producing the syngas and aromatic hydrocarbons includes a PFO stream containing Pyrolysis Fuel Oil (PFO) and PGO containing Pyrolysis Gas Oil (PGO) discharged from the naphtha cracking process (S1). supplying the stream to the distillation column 50 as a feed stream (S10); and supplying the lower discharge stream of the distillation column 50 to a combustion chamber for the gasification process (S3) and supplying the upper discharge stream to the SM/BTX manufacturing process (S4) (S20).
- PFO Pyrolysis Fuel Oil
- PGO Pyrolysis Gas Oil
- the syngas is an artificially produced gas and is produced through a gasification process.
- the gasification process is a process of converting hydrocarbons, such as coal, petroleum, and biomass, into syngas mainly containing hydrogen and carbon monoxide by thermal decomposition or chemical reaction with gasifiers such as oxygen, air, and water vapor.
- syngas may include hydrogen and carbon monoxide.
- a gasifier and raw materials are supplied to the combustion chamber located at the forefront of the gasification process to generate syngas through a combustion process at a temperature of 700 ° C. or higher. Since atomizing is not performed smoothly, combustion performance is reduced and the risk of explosion due to excess oxygen is increased.
- raw materials for the gasification process for producing syngas using liquid hydrocarbon raw materials include vacuum residue (VR) and bunker-C oil discharged from refineries that refine crude oil.
- Refinery residues such as bunker-c oil were mainly used.
- these refinery residues are high in kinematic viscosity and require pretreatment such as heat treatment for viscosity mitigation and addition of diluents or water to be used as a raw material for the gasification process.
- the amount of acid gas such as hydrogen sulfide and ammonia is increased, the need to replace the refining residue with a raw material having low sulfur and nitrogen content is emerging in order to cope with the strengthened environmental regulations.
- the vacuum residue may contain about 3.5% by weight of sulfur and about 3600 ppm of nitrogen
- the bunker-C oil may contain about 4.5% by weight of sulfur.
- pyrolysis fuel oil (PFO) discharged from the naphtha cracking process which is a process of manufacturing basic petrochemical materials such as ethylene and propylene by cracking naphtha, is generally used as a fuel, but its sulfur content is low in fuel without pretreatment. It is a high level to be used as a furnace, so the market is getting narrower due to environmental regulations, and it is necessary to prepare for a situation where sales are impossible in the future.
- a pretreatment process (S2) for replacing the PFO stream containing pyrolysis fuel oil (PFO) and the PGO stream containing pyrolysis gas oil (PGO) discharged from the naphtha cracking process as a raw material for the gasification process is provided.
- S2 a pretreatment process for replacing the PFO stream containing pyrolysis fuel oil (PFO) and the PGO stream containing pyrolysis gas oil (PGO) discharged from the naphtha cracking process as a raw material for the gasification process.
- the RPG stream including raw pyrolysis gasoline (RPG), the PFO stream including pyrolysis fuel oil (PFO), and the PGO stream including the pyrolysis gas oil (PGO) may be discharged from the naphtha cracking process (S1).
- the naphtha cracking process decomposes naphtha containing paraffin, naphthene and aromatics to produce ethylene, propylene, butylene and BTX ( As a process for producing Benzene, Toluene, Xylene), etc., the naphtha cracking process can be largely composed of a cracking process, a quenching process, a compression process, and a refining process.
- the cracking process is a process of thermally cracking naphtha into hydrocarbons having a low carbon number in a cracking furnace at 800 ° C. or higher, and high-temperature cracked gas can be discharged.
- the naphtha may be supplied to the cracking furnace after undergoing a preheating process from high-pressure steam before entering the cracking furnace.
- the quenching process is a step of suppressing the polymerization reaction of hydrocarbons in the high-temperature cracked gas discharged from the cracking furnace, and cooling the high-temperature cracked gas for the purpose of recovering waste heat and reducing heat load in a subsequent process (compression process).
- the quenching process may include firstly cooling the high-temperature cracked gas with quench oil and secondarily cooling with quench water.
- the cracked gas is supplied to a gasoline fractionator to produce light oil, pyrolysis gasoline (RPG), pyrolysis fuel oil (including hydrogen, methane, ethylene, propylene, etc.) PFO) and pyrolysis gas oil (PGO) can be separated. Thereafter, the light fraction may be transferred to a subsequent compression process.
- a gasoline fractionator to produce light oil
- pyrolysis fuel oil including hydrogen, methane, ethylene, propylene, etc.
- PGO pyrolysis gas oil
- the compression process may be a process of generating a compressed gas having a reduced volume by increasing the pressure of the light fraction under high pressure in order to economically separate and purify the light fraction.
- the purification process is a process of cooling the compressed gas compressed at high pressure to an ultra-low temperature and then separating components step by step by boiling point difference, hydrogen, ethylene, propylene, propane, C4 oil, pyrolysis gasoline (RPG), etc. are produced It can be.
- pyrolysis gasoline RPG
- pyrolysis fuel oil PFO
- pyrolysis gas oil PGO
- the pyrolysis fuel oil (PFO) contains about 0.1% by weight or less of sulfur and about 20 ppm or less of nitrogen, so that when used as a fuel, sulfur oxides (SOx) and nitrogen oxides (NOx) are reduced in the combustion process. Since this is emitted, environmental issues may be caused, but when it is used as a raw material for syngas, it is at a fairly low level.
- the above problems can be solved by pretreating pyrolysis fuel oil (PFO) and pyrolysis gas oil (PGO) through a pretreatment process (S2) and using them as raw materials for a gasification process for producing syngas, and further Greenhouse gas emissions can be reduced compared to the case of using conventional oil residue as a raw material for the gasification process, the operating cost of the gasification process can be reduced, and the process efficiency can be improved.
- PFO pyrolysis fuel oil
- PGO pyrolysis gas oil
- S2 pretreatment process
- the PFO stream and the PGO stream of the present invention include pyrolysis fuel oil (PFO) and pyrolysis gas oil (PGO) discharged from the gasoline rectifier 10 of the naphtha cracking process (S1), respectively.
- PFO pyrolysis fuel oil
- PGO pyrolysis gas oil
- the pyrolysis fuel oil (PFO) is compared to the total number of stages of the gasoline rectifying column 10 ) may be released from at least 90% of the stage, at least 95% of the stage, or from 95% to 100% of the stage.
- the pyrolysis gas oil (PGO) may be discharged from a stage of 10% to 70%, a stage of 15% to 65%, or a stage of 20% to 60%.
- the uppermost stage may be 1 stage and the lowest stage may be 100 stages, and 90% or more of the total number of stages of the gasoline rectifying column 10 are gasoline rectifying columns ( 10) may mean stages 90 to 100.
- the PGO stream is discharged from the side of the gasoline rectification column 10 of the naphtha cracking process (S1), and after supplying the side discharge stream containing pyrolysis gas oil (PGO) to the first stripper 20, the first 1 may be a bottom discharge stream discharged from the bottom of the stripper 20.
- the PFO stream is discharged from the bottom of the gasoline rectifier 10 of the naphtha cracking process (S1), and after supplying the bottom discharge stream containing pyrolysis fuel oil (PFO) to the second stripper 30, It may be a lower discharge stream discharged from the lower portion of the second stripper 30.
- the first stripper 20 and the second stripper 30 may be a device in which a stripping process for separating and removing gas or vapor dissolved in a liquid is performed, for example, steam or inert gas It may be performed by methods such as direct contact, heating, and pressurization.
- a stripping process for separating and removing gas or vapor dissolved in a liquid for example, steam or inert gas It may be performed by methods such as direct contact, heating, and pressurization.
- the side discharge stream of the gasoline rectification column 10 is supplied to the first stripper 20, and the light content separated from the side discharge stream of the gasoline rectification column 10 from the first stripper 20 is included.
- the upper discharge stream to be refluxed may be refluxed to the gasoline rectifying column (10).
- the bottom discharge stream of the gasoline rectification column 10 is supplied to the second stripper 30, and the second stripper 30 contains a light component separated from the bottom discharge stream of the gasoline rectification column 10
- the top discharge stream may be refluxed to the gasoline rectifying column (10).
- the PGO stream contains 70 wt% or more or 70 wt% to 95 wt% of C10 to C12 hydrocarbons
- the PFO stream contains 70 wt% or more or 70 wt% of C13+ hydrocarbons. to 98% by weight.
- the PGO stream containing 70% by weight or more of C10 to C12 hydrocarbons may have a kinematic viscosity at 40 °C of 1 to 200 cSt and a flash point of 10 to 50 °C.
- the kinetic viscosity at 40 ° C may have a kinematic viscosity at 40 °C of 1 to 200 cSt and a flash point of 10 to 50 °C.
- the PFO stream containing 70% by weight or more of C13+ hydrocarbons may be 400 to 100,000 cSt, and the flash point may be 70 to 200 ° C.
- the PFO stream containing more heavy hydrocarbons than the PGO stream may have higher kinematic viscosity and flash point than pyrolysis gas oil under the same temperature conditions.
- the boiling point of the PGO stream may be 200 to 288 °C, or 210 to 270 °C, and the boiling point of the PFO stream may be 289 °C to 550 °C, or 300 to 500 °C.
- the boiling points of the PGO stream and the PFO stream may refer to the boiling points of the bulk PGO stream and the PFO stream, respectively, composed of a plurality of hydrocarbons.
- the types of hydrocarbons included in the PGO stream and the types of hydrocarbons included in the PFO stream may be different from each other, and some types may be the same.
- the types of hydrocarbons included in the PGO stream and the PFO stream may be included as described above.
- the RPG stream containing pyrolysis gasoline (RPG) discharged from the gasoline rectifier 10 of the naphtha cracking process (S1) is supplied to the SM / BTX manufacturing process (S4) to produce styrene and BTX can be produced.
- the BTX is an abbreviation of benzene, toluene, and xylene
- the xylene is ethylbenzene, m-xylene, and o-xylene.
- (o-Xylene) and p-xylene (p-Xylene) may be included.
- the RPG stream may be a stream containing pyrolysis gasoline (RPG) discharged from stages of 5% or less or 1% to 5% of the total number of stages of the gasoline rectifying column 10.
- the RPG stream containing pyrolysis gasoline (RPG) discharged from the gasoline rectifier 10 is discharged from the top of the gasoline rectifier 10 of the naphtha cracking process (S1), and the pyrolysis gasoline (RPG) It may be a separated stream after supplying the upper discharge stream containing hydrogen and C4- hydrocarbon materials to a downstream process (not shown) of the NCC.
- the RPG stream is discharged from a lower portion of a gasoline stripper (not shown) of the NCC post process (not shown), and an RPG stream containing styrene and a C4 separation column (not shown) of the NCC post process (not shown) (not shown) discharged from the bottom, and may include an RPG stream that does not contain styrene.
- the RPG stream containing styrene may be a C5+ hydrocarbon mixture, specifically a mixture rich in C5 hydrocarbons to C10 hydrocarbons.
- the RPG stream containing styrene includes isopentane (Iso-Pentane), n-Pentane, 1,4-pentadiene (1,4-Pentadiene), dimethylacetylene, 1 -Pentene (1-Pentene), 3-methyl-1-butene (3-Methyl-1-butene), 2-methyl-1-butene (2-Methyl-1-butene), 2-methyl-2-butene ( 2-Methyl-2-butene), isoprene (Iso-Prene), trans-2-Penstene, cis-2-Penstene, trans-1,3-pentadiene (trans-1,3-Pentadiene), Cyclopentadiene, Cyclopentane, Cyclopentene, n-H
- the content of C6 to C8 hydrocarbons in the RPG stream may be 40 wt% or more, 45 wt% to 75 wt%, or 50 wt% to 70 wt%.
- the RPG stream containing styrene may be supplied to the SM process unit of the SM/BTX manufacturing process (S4). Specifically, the RPG stream containing styrene may be supplied to the SM processing unit to separate styrene, and the residual stream from the separation of styrene in the SM processing unit may be supplied to the BTX processing unit to separate benzene, toluene, and xylene.
- the styrene-free stream is, for example, cyclopentadiene, pentadiene, isoprene, cyclopentene, 1-pentene, 3-methyl-1-butene, cyclopentane, 2-methyl-butene, normalpentane, It may include at least one selected from the group consisting of benzene, toluene and C6 non-aromatic hydrocarbons.
- the RPG stream not containing styrene may be supplied to the BTX process unit of the SM/BTX manufacturing process (S4).
- RPG streams that do not contain styrene are supplied to the BTX process unit of the SM / BTX manufacturing process (S4) without passing through the SM process unit, and thus generated when supplied to the SM process unit of the SM / BTX manufacturing process (S4) It is possible to save energy by not going through unnecessary process steps such as separation and mixing.
- a PFO stream containing pyrolysis fuel oil (PFO) and a PGO stream containing pyrolysis gas oil (PGO) discharged from the naphtha cracking process (S1) may be supplied to the distillation column 50 as a feed stream.
- the feed stream supplied to the distillation tower 50 includes both a PGO stream and a PFO stream, and may include both heavy oils (heavies) and light oils (lights).
- the feed stream containing both the heavy oil and the light oil is supplied to the distillation tower 50, and through the discharge of the upper discharge stream containing the light PFO stream from the top of the distillation tower 50, the distillation tower 50 ) from the bottom of the bottom discharge stream with controlled kinematic viscosity and flash point can be discharged.
- the PFO stream having a higher content of heavy oil than the PGO stream has a higher kinematic viscosity and flash point than the PGO stream
- the PGO stream having a higher content of light oil than the PFO stream has a lower kinematic viscosity and flash point than the PFO stream.
- a stream having a desired kinematic viscosity and flash point can be discharged from the bottom of the distillation column 50 through the removal of the light oil in the feed stream including both of the two streams in conflict with each other as described above.
- the feed stream may be a mixed oil stream in which the PFO stream and the PGO stream are mixed.
- the ratio of the flow rate of the PGO stream in the mixed oil stream to the flow rate of the mixed oil stream (hereinafter referred to as 'the flow rate ratio of the PGO stream') is 0.35 to 0.7, 0.4 to 0.65, or 0.4 to 0.6, but is not limited thereto.
- 'flow rate' may mean the flow of weight per unit time.
- the unit of the flow rate may be kg/h.
- the boiling point of the mixed oil stream may be 200 °C to 600 °C, 210 °C to 550 °C, or 240 °C to 500 °C.
- the boiling point of the mixed oil stream may mean the boiling point of a mixed oil stream in a bulk form composed of a plurality of hydrocarbons.
- the mixed oil stream may be supplied to the distillation column 50 after passing through the first heat exchanger 40 before being supplied to the distillation column 50 .
- the mixed oil stream is produced by mixing the high-temperature PGO stream and the PFO stream discharged from the first stripper 20 or the second stripper 30, and the supply temperature of the mixed oil stream to the distillation tower 50 In addition to optimal control, process energy can be saved by reusing sensible heat within the process when necessary.
- the mixed oil stream may be supplied at a stage of 10% to 70%, 15% to 60%, or 20% to 50% of the total number of stages of the distillation column 50. can Within this range, the distillation column 50 can be efficiently operated, and unnecessary energy consumption can be significantly reduced.
- the ratio of the flow rate of the upper discharge stream of the distillation tower 50 to the flow rate of the feed stream supplied to the distillation tower 50 (hereinafter referred to as 'distillation ratio of the distillation tower 50' ) may be 0.01 to 0.2, 0.01 to 0.15, or 0.03 to 0.15. That is, the distillation ratio of the distillation column 50 may be adjusted to 0.01 to 0.2, 0.01 to 0.15, 0.03 to 0.15, or 0.1 to 0.2.
- the distillation ratio of the distillation column 50 within the above range is controlled through a flow control device (not shown) installed in a pipe through which the upper discharge stream of the distillation tower 50 is transported, and the performance of the distillation column 50 is determined by the distillation ratio and the It can be performed by adjusting the reflux ratio of the upper discharge stream of the distillation column 50 using the two heat exchangers 51.
- the reflux ratio may refer to the ratio of the flow rate of the reflux stream to the flow rate of the effluent stream.
- the reflux ratio of the upper discharge stream of the distillation column 50 refers to the upper discharge stream of the distillation column 50 When a part of is branched and refluxed to the distillation column 50 as a reflux stream, and the remainder is supplied as an effluent stream to the SM / BTX manufacturing process (S4), the ratio of the flow rate of the reflux stream to the flow rate of the effluent stream (hereinafter , referred to as 'reflux ratio').
- the reflux ratio may be 0.01 to 10, 0.1 to 7, or 0.15 to 5.
- a gasifier and a raw material are supplied to a combustion chamber (not shown) located at the forefront of the gasification process (S3), and synthesis gas can be generated through a combustion process at a temperature of 700 ° C. or higher.
- the synthesis gas generation reaction is performed at a high pressure of 20 to 80 atm, and the raw material must move at a high flow rate of 2 to 40 m/s in the combustion chamber. Therefore, the raw material needs to be pumped at a high flow rate at a high pressure for the synthesis gas generation reaction.
- an expensive pump must be used due to a decrease in pumpability.
- the raw material cannot be uniformly supplied to the combustion chamber because pumping is not performed smoothly.
- the differential pressure in the combustion chamber rises or the uniform atomization of raw materials with small particle sizes is not smoothly performed, which can deteriorate combustion performance and productivity, require a large amount of gasifier, and cause excess oxygen. will increase the risk of explosion.
- the appropriate range of the kinematic viscosity may vary slightly depending on the type of syngas to be synthesized and the conditions of the combustion process performed in the combustion chamber, but in general, the kinematic viscosity of the raw material is the combustion chamber in the gasification process (S3).
- the appropriate range of the flash point may vary depending on the type of syngas to be synthesized in the combustion chamber, the conditions of the combustion process performed in the combustion chamber, etc., but in general, the flash point of the raw material is transferred to the combustion chamber in the gasification process (S3). It may be desirable to have a range of 25 ° C. or more higher than the temperature of the raw material at the time when the raw material is supplied, and within this range, loss of the raw material, risk of explosion, and damage to the refractory of the combustion chamber can be prevented.
- the distillation ratio of the distillation column 50 is adjusted in order to control the kinetic viscosity and flash point of the lower discharge stream of the distillation column 50, which is a raw material supplied to the combustion chamber in the gasification process (S3), to an appropriate range.
- the distillation ratio of the distillation column 50 can be controlled.
- the upper discharge stream of the distillation column 50 is supplied to the SM / BTX manufacturing process (S4) , can increase the production of styrene and BTX.
- the third heat exchanger 52 can be operated as a general reboiler.
- the temperature at the time of supply of the bottom discharge stream of the distillation column 50 to the combustion chamber is 25 ° C. or higher than the flash point at the time of supply of the bottom discharge stream of the distillation column 50 to the combustion chamber. It may be a temperature with a low, kinematic viscosity of 300 cSt or less. That is, the bottom discharge stream of the distillation column 50 may have a kinematic viscosity of 300 cSt or less or 1 cSt to 300 cSt at the time of supply to the combustion chamber, and the flash point of the bottom discharge stream of the distillation column 50 may be in the combustion chamber. It may be at least 25° C. or between 25° C. and 150° C.
- the temperature at the time of supplying the lower discharge stream of the distillation column 50 to the combustion chamber may be 20 °C to 90 °C or 30 °C to 80 °C.
- the kinematic viscosity may be 300 cSt or less, and may be 25 ° C. or more lower than the flash point, process operating conditions for use as a raw material for the gasification process (S3) can satisfy
- the distillation tower 50 by adjusting the distillation ratio of the distillation tower 50 to 0.01 to 0.2, 0.01 to 0.15, or 0.03 to 0.15, the distillation tower 50
- the flash point of the bottom discharge stream of is 25 ° C. or more higher than the temperature of the bottom discharge stream of the distillation column 50 at the time of feeding, and the kinematic viscosity is in the range of 300 cSt or less at the temperature of the bottom discharge stream of the distillation column 50 at the time of feeding.
- the lower discharge stream of the distillation column 50 increases the flash point increase rate rather than the increase rate of the kinematic viscosity by removing light substances having low flash points in a situation where both flash point and kinematic viscosity are low.
- the flash point and kinematic viscosity at the time of supply to the combustion chamber can be controlled within the aforementioned flash point and kinematic viscosity ranges.
- the distillation ratio of the distillation column 50 is less than 0.01, the flash point at the point of supply of the bottom discharge stream of the distillation column 50 to the combustion chamber is higher than the temperature at the point of supply of the bottom discharge stream of the distillation column 50 to the combustion chamber.
- the gasification step (S3) It can be made to have physical properties suitable for use as a raw material.
- the PFO stream is directly supplied to the combustion chamber without a pretreatment process (S2), or as shown in FIG. 3, the PGO stream is directly supplied to the combustion chamber without a pretreatment process (S2).
- S2 the mixed oil stream of the PGO stream and the PFO stream is directly supplied to the combustion chamber without the pretreatment process (S2) according to the present invention, both the kinematic viscosity and flash point within the appropriate ranges are satisfied. There may be a problem that the temperature does not exist.
- the differential pressure in the combustion chamber increases or the atomization is not smoothly performed.
- Combustion performance may be reduced, the risk of explosion due to excess oxygen may be increased, or a burner may generate a flame before a combustion reaction occurs, and there is a risk of explosion due to a backfire phenomenon of the flame in the combustion chamber, and the refractory material in the combustion chamber may deteriorate. Damage may occur.
- the PFO stream and the PGO stream are the heaviest residues in the NCC process and have been used as simple fuels.
- simple fuels there is no need to adjust the composition and physical properties.
- specific physical properties for example, kinematic viscosity and flash point must be satisfied at the same time.
- the flash point is too low, and the PFO stream has a high flash point but the kinematic viscosity is too high, so that each stream cannot simultaneously satisfy the kinematic viscosity and the flash point.
- the ratio of the flow rate of the PGO stream to the flow rate of the entire PFO stream and the PGO stream is generally about 0.35 to 0.7, even in this case, the gasification process below the flash point. It was difficult to use as a raw material for synthesis gas because it could not satisfy the kinematic viscosity condition for use as a raw material for synthetic gas.
- the flash point of the lower discharge stream of the distillation column 50 is supplied to the combustion chamber by supplying the entire amount of the PFO stream and the PGO stream to the distillation column 50 for pretreatment.
- the temperature of the lower discharge stream of the distillation column 50 at the time of supply is controlled to a range of 25 ° C. or more, and the kinematic viscosity is controlled to a range of 300 cSt or less at the temperature of the bottom discharge stream of the distillation column 50 at the time of supply.
- the discharge stream from the bottom of the distillation tower 50 may be supplied to the gasification process S3 after passing through the fourth heat exchanger 53 before being supplied to the gasification process S3.
- the supply temperature of the lower discharge stream of the distillation column 50 to the gasification process (S3) is adjusted, and the sensible heat of the lower discharge stream of the distillation column 50 to be discarded as waste heat is reused in the process using a heat exchanger. Process energy can be saved.
- the top discharge stream of the distillation column 50 may be supplied to the SM/BTX manufacturing process (S4) to produce aromatic hydrocarbons including styrene.
- the bottom discharge stream of the distillation column 50 has a content of C10+ hydrocarbons of 80% by weight or more, or 80% to 98% by weight, and a content of C8- hydrocarbons of 5% by weight or less or 0.01% by weight. % to 5% by weight, and the top discharge stream of the distillation column 50 has a content of C6 to C8 aromatic hydrocarbons of 50% by weight or more, 55% by weight to 95% by weight, or 55% to 85% by weight,
- the content of styrene may be 20% to 50%, 20% to 45% or 25% to 45% by weight.
- the C8- hydrocarbon is selected from the group consisting of pentane, pentene, pentadiene, methylbutene, cyclopentane, cyclopentene, hexane, cyclohexane, heptane, methylhexane, octane, benzene, toluene, xylene and styrene.
- the C8- hydrocarbon may include all of the aforementioned C8- hydrocarbons, but is not limited thereto.
- the C10+ hydrocarbon may include at least one selected from the group consisting of dicyclopentadiene, naphthalene, methylnaphthalene, tetramethylbenzene, fluorene, and anthracene.
- the C10+ hydrocarbon may include all of the aforementioned C10+ hydrocarbons, but is not limited thereto.
- the C6 to C8 aromatic hydrocarbons may include at least one selected from the group consisting of benzene, toluene, xylene, and styrene, and the C8 aromatic hydrocarbon may include styrene.
- the C6 to C8 aromatic hydrocarbons may include all of the aforementioned C6 to C8 aromatic hydrocarbons, but are not limited thereto.
- the distillation column in which the bottom discharge stream of the distillation column 50 is used as a raw material for syngas the content of C6 to C8 aromatic hydrocarbons is 50% by weight or more, and the content of styrene is 20% to 50% by weight ( 50) is supplied to the SM/BTX manufacturing process (S4), thereby replacing pyrolysis fuel oil as a raw material for the gasification process, and at the same time recovering aromatic hydrocarbons in pyrolysis fuel oil to increase the production of aromatic hydrocarbons including styrene.
- S4 SM/BTX manufacturing process
- the step of burning the lower discharge stream of the distillation column 50 supplied to the combustion chamber in the gasification process (S3) at a temperature of 700 ° C. or higher, 700 ° C. to 2000 ° C., or 800 ° C. to 1800 ° C. can include more.
- the bottom discharge stream of the distillation column 50 may be supplied to the combustion chamber together with the gasification agent.
- the gasification agent may include at least one selected from the group consisting of oxygen, air, and water vapor, and as a specific example, the gasification agent may be oxygen and water vapor.
- syngas can be produced by burning the lower discharge stream of the distillation column 50 at a high temperature in the presence of a gasifying agent.
- the syngas produced according to the production method of the present invention includes carbon monoxide and hydrogen, and may further include at least one selected from the group consisting of carbon dioxide, ammonia, hydrogen sulfide, hydrogen cyanide, and carbonyl sulfide.
- the SM / BTX manufacturing process is a process of receiving the RPG stream and the upper discharge stream of the distillation column 50 to produce BTX together with styrene, SM process unit and BTX process wealth may be included.
- the SM process unit may be located in front of the BTX process unit.
- the RPG stream containing styrene among the RPG streams and the upper discharge stream of the distillation tower 50 are supplied to the SM process unit of the SM/BTX manufacturing process S4 to produce styrene.
- the RPG stream containing styrene and the upper discharge stream of the distillation tower 50 may be supplied to the SM process unit of the SM/BTX manufacturing process S4 as separate streams or mixed streams.
- the RPG stream containing styrene and the upper discharge stream of the distillation column 50 may be supplied to the C7 separation column of the SM processing unit.
- the C7 separation column of the SM process unit it can be separated into an upper discharge stream containing C7- hydrocarbons and a lower discharge stream containing C8+ hydrocarbons.
- the bottoms discharge stream containing the C8+ hydrocarbons may be supplied to the C8 separation column of the SM processing unit.
- the C8 separation column of the SM process unit it can be separated into an upper discharge stream containing C8 hydrocarbons and a lower discharge stream containing C9+ hydrocarbons.
- the C8 separation column overhead stream of the SM processing unit may be supplied to the extractive distillation column of the SM processing unit, and the extractive distillation column of the SM processing unit uses an extraction solvent to obtain styrene contained in the C8 separation column overhead stream of the SM processing unit. and other hydrocarbons including xylenes.
- styrene in the upper discharge stream of the C8 separation column may be selectively extracted and separated as a lower discharge stream, and other hydrocarbons may be separated as an upper discharge stream.
- the bottom discharge stream of the extractive distillation column of the SM processing unit may be supplied to a solvent recovery column to remove the extraction solvent and then separate styrene.
- the remaining stream discharged from the SM processing unit may be supplied to the BTX processing unit.
- the top discharge stream of the C7 separation column of the SM processing unit, the bottom discharge stream of the C8 separation column, and the top discharge stream of the extractive distillation column may be mixed and supplied as a residual stream to the hydrodesulfurization unit of the BTX processing unit.
- benzene, toluene and xylene may be produced using the residual stream of the SM processing unit supplied to the BTX processing unit.
- the RPG stream not containing styrene and the residual stream of the SM processing unit may be supplied to the BTX processing unit to produce benzene or BTX.
- the RPG stream not containing styrene and the residual stream of the SM processing unit are supplied to the hydrodesulfurization unit of the BTX processing unit and hydrodesulfurized in the presence of separately supplied hydrogen and a catalyst.
- the catalyst may be a catalyst capable of selective hydrogenation.
- the catalyst may include at least one selected from the group consisting of palladium, platinum, copper, and nickel.
- the catalyst may be used by being supported on at least one carrier selected from the group consisting of gamma alumina, activated carbon, and zeolite.
- the discharge stream of the hydrodesulfurization unit of the BTX processing unit may be supplied to the C5 separation column of the BTX processing unit.
- An overhead discharge stream containing C5- aromatic hydrocarbons may be discharged from the C5 separation column, and a bottom discharge stream containing C6+ aromatic hydrocarbons may be supplied to a C7 separation column.
- the top discharge stream containing C7- aromatic hydrocarbons is supplied to the extractive distillation column of the BTX process unit, and the bottom discharge stream containing C8 + aromatic hydrocarbons is supplied to the xylene separation column of the BTX process unit.
- aromatic hydrocarbons and non-aromatic hydrocarbons included in the upper discharge stream of the C7 separation column may be separated using an extraction solvent.
- aromatic hydrocarbons in the upper discharge stream of the C7 separation column of the BTX processing unit may be selectively extracted and separated as a lower discharge stream, and non-aromatic hydrocarbons may be separated as an upper discharge stream.
- the extraction solvent is at least one selected from the group consisting of sulfolane, alkyl-sulfolane, N-formyl morpholine, N-methyl pyrrolidone, tetraethylene glycol, triethylene glycol and diethylene glycol.
- the extraction solvent may further include water as a co-solvent.
- the bottom discharge stream of the extractive distillation column of the BTX processing unit contains C7- aromatic hydrocarbons and is supplied to the benzene separation column of the BTX processing unit to separate benzene from the upper discharge stream of the benzene separation column of the BTX processing unit, and the bottom discharge stream is It can be supplied to the toluene separation column of the BTX process unit.
- the bottom discharge stream of the extractive distillation column supplied to the benzene separation column of the BTX processing unit may be supplied to the benzene separation column after passing through a solvent recovery column for removing the extraction solvent.
- the bottom discharge stream of the benzene separation column of the BTX processing unit contains C7 aromatic hydrocarbons and is supplied to the toluene separation column of the BTX processing unit to separate toluene from the toluene separation column top discharge stream, and the bottom discharge stream is It can be fed to a Len separation column.
- the C7 separation column bottom discharge stream and the toluene separation column bottom discharge stream of the BTX processing unit are supplied, xylene is separated from the top discharge stream, and the remaining C9 + hydrocarbon heavy materials are discharged from the bottom can
- devices such as valves, pumps, separators and mixers may be additionally installed.
- the upper discharge stream discharged from 1% of the total number of stages of the gasoline rectification column 10 of the naphtha cracking process (S1) is supplied to the NCC downstream process (not shown), and contains styrene from the NCC downstream process and an RPG stream that does not contain styrene.
- the side discharge stream discharged from 40% of the total number of stages of the gasoline rectification column 10 to the first stripper 20 pyrolysis gas oil (PGO) from the bottom of the first stripper 20
- PGO pyrolysis gas oil
- pyrolysis fuel oil from the lower portion of the second stripper 30 A PFO stream containing was discharged, and at this time, the content of C13+ hydrocarbons in the PFO stream was confirmed to be 89% by weight.
- the flash point of the PGO stream was 25.5 °C and the kinematic viscosity at 40 °C was 75 cSt, and the flash point of the PFO stream was 98 °C and the kinematic viscosity at 40 °C was 660 cSt.
- the mixed oil stream obtained by mixing the PGO stream and the PFO stream was supplied to the distillation tower 50, and then the distillation ratio of the distillation tower 50 was adjusted to discharge the upper discharge stream of the distillation tower 50.
- the bottom discharge stream was supplied to the combustion chamber in the gasification process (S3) together with oxygen and steam to produce syngas containing hydrogen and carbon monoxide.
- the ratio of the flow rate of the PGO stream to the flow rate of the mixed oil stream was 0.42
- the flash point was 70 °C
- the kinematic viscosity at 40 °C was 365 cSt.
- the reflux ratio of the distillation column 50 of the mixed oil stream was controlled to 2.5.
- the RPG stream containing styrene and the upper discharge stream of the distillation column 50 were supplied to the SM process part of the SM / BTX manufacturing process (S4), and styrene was prepared using a C7 separation column, a C8 separation column, and an extractive distillation column, , The remaining stream of the SM processing unit was supplied to the BTX processing unit.
- the RPG stream not containing styrene and the remaining stream of the SM process unit are supplied to the BTX process unit of the SM / BTX manufacturing process (S4) to obtain hydrodesulfurization unit, C5 separation column, C7 separation column, extractive distillation column, and benzene separation column , Benzene, toluene and xylene were prepared using a toluene separation column and a xylene separation column.
- Table 1 below shows the content ratio of C6 to C8 aromatic hydrocarbons in the bottom discharge stream and the top discharge stream of the distillation column 50, the distillation rate of the distillation column 50, and the supply point of the bottom discharge stream of the distillation column 50 to the combustion chamber. Temperature and flash point were measured and indicated. In addition, it was confirmed whether the process operation standards were satisfied according to the above measurement results. At this time, the point at which the exhaust stream from the bottom of the distillation column 50 is supplied to the combustion chamber is set to a temperature condition in which the kinematic viscosity is controlled to 300 cSt using the fourth heat exchanger 53.
- the kinematic viscosity of the sample was measured for each temperature, and then a correlation between temperature and viscosity was established and calculated using interpolation.
- Table 3 shows the amount of styrene, benzene, toluene and xylene produced in the SM/BTX manufacturing process (S4).
- Kinematic viscosity A sample was obtained from the stream of the sample to be measured and measured according to ASTM D7042 using SVM 3001 manufactured by Anton Paar. In addition, the temperature of each of the above samples was maintained at 10° C. lower than the kinematic viscosity measurement temperature, and vapor generation was minimized by storing the samples in a closed container to prevent evaporation of hard materials (Light).
- the PFO stream was supplied to the combustion chamber in the gasification process (S3) together with oxygen and steam. At this time, the content of C13+ in the PFO stream was confirmed to be 89% by weight, the flash point of the PFO stream was 98 ° C, and the kinematic viscosity at 40 ° C was 660 cSt.
- the upper discharge stream discharged from 1% of the total number of stages of the gasoline rectification column 10 of the naphtha cracking process (S1) is supplied to the NCC downstream process (not shown), and contains styrene from the NCC downstream process and an RPG stream that does not contain styrene.
- the RPG stream containing styrene was supplied to the SM processing unit of the SM/BTX manufacturing process (S4), and styrene was produced using a C7 separation column, a C8 separation column, and an extractive distillation column, and the remaining stream of the SM processing unit was BTX supplied to the process department.
- the styrene-free RPG stream and the remaining stream of the SM processing unit are supplied to the BTX processing unit of the SM / BTX manufacturing process (S4), and are used in a hydrodesulfurization unit, a C5 separation column, a C7 separation column, an extractive distillation column, a benzene separation column, Benzene, toluene and xylene were prepared using a toluene separation column and a xylene separation column.
- Table 3 shows the amount of styrene, benzene, toluene and xylene produced in the SM/BTX manufacturing process (S4).
- the first stripper 20 After supplying the side discharge stream discharged from 40% of the total number of stages of the gasoline rectifying column 10 of the naphtha cracking process (S1) to the first stripper 20, the first stripper 20 A PGO stream containing pyrolysis gas oil (PGO) was discharged from the bottom.
- PGO pyrolysis gas oil
- the PGO stream was supplied to the combustion chamber in the gasification process (S3) together with oxygen and steam. At this time, the content of C10 to C12 in the PGO stream was confirmed to be 86% by weight, the flash point of the PGO stream was 25.5 ° C, and the kinematic viscosity at 40 ° C was 75 cSt.
- the upper discharge stream discharged from 1% of the total number of stages of the gasoline rectification column 10 of the naphtha cracking process (S1) is supplied to the NCC downstream process (not shown), and contains styrene from the NCC downstream process and an RPG stream that does not contain styrene.
- the RPG stream containing styrene was supplied to the SM processing unit of the SM/BTX manufacturing process (S4), and styrene was produced using a C7 separation column, a C8 separation column, and an extractive distillation column, and the remaining stream of the SM processing unit was BTX supplied to the process department.
- the styrene-free RPG stream and the remaining stream of the SM processing unit are supplied to the BTX processing unit of the SM / BTX manufacturing process (S4), and are used in a hydrodesulfurization unit, a C5 separation column, a C7 separation column, an extractive distillation column, a benzene separation column, Benzene, toluene and xylene were prepared using a toluene separation column and a xylene separation column.
- Table 3 shows the amount of styrene, benzene, toluene and xylene produced in the SM/BTX manufacturing process (S4).
- the first stripper 20 A PGO stream containing pyrolysis gas oil (PGO) was discharged from the bottom, and at this time, the content of C10 to C12 in the PGO stream was confirmed to be 86% by weight.
- pyrolysis fuel oil (PFO) from the bottom of the second stripper 30 A PFO stream containing was discharged, and at this time, the content of C13+ in the PFO stream was confirmed to be 89% by weight.
- a mixed oil stream was produced by mixing the PGO stream and the PFO stream.
- the flash point of the PGO stream was 25.5 °C and the kinematic viscosity at 40 °C was 75 cSt
- the flash point of the PFO stream was 98 °C and the kinematic viscosity at 40 °C was 660 cSt.
- the ratio of the flow rate of the PGO stream to the flow rate of the mixed oil stream was 0.42.
- the mixed oil stream was supplied to a combustion chamber in the gasification process (S3) together with oxygen and steam.
- the upper discharge stream discharged from 1% of the total number of stages of the gasoline rectification column 10 of the naphtha cracking process (S1) is supplied to the NCC downstream process (not shown), and contains styrene from the NCC downstream process and an RPG stream that does not contain styrene.
- the RPG stream containing styrene was supplied to the SM processing unit of the SM/BTX manufacturing process (S4), and styrene was produced using a C7 separation column, a C8 separation column, and an extractive distillation column, and the remaining stream of the SM processing unit was BTX supplied to the process department.
- the styrene-free RPG stream and the remaining stream of the SM processing unit are supplied to the BTX processing unit of the SM / BTX manufacturing process (S4), and are used in a hydrodesulfurization unit, a C5 separation column, a C7 separation column, an extractive distillation column, a benzene separation column, Benzene, toluene and xylene were prepared using a toluene separation column and a xylene separation column.
- Table 3 shows the amount of styrene, benzene, toluene and xylene produced in the SM/BTX manufacturing process (S4).
- Example 1 styrene and BTX were produced in the same manner as in Example 1, except that the top discharge stream of the distillation column 50 was not supplied to the SM/BTX manufacturing process (S4).
- Table 3 shows the amount of styrene, benzene, toluene and xylene produced in the SM/BTX manufacturing process (S4).
- Example 1 100.0 100.0 100.0 100.0
- Example 2 100.1 100.1 100.0 100.0
- Example 3 100.2 100.8 107.0 111.0
- Example 4 100.2 100.8 107.0 111.0
- Example 5 100.2 100.8 107.0 111.0 Comparative Example 1 100.0 100.0 100.0 100.0 100.0 Comparative Example 2 100.0 100.0 100.0 100.0 Comparative Example 3 100.0 100.0 100.0 100.0 Comparative Example 4 100.0 100.0 100.0 100.0 100.0
- the distillation ratio of the distillation tower 50 is adjusted to an appropriate range (0.01 to 0.2) to generate a bottom discharge stream, and then the distillation tower 50 )
- the flash point of the lower discharge stream of the distillation column 50 at the point of supply of the lower discharge stream to the combustion chamber. is 25 ° C.
- the kinematic viscosity is in the range of 300 cSt or less at the temperature of the bottom discharge stream of the distillation column 50 at the time of supply to the combustion chamber.
- Example 3 in which the distillation ratio of the distillation tower 50 is controlled within the range of 0.03 to 0.15 in the pretreatment process (S2), at the point of supply of the lower discharge stream of the distillation tower 50 to the combustion chamber , It was confirmed that the flash point of the lower discharge stream of the distillation column 50 was higher than the temperature of the lower discharge stream of the distillation column 50 by 30 ° C. at the time of supply to the combustion chamber, enabling more stable operation.
- the PFO stream is directly supplied to the combustion chamber without a pretreatment step (S2) (Comparative Example 1), or as shown in FIG. 3, the PGO stream is directly supplied without a pretreatment step (S2).
- S2 the combustion chamber without a pretreatment step
- S2 the mixed oil stream of the PGO stream and the PFO stream is directly supplied to the combustion chamber without the pretreatment process (S2) according to the present invention as shown in FIG. 4 (Comparative Example 3)
- each of the streams of Comparative Examples 1 to 3 that did not satisfy both the kinematic viscosity and the flash point within the proper range did not satisfy the process operating conditions for use as a raw material for the gasification process (S3).
- the differential pressure in the combustion chamber may increase or the spray may not be smoothly performed, resulting in deterioration in combustion performance.
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Abstract
Description
증류 비율 |
C6~C8 방향족 탄화수소 비율 |
하부 배출 스트림 공급 시점 온도 (℃) |
하부 배출 스트림 공급 시점 동점도 (cSt) |
하부 배출 스트림 인화점 (℃) |
공정운전 기준 충족 여부 |
||
상부 배출 스트림 |
하부 배출 스트림 |
||||||
실시예 1 | 0.005 | 0 | 1 | 48.3 | 300 | 73 | X |
실시예 2 | 0.01 | 0.08 | 0.92 | 49.2 | 300 | 75 | O |
실시예 3 | 0.1 | 1 | 0 | 60 | 300 | 90.5 | O |
실시예 4 | 0.2 | 1 | 0 | 73.3 | 300 | 99 | O |
실시예 5 | 0.3 | 1 | 0 | 97.6 | 300 | 105.5 | X |
스트림 인화점(℃) |
스트림 공급 시점 동점도(cSt) |
스트림 공급 시점 온도(℃) |
공정운전 기준 충족 여부 |
|
비교예 1 (PFO) |
98 | 300 | 78 | X |
비교예 2 (PGO) |
25.5 | 300 | 14 | X |
비교예 3 (혼합유) |
70 | 300 | 47 | X |
벤젠 생산량 (%) |
톨루엔 생산량 (%) |
자일렌 생산량 (%) |
스티렌 생산량 (%) |
|
실시예 1 | 100.0 | 100.0 | 100.0 | 100.0 |
실시예 2 | 100.1 | 100.1 | 100.0 | 100.0 |
실시예 3 | 100.2 | 100.8 | 107.0 | 111.0 |
실시예 4 | 100.2 | 100.8 | 107.0 | 111.0 |
실시예 5 | 100.2 | 100.8 | 107.0 | 111.0 |
비교예 1 | 100.0 | 100.0 | 100.0 | 100.0 |
비교예 2 | 100.0 | 100.0 | 100.0 | 100.0 |
비교예 3 | 100.0 | 100.0 | 100.0 | 100.0 |
비교예 4 | 100.0 | 100.0 | 100.0 | 100.0 |
Claims (14)
- 나프타 분해 공정(NCC)으로부터 배출되는 열분해 연료유(Pyrolysis Fuel Oil, PFO)를 포함하는 PFO 스트림 및 열분해 가스유(Pyrolysis Gas Oil, PGO)를 포함하는 PGO 스트림을 피드 스트림으로서 증류탑으로 공급하는 단계(S10); 및상기 증류탑의 하부 배출 스트림을 가스화 공정을 위한 연소실로 공급하고, 상부 배출 스트림은 SM/BTX 제조 공정으로 공급하는 단계(S20)를 포함하는 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 증류탑으로 공급되는 피드 스트림의 유량에 대한, 상기 증류탑의 상부 배출 스트림의 유량 비율은 0.01 내지 0.2인 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 증류탑으로 공급되는 피드 스트림의 유량에 대한, 상기 증류탑의 상부 배출 스트림의 유량 비율은 0.1 내지 0.2인 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 증류탑의 하부 배출 스트림은 상기 연소실로의 공급 시점에서의 동점도가 300 cSt 이하이고,상기 증류탑의 하부 배출 스트림의 인화점은 상기 연소실로의 공급 시점에서의 온도보다 25 ℃ 이상 높은 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 증류탑의 하부 배출 스트림의 연소실로의 공급 시점 온도는 20 ℃ 내지 90 ℃인 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 증류탑의 하부 배출 스트림을 상기 연소실로 공급하기 전에 제4 열교환기를 통과시키는 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 PGO 스트림은 C10 내지 C12의 탄화수소를 70 중량% 이상 포함하고,상기 PFO 스트림은 C13+ 탄화수소를 70 중량% 이상 포함하는 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 PGO 스트림의 인화점은 10 내지 50 ℃이고,상기 PFO 스트림의 인화점은 70 내지 200 ℃인 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 PGO 스트림은 40 ℃에서의 동점도가 1 내지 200 cSt이고,상기 PFO 스트림은 40 ℃에서의 동점도가 400 내지 100,000 cSt인 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 나프타 분해 공정(NCC)으로부터 배출되는 열분해 가솔린(Raw Pyrolysis Gasoline, RPG)을 포함하는 RPG 스트림을 SM/BTX 제조 공정으로 공급하는 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 PGO 스트림은 상기 나프타 분해 공정의 가솔린 정류탑의 측부로부터 배출된 측부 배출 스트림을 제1 스트리퍼에 공급한 후, 상기 제1 스트리퍼의 하부로부터 배출된 하부 배출 스트림이고,상기 PFO 스트림은 상기 나프타 분해 공정의 가솔린 정류탑의 하부로부터 배출된 하부 배출 스트림을 제2 스트리퍼에 공급한 후, 상기 제2 스트리퍼의 하부로부터 배출된 하부 배출 스트림인 합성가스 및 방향족 탄화수소의 제조방법.
- 제11항에 있어서,상기 가솔린 정류탑의 하부 배출 스트림은 상기 가솔린 정류탑의 전체 단수 대비 90% 이상의 단에서 배출되고,상기 가솔린 정류탑의 측부 배출 스트림은 상기 가솔린 정류탑의 전체 단수 대비 10% 내지 70%의 단에서 배출되는 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 증류탑의 환류비는 0.01 내지 10인 합성가스 및 방향족 탄화수소의 제조방법.
- 제1항에 있어서,상기 SM/BTX 제조 공정은 SM 공정부 및 BTX 공정부를 포함하고, 상기 증류탑의 상부 배출 스트림은 SM/BTX 제조 공정의 SM 공정부로 공급되는 합성가스 및 방향족 탄화수소의 제조방법.
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CN202180018112.8A CN115720572B (zh) | 2021-06-24 | 2021-12-11 | 制备合成气和芳烃的方法 |
EP21920111.8A EP4155256A4 (en) | 2021-06-24 | 2021-12-11 | METHOD FOR PRODUCING SYNTHESIS GAS AND AROMATIC HYDROCARBONS |
US17/796,837 US20230340345A1 (en) | 2021-06-24 | 2021-12-11 | Method for preparing synthesis gas and aromatic hydrocarbon |
BR112022017005A BR112022017005A2 (pt) | 2021-06-24 | 2021-12-11 | Método para preparar gás de síntese e hidrocarboneto aromático |
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TW202300440A (zh) | 2023-01-01 |
KR20230000240A (ko) | 2023-01-02 |
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