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WO2016098909A1 - Procédé et dispositif de production d'oléfines inférieures, procédé de construction pour équipement de production d'oléfines inférieures, et catalyseur de type zéolithe - Google Patents

Procédé et dispositif de production d'oléfines inférieures, procédé de construction pour équipement de production d'oléfines inférieures, et catalyseur de type zéolithe Download PDF

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Publication number
WO2016098909A1
WO2016098909A1 PCT/JP2015/085649 JP2015085649W WO2016098909A1 WO 2016098909 A1 WO2016098909 A1 WO 2016098909A1 JP 2015085649 W JP2015085649 W JP 2015085649W WO 2016098909 A1 WO2016098909 A1 WO 2016098909A1
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Prior art keywords
propylene
ethylene
component
catalytic cracking
cracking
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English (en)
Japanese (ja)
Inventor
健一 味村
冬樹 八木
真哉 程島
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Chiyoda Corp
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Chiyoda Corp
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Priority claimed from JP2014257098A external-priority patent/JP6480726B2/ja
Priority claimed from JP2014257094A external-priority patent/JP2016117800A/ja
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Publication of WO2016098909A1 publication Critical patent/WO2016098909A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only including only thermal and catalytic cracking steps
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/04—Ethylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/02—Alkenes
    • C07C11/06—Propene
    • 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
    • C07C4/06—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/04—Purification; Separation; Use of additives by distillation
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4056—Retrofitting operations

Definitions

  • the present invention relates to a lower olefin production method, a lower olefin production apparatus, a lower olefin production facility construction method, and a zeolite catalyst for producing a lower olefin from a light paraffinic hydrocarbon raw material.
  • Petrochemical industry uses light naphtha from a refinery as a raw material to produce lower olefins such as ethylene and propylene by steam cracking. These lower olefins are important basic raw materials for various chemical products such as fibers and plastics (synthetic resins).
  • light naphtha and steam are mixed at a certain ratio and then pyrolyzed under conditions of high temperature and no catalyst above 800 ° C to produce lower olefins.
  • the production ratio is about 2: 1 and is a simple pyrolysis reaction, so it is difficult to change this ratio.
  • OCT Olefin Conversion Technology
  • Commercial equipment using the OCT process (hereinafter referred to as the OCT process) is moving.
  • the OCT process can produce 2 moles of propylene from 1 mole of ethylene and 1 mole of butene using a special catalyst.
  • OCT Pros commercial equipment is used in combination with light naphtha steam cracking to produce propylene using ethylene and butene produced by steam cracking.
  • the production amount of propylene is governed by the production amount of butene produced by steam cracking, for example, the production ratio of ethylene and propylene in the facility in which the commercial equipment of the OCT process is installed in the facility of the steam cracker is About 1: 1 is the limit.
  • the production ratio of ethylene and propylene is about 1: 1.5 to 1: 3 depending on the reaction conditions, which is more than in the case of steam cracking or combining the OCT process with steam cracking. Propylene production ratio can be dramatically increased.
  • the production ratio of propylene to ethylene can be dramatically increased.
  • the production ratio of ethylene to propylene can be dramatically increased.
  • the production ratio of ethylene to propylene can be high. Therefore, for example, when a facility for catalytic cracking reaction using a zeolite catalyst is provided instead of the existing steam cracker facility, the production amount of propylene and the energy efficiency can be improved. It is difficult to change the production ratio, and it is impossible to cope with the rapid increase in demand for ethylene.
  • the present invention was made in view of the above circumstances, and when ethylene and propylene are produced from light paraffinic hydrocarbon materials such as light naphtha, the production ratio of these ethylene and propylene can be easily changed, and
  • An object of the present invention is to provide a method for producing a lower olefin, a production apparatus for a lower olefin, a construction method for a production facility for a lower olefin, and a zeolite catalyst that can reduce the cost of the equipment.
  • the method for producing a lower olefin of the present invention is a method for producing a lower olefin, which produces ethylene and propylene as a lower olefin from a light paraffin hydrocarbon raw material, A catalytic cracking reaction step for producing the ethylene and the propylene from the light paraffinic hydrocarbon raw material by a catalytic cracking reaction using a zeolite catalyst; And a steam cracking step of producing the ethylene and the propylene from the light paraffinic hydrocarbon raw material by steam cracking.
  • ethylene and propylene are produced from a light paraffinic hydrocarbon raw material by a catalytic cracking reaction using a zeolite catalyst, and ethylene and propylene are produced from a light paraffinic hydrocarbon raw material by steam cracking.
  • ethylene and propylene are not restricted to ethylene and propylene,
  • a butadiene, a butene, etc. may be included and you may make it possible to isolate
  • the production ratio (weight ratio) of propylene to ethylene can be reduced to about 1.5 to 3.0 by appropriately setting the reaction conditions. Propylene can be selectively produced.
  • the production ratio (weight ratio) of propylene to ethylene is about 0.5, and the production amount of ethylene is higher than the production amount of propylene.
  • the catalytic cracking reaction has a lower reaction temperature compared to steam cracking, and the catalytic cracking reaction is more energy efficient, but by combining steam cracking with catalytic cracking reaction, compared with steam cracking alone.
  • energy efficiency can be improved. Since both steam cracking and catalytic cracking reaction in the present invention produce ethylene and propylene from the same raw material, the same equipment can be used for the separation (separation and purification) of ethylene and propylene, When the equipment for catalytic cracking reaction is installed in the steam cracking equipment, it becomes possible to effectively utilize the existing separation and purification equipment for steam cracking for the separation and purification of ethylene and propylene after the catalytic cracking reaction. The construction cost can be reduced.
  • the light paraffin hydrocarbon raw material is, for example, a paraffin having about 7 carbon atoms (C7) or less as a main component, for example, a light naphtha having a paraffin of about C4 to C7 as a main component is suitable.
  • Light naphtha is a fraction containing a large amount of paraffins of about C5 and C6 when crude oil is separated by distillation, but the raw material is not limited to petroleum, and may be shale oil, condensate, or the like.
  • the light paraffin hydrocarbon raw material is not limited to light naphtha, and may basically be a hydrocarbon raw material having a high paraffin content of about C4 to C7.
  • naphtha including heavy naphtha may be used.
  • the light paraffinic hydrocarbon raw material is distributed into a pyrolysis component to be sent to the steam cracking step and a catalytic cracking component to be sent to the catalytic cracking reaction step, and the pyrolysis is performed during the distribution. It is preferable that the distribution ratio between the minute fraction and the catalytic cracking fraction can be adjusted.
  • the production ratio of propylene is increased, or the distribution ratio of thermal cracking is increased.
  • Ethylene production ratio can be increased.
  • Each demand for ethylene and propylene changes with the passage of time, and there is a possibility that demand for ethylene will increase in the short term and demand for propylene will increase.
  • the production ratio of ethylene and propylene can be changed relatively easily.
  • lower hydrocarbon separation which separates a lower hydrocarbon component mainly composed of lower hydrocarbons having 4 or less carbon atoms and containing ethylene and propylene from the cracked mixture obtained through the catalytic cracking reaction step.
  • ethylene and propylene produced by the catalytic cracking reaction and ethylene and propylene produced by steam cracking can be separated in the same shared separation step. That is, both the separation of ethylene and propylene produced by the catalytic cracking reaction and the separation of ethylene and propylene produced by the steam cracking can be performed using the same separation and purification equipment.
  • the separation and purification equipment in the steam cracking equipment is also used for the catalytic cracking reaction without providing the separation and purification equipment for the catalytic cracking reaction. It is possible to reduce the construction cost of the equipment, reduce the equipment cost, and improve the space efficiency of the equipment.
  • ethylene and propylene and other components are not separated, but basically only the lower hydrocarbon component and the re-cracking component described later are separated.
  • Equipment such as a distillation tower to be used can be simplified. Therefore, even if it is necessary to increase the number of distillation columns when providing catalytic cracking equipment to existing steam cracking equipment, it is only necessary to provide a small number of distillation towers compared to existing separation and purification equipment.
  • a residue obtained by removing the lower hydrocarbon component from the cracked mixture obtained through the catalytic cracking reaction step is used as a re-cracking component in the catalytic cracking reaction step. It is preferable to return.
  • the above-described lower hydrocarbon component is sent to the common separation step with a simple distillation facility, and the re-cracking component excluding the lower hydrocarbon component from the raw material is returned to the catalytic cracking step.
  • the component for re-decomposition does not contain heavy components, such as BTX of an aromatic compound.
  • a lower paraffin component having a lighter (C1 to C3) paraffin as a main component than C4 is separated, and the lower paraffin component is returned to the steam cracking step. preferable.
  • paraffin that is lighter than C4 can be processed by steam cracking and used, for example, as a raw material for ethylene or propyne.
  • the catalytic cracking reaction for example, it is difficult to use ethane or propane as ethylene or propylene as paraffins lighter than C4 (C1 to C3). That is, even if these ethanes and propanes are returned to the catalytic cracking reaction, the cracking is difficult.
  • ethane is difficult to be decomposed by the catalytic cracking reaction, and if ethane is returned to the catalytic cracking reaction, the content of unreacted ethane increases, so that it is necessary to remove ethane.
  • ethane can be effectively used.
  • the zeolite in the zeolite catalyst used in the catalytic cracking reaction step is preferably MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • the amount of propylene produced in the catalytic cracking reaction is increased by using a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium When combined with the production of ethylene and propylene by steam cracking, the production ratio of propylene can be further increased.
  • the method for producing a lower olefin of the present invention is a method for producing a lower olefin, wherein ethylene and propylene are produced as a lower olefin from a light paraffin hydrocarbon raw material,
  • the re-cracking component separated so as to contain no unreacted raw material in the catalytic cracking reaction is supplied, the ethylene and the propylene are removed from the re-cracking component by steam cracking. And a steam cracking process to be manufactured.
  • ethylene and propylene are produced from a light paraffinic hydrocarbon raw material by a catalytic cracking reaction using a zeolite catalyst, and from the cracked mixture after the light paraffinic hydrocarbon raw material is catalytically cracked. While being separated so as not to contain ethylene and propylene, ethylene and propylene are produced by steam cracking from the re-decomposition component separated so as to contain paraffin which is an unreacted raw material.
  • what is manufactured in this invention is not restricted to ethylene and propylene, For example, a butadiene may be included and you may make it possible to isolate
  • the production ratio (weight) of propylene / ethylene can be adjusted from about 1.5 to about 3.0 by appropriately setting the reaction conditions. Propylene production can be increased.
  • the production ratio (weight) of propylene / ethylene is about 0.5, and the production amount of ethylene is higher than the production amount of propylene.
  • the catalytic cracking reaction has a lower reaction temperature and better energy efficiency, so combining steam cracking with catalytic cracking reaction improves energy efficiency compared to steam cracking alone.
  • the light paraffin hydrocarbon raw material is, for example, a paraffin having about 7 carbon atoms (C7) or less as a main component, for example, a light naphtha having a paraffin of about C4 to C7 as a main component is suitable.
  • Light naphtha is a fraction containing a large amount of paraffins of about C5 and C6 when crude oil is separated by distillation, but the raw material is not limited to petroleum, and may be shale oil, condensate, or the like.
  • the light paraffin hydrocarbon raw material is not limited to light naphtha, and may basically be a hydrocarbon raw material having a high paraffin content of about C4 to C7.
  • naphtha including heavy naphtha may be used.
  • the re-decomposition component can be returned to the catalytic decomposition reaction step.
  • the re-decomposition component is divided into a forward flow portion to be sent to the steam cracking step and a reflux portion to be returned to the catalytic cracking reaction step, and the forward flow portion and the It is preferable that the distribution ratio with respect to the reflux component can be adjusted.
  • the production ratio of propylene can be increased, or cracking can be performed among the components for re-decomposition.
  • the ethylene production ratio can be increased.
  • a lower paraffin component mainly containing lighter (C1 to C3) paraffin than C4 is separated, and the lower paraffin component is supplied to the steam cracking step. It is preferable.
  • paraffin that is lighter than C4 can be processed by steam cracking and used, for example, as a raw material for ethylene or propyne.
  • the catalytic cracking reaction for example, it is difficult to use ethane or propane as ethylene or propylene as paraffins lighter than C4 (C1 to C3). That is, even if these ethanes and propanes are returned to the catalytic cracking reaction, the cracking is difficult.
  • ethane is difficult to be decomposed by the catalytic cracking reaction, and if ethane is returned to the catalytic cracking reaction, the content of unreacted ethane increases, so that it is necessary to remove ethane.
  • ethane can be effectively used.
  • lower hydrocarbon separation which separates a lower hydrocarbon component mainly composed of lower hydrocarbons having 4 or less carbon atoms and containing ethylene and propylene from the cracked mixture obtained through the catalytic cracking reaction step. It is preferable to include a process, and a residue obtained by removing the lower hydrocarbon component from the cracked mixture obtained through the catalytic cracking reaction process is used as the recracking component.
  • the cracked mixture that has undergone the catalytic cracking reaction is separated into a lower hydrocarbon component containing ethylene and propylene and a re-cracking component containing unreacted paraffin by a lower hydrocarbon separation step,
  • the re-decomposition component is sent to the steam cracking process.
  • ethylene, propylene and other components are not separated, but basically only the lower hydrocarbon component and the re-cracking component are separated.
  • a distillation column used for separation is used. It is possible to simplify the equipment such as the above, and to send the components for re-decomposition to the steam cracking process.
  • a shared separation step for separating the ethylene and the propylene from the lower hydrocarbon component and the cracked mixture that has undergone the steam cracking step is provided.
  • ethylene and propylene produced by the catalytic cracking reaction and ethylene and propylene produced by steam cracking can be separated in the same shared separation step. That is, both the separation of ethylene and propylene produced by the catalytic cracking reaction and the separation of ethylene and propylene produced by the steam cracking can be performed using the same separation and purification equipment.
  • the separation and purification equipment in the steam cracking equipment is also used for the catalytic cracking reaction without providing the separation and purification equipment for the catalytic cracking reaction. It is possible to reduce the construction cost of the equipment, reduce the equipment cost, and improve the space efficiency of the equipment.
  • a lower paraffin component having a lighter (C1 to C3) paraffin as a main component than C4 is separated, and the lower paraffin component is returned to the steam cracking step. preferable.
  • the zeolite in the zeolite catalyst used in the catalytic cracking reaction step is preferably MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • the amount of propylene produced in the catalytic cracking reaction is increased by using a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium When combined with the production of ethylene and propylene by steam cracking, the production ratio of propylene can be further increased.
  • the lower olefin production apparatus of the present invention is a lower olefin production apparatus for producing ethylene and propylene as a lower olefin from a light paraffinic hydrocarbon raw material
  • a catalytic cracking means comprising a reactor for producing the ethylene and the propylene from a light paraffinic hydrocarbon raw material by a catalytic cracking reaction using a zeolite catalyst;
  • a thermal decomposition means including a decomposition furnace for producing the ethylene and the propylene from the light paraffinic hydrocarbon raw material by steam cracking.
  • the light paraffinic hydrocarbon raw material is distributed into a pyrolysis component to be sent to the pyrolysis means and a catalytic cracking component to be sent to the catalytic cracking device. It is preferable to provide a distribution means capable of adjusting the distribution ratio between the contact decomposition amount and the catalytic decomposition component.
  • the production ratio of propylene can be increased by increasing the distribution ratio of the catalytic cracking of the light paraffinic hydrocarbon raw material in the same manner as the above-described production method of the lower olefin, By increasing the distribution ratio of the pyrolyzed portion of the hydrocarbon raw material, the ethylene production ratio can be increased.
  • a lower hydrocarbon separation means for separating a lower hydrocarbon component mainly comprising a lower hydrocarbon having 4 or less carbon atoms and containing the ethylene and the propylene from the decomposition mixture flowing out from the reactor.
  • a common separation and purification means for separating the ethylene and the propylene from the lower hydrocarbon component and the cracked mixture flowing out from the cracking furnace.
  • the ethylene and propylene produced by the catalytic cracking reaction and the ethylene and propylene produced by the steam cracking can be separated in the same shared separation step, as in the above-described method for producing a lower olefin. Therefore, when the catalytic cracking equipment is installed in the existing steam cracking equipment, only the lower hydrocarbon separation means is provided without providing the separation and purification equipment for the catalytic cracking reaction, and the separation and purification equipment in the steam cracking equipment is subjected to the catalytic cracking reaction. It is possible to reduce the construction cost of the equipment, reduce the equipment cost, and improve the space efficiency of the equipment.
  • the zeolite in the zeolite catalyst used in the reactor is preferably MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium in the catalytic cracking reaction as in the above-described method for producing lower olefins,
  • the amount of propylene produced in the catalytic cracking reaction can be increased, and the production ratio of propylene can be further increased when combined with the production of ethylene and propylene by steam cracking.
  • the lower olefin production apparatus of the present invention is a lower olefin production apparatus for producing ethylene and propylene as a lower olefin from a light paraffinic hydrocarbon raw material
  • a catalytic cracking means comprising a reactor for producing the ethylene and the propylene from a light paraffinic hydrocarbon raw material by a catalytic cracking reaction using a zeolite catalyst; and the ethylene and the propylene from a cracked mixture discharged from the reactor
  • the ethylene and the propylene are produced by steam cracking from the re-decomposition component when the re-decomposition component separated so as to contain the unreacted component in the catalytic decomposition reaction is supplied.
  • a thermal decomposition means including a decomposition furnace.
  • the re-cracking component separated from the cracked mixture flowing out of the reactor can be returned to the reactor, Distributing means capable of distributing the re-cracking component into a forward flow portion to be sent to the cracking furnace and a reflux portion to be returned to the reactor, and adjusting a distribution ratio between the forward flow portion and the reflux portion at the time of the distribution. It is preferable to provide.
  • the propylene production ratio is increased by increasing the distribution ratio of the reflux component of the re-cracking component in the same manner as the above-described method for producing lower olefins.
  • the production ratio of ethylene can be increased by increasing the distribution ratio of the forward flow.
  • the catalytic cracking separation and purification means for separating the ethylene, the propylene and the re-cracking component, respectively, from the cracking mixture flowing out from the cracking furnace It is preferable to include a separation and purification means for thermal decomposition for separating at least the ethylene and the propylene, respectively.
  • ethylene and propylene produced by a catalytic cracking reaction are produced from a light paraffinic hydrocarbon raw material and then separated from each other, and unreacted paraffin is produced. Can be separated and supplied to the steam cracking process. Further, ethylene and propylene generated by steam cracking can be separated.
  • a lower hydrocarbon separation means for separating a lower hydrocarbon component mainly comprising a lower hydrocarbon having 4 or less carbon atoms and containing the ethylene and the propylene from the decomposition mixture flowing out from the reactor.
  • a residue obtained by removing the lower hydrocarbon component from the cracked mixture flowing out of the reactor is used as the recracking component, It is preferable to provide a common separation and purification means for separating the ethylene and the propylene from the lower hydrocarbon component and the cracked mixture flowing out from the cracking furnace.
  • the ethylene and propylene produced by the catalytic cracking reaction and the ethylene and propylene produced by the steam cracking can be separated in the same shared separation step, as in the above-described method for producing a lower olefin. Therefore, when the equipment for catalytic cracking reaction is installed in the existing steam cracking equipment, the separation and purification equipment in the steam cracking equipment is also used for the catalytic cracking reaction without providing the separation and purification equipment for the catalytic cracking reaction. Therefore, the construction cost of the equipment can be reduced, the equipment cost can be reduced, and the space efficiency in the equipment can be improved.
  • the zeolite in the zeolite catalyst used in the reactor is preferably MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium in the catalytic cracking reaction as in the above-described method for producing lower olefins,
  • the amount of propylene produced in the catalytic cracking reaction can be increased, and the production ratio of propylene can be further increased when combined with the production of ethylene and propylene by steam cracking.
  • the construction method of the lower olefin production facility of the present invention is a construction method of a lower olefin production facility for producing ethylene and propylene as a lower olefin from a light paraffinic hydrocarbon raw material, From a light paraffin hydrocarbon raw material to a zeolite catalyst, an existing steam cracking facility comprising a cracking furnace for producing the ethylene and propylene by steam cracking and a separation and purification facility for separating and purifying the cracked mixture flowing out of the cracking furnace
  • a catalytic cracking reaction facility equipped with a reactor for producing the ethylene and the propylene by a catalytic cracking reaction using a catalyst is provided.
  • the production ratio of propylene in the production of ethylene and propylene combined with these facilities is determined by the steam cracking facility alone. Can be higher than in the case of.
  • the cost for disposal of the steam cracking equipment is not required, and the cost can be reduced.
  • post-process equipment for steam cracking can be used as post-process equipment up to separation and purification after catalytic cracking reaction. The construction cost can be reduced.
  • the construction method of the lower olefin production facility of the present invention is a construction method of a lower olefin production facility for producing ethylene and propylene as a lower olefin from a light paraffinic hydrocarbon raw material, From a light paraffin hydrocarbon raw material to a zeolite catalyst, an existing steam cracking facility comprising a cracking furnace for producing the ethylene and propylene by steam cracking and a separation and purification facility for separating and purifying the cracked mixture flowing out of the cracking furnace
  • a catalytic cracking reaction facility equipped with a reactor for producing the ethylene and the propylene by a catalytic cracking reaction using A re-cracking component separated from the cracked mixture flowing out from the reactor so as not to contain ethylene and propylene and separated to contain unreacted components in the catalytic cracking reaction can be supplied to the cracking furnace. It is characterized by doing.
  • the production ratio of propylene in the production of ethylene and propylene combined with these facilities is determined by the steam cracking facility alone. Can be higher than in the case of.
  • the cost for disposal of the steam cracking equipment is not required, and the cost can be reduced.
  • post-process equipment for steam cracking can be used as post-process equipment up to separation and purification after catalytic cracking reaction. The construction cost can be reduced.
  • the zeolite catalyst of the present invention is a zeolite catalyst used in the catalytic cracking reaction step of the method for producing a lower olefin, Zeolite is included, and the zeolite is MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • the amount of propylene produced in the catalytic cracking reaction is increased by using a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium.
  • a zeolite catalyst containing zeolite that is MFI type crystalline aluminosilicate containing iron or iron and gallium When combined with the production of ethylene and propylene by steam cracking, the production ratio of propylene can be further increased.
  • the production ratio of propylene can be increased as compared with the case of producing ethylene and propylene by steam cracking alone. Energy efficiency.
  • FIG. 4 is a process diagram for explaining a catalytic cracking reaction in which steam is introduced in the method for producing a lower olefin. It is process drawing which shows the manufacturing method of a lower olefin same as the above. It is process drawing corresponding to Example 1 which shows the manufacturing method of a lower olefin similarly. It is process drawing corresponding to Example 2 which shows the manufacturing method of a lower olefin similarly. It is process drawing corresponding to Example 3 which shows the manufacturing method of a lower olefin similarly.
  • Example 4 It is process drawing corresponding to Example 4 which shows the manufacturing method of a lower olefin similarly. It is a block diagram which shows the outline of the manufacturing apparatus of a lower olefin same as the above. It is a figure for demonstrating the experimental result of manufacture of a lower olefin by a catalytic cracking reaction, and the calculation result based on it. It is a figure for demonstrating the experimental result of the manufacture of a lower olefin by the catalytic cracking reaction which introduce
  • Example 5 which shows the manufacturing method of the lower olefin of the 2nd Embodiment of this invention.
  • Example 6 which shows the manufacturing method of a lower olefin similarly.
  • Example 7 which shows the manufacturing method of a lower olefin similarly.
  • Example 8 which shows the manufacturing method of a lower olefin similarly.
  • It is a block diagram which shows the outline of the manufacturing apparatus of a lower olefin same as the above.
  • Example 9 which shows the manufacturing method of the lower olefin of the 3rd Embodiment of this invention.
  • Example 10 It is process drawing corresponding to Example 10 which shows the manufacturing method of a lower olefin similarly. It is process drawing corresponding to Example 11 which shows the manufacturing method of a lower olefin similarly. It is process drawing corresponding to Example 12 which shows the manufacturing method of a lower olefin similarly. It is a block diagram which shows the outline of the manufacturing apparatus of a lower olefin same as the above. It is a figure which shows the experimental result by the simulation (calculation) of Example 5-Example 8. FIG. It is a figure which shows the experimental result by the simulation (calculation) of Example 9-12.
  • a light olefin which is a light paraffinic hydrocarbon material
  • the construction method of is described.
  • ethylene and propylene are produced by combining ethylene and propylene production by a catalytic cracking reaction using a zeolite catalyst and ethylene and propylene production by steam cracking.
  • the production ratio of ethylene and propylene by the catalytic cracking reaction of the present embodiment is about 1: 1.5 to 3.0 depending on various conditions, whereas in the case of steam cracking, the production ratio of ethylene and propylene is Since it becomes about 2: 1, the production ratio of ethylene and propylene can be adjusted by combining these production methods.
  • ethylene and propylene are obtained by performing a separation and purification step (separation step for catalytic cracking) S3 on the cracked mixture that has been catalytically cracked in the catalytic cracking reaction step S1 and has undergone the quench, gas pressurization, and dehydration step S2.
  • a composite catalyst containing gallium (Ga) and iron (Fe) or crystalline aluminosilicate containing iron and silicon dioxide functioning as a binder for molding is used.
  • the binder may be alumina (aluminum oxide), but silicon dioxide is preferred.
  • the zeolite which is a crystalline aluminosilicate has, for example, an MFI type skeleton structure.
  • the framework structure of zeolite has been made into a database by the International Zeolite Society, and a structure code consisting of three capital letters is given.
  • the MFI type is one of the structure codes.
  • Fe contained in the zeolite catalyst has a function of suppressing the acid strength of the acid point of the zeolite.
  • Ga has a function of promoting alkane dehydrogenation.
  • the zeolite catalyst of the present embodiment is a composite catalyst obtained by molding and firing with a binder (binder) added, and silicon dioxide is used as the binder.
  • the elemental molar composition ratio of iron element is 0.4 to 0.7. More preferably, it is 0.4 to 0.6.
  • the acid density (molar composition ratio defined as Si / (Fe + Al)) is 75.0 to 200. It is preferably 0, and more preferably 80.0 to 200.0.
  • the element ratio is a composition ratio based on the number of moles of each element described above.
  • the elemental molar composition ratio (Fe / (Fe + Ga + Al)) of the iron element is preferably 0.2 to 0.6. Further, it is more preferably 0.3 to 0.5.
  • the elemental molar composition ratio (Ga / (Fe + Ga + Al)) of the gallium element is preferably 0.1 to 0.4. Further, it is more preferably 0.2 to 0.4.
  • the acid density (molar composition ratio defined as Si / (Fe + Ga + Al)) is preferably 75.0 to 200.0, and 80 More preferably, it is 0.0 to 200.0.
  • the acid strength can be adjusted from the content of the iron element and the acid density.
  • gallium element By adding gallium element, the promoting action of dehydrogenation of alkane can be improved.
  • the alkane is divided and a carbon double bond is generated by the decarbonization reaction, resulting in a lower olefin.
  • the composition ratio of the number of moles of the iron element, the composition ratio of the number of moles of the gallium element, and the acid density within the above-mentioned ranges, the yield of propylene can be further improved, and the fragrance that causes the production of coke. The generation of group carbon can be further suppressed.
  • the content of silicon dioxide (silica) as a binder in the composite catalyst is preferably 5 to 50 wt% (wt%), more preferably 5 to 40 wt%. .
  • silicon dioxide as a binder has a stronger action to coat and inactivate acid sites on the outer surface of zeolite than aluminum oxide (alumina) as a binder.
  • composition of the above-mentioned zeolite is suitable when, for example, silicon dioxide is used as a binder.
  • a raw material gas such as light naphtha is supplied to a reactor in which a zeolite catalyst is arranged in a fixed bed system. That is, light naphtha is reacted with the composite catalyst.
  • the raw material gas may contain, for example, steam or nitrogen gas as a diluent.
  • the gas supplied to the composite catalyst preferably contains 15 wt% or more of light naphtha. More preferably, it is contained in an amount of 50 wt% or more.
  • a method is used in which the composite catalyst described above is arranged as a fixed bed in the reactor, and the raw material gas supplied into the reactor is passed while contacting the composite catalyst. At this time, the reaction is allowed to proceed in a moderate temperature range of 530 ° C. to 650 ° C., more preferably 550 ° C. to 640 ° C. to produce ethylene and propylene.
  • the lower olefin hydrocarbon feedstock is, for example, light paraffinic hydrocarbon feedstock (low-boiling hydrocarbon feedstock) such as light naphtha, but naphtha (full-range naphtha) is separated by distillation of crude oil using an atmospheric distillation unit.
  • the product obtained in this way has a boiling range of about 35 to 180 (200) ° C.
  • these naphtha those having a boiling range of about 35 to 80 (100) ° C. are called light (light) naphtha, and those having a boiling range of about 80 (100) to 180 (200) ° C. are called heavy (heavy) naphtha. .
  • Light naphtha corresponds to a fraction mainly composed of pentane having 5 carbon atoms and hexane having 6 carbon atoms. C4 or C7 may be included. Light naphtha can be obtained not only by distillation of crude oil but also by distillation from shale oil or condensate.
  • the raw material may be other than naphtha distilled from crude oil.
  • shale oil other than petroleum, condensate, and other hydrocarbon raw materials that basically use a fraction equivalent to light naphtha. Can do.
  • by-products and the like when various products are produced from petroleum and natural gas can be used as the hydrocarbon raw material, and basically a hydrocarbon having a low boiling point can be used as the raw material.
  • the lower olefin includes, for example, ethylene, propylene, butene, or an olefin having a higher carbon number (for example, 5 to 8 carbon atoms) as the olefin having a lower carbon number.
  • the lower olefin includes ethylene having 2 carbon atoms and propylene having 3 carbon atoms.
  • the lower olefin may contain butene or butadiene having 4 carbon atoms.
  • the contact time as the reciprocal of LHSV (Liquid Hourly Space Velocity) of the raw material hydrocarbon in the composite catalyst of the present embodiment is 0.08 to 1.0 h. It is preferable to set it to 0.08 to 0.4 h.
  • the LHSV is preferably 1.0 to 12.5h-1, and more preferably 2.5 to 12.5h-1.
  • LHSV is the speed at which the raw material hydrocarbon is supplied as a liquid to the composite catalyst
  • the contact time is the time for the raw material hydrocarbon to pass through the composite catalyst as a liquid (composite catalyst).
  • the raw material When the raw material is supplied to the reactor, the raw material is gasified from the liquid as described above, but here, the space velocity of the raw material as the liquid before gasification supplied to the reactor is used) .
  • the space velocity (GHSV) of source gas (gas) may be used as the space velocity, or the space velocity (WHSV) of weight (weight) may be used.
  • the gas flowing out from the catalytic cracking reaction step S1 is quenched (reaction stopped by cooling (rapid cooling)) in a quench tower that is a heat exchanger.
  • the liquefied heavy component is separated, and further the liquefied water is separated.
  • steam may be added as a diluent to light naphtha in the catalytic cracking reaction. In this case, steam is liquefied and separated by cooling.
  • the gas supplied after being pressurized from the quenching / gas pressure raising / dehydration step S2 as described above is cooled and liquefied, and separated from low-boiling substances by a plurality of distillation towers.
  • the undecomposed component (unreacted component) of light naphtha as a raw material is separated as a component for re-decomposition.
  • undecomposed components in the case of night naphtha are mainly composed of C5 (carbon number 5) and C6 (carbon number 6) paraffins.
  • the boiling point is higher than that of C5 and C6 paraffins.
  • an undecomposed component mainly composed of C5 and C6 paraffins is separated as a re-decomposing component (undegraded component: undegraded light naphtha).
  • the re-decomposition component has an undecomposed component as a main component, ethylene and propylene are separated, and hardly contains ethylene and propylene.
  • the separated undecomposed component (redecomposition component) is returned to the catalytic cracking reaction step S1, and again catalytically cracked using a zeolite catalyst.
  • the undecomposed components returned from the separation and purification step S3 to the catalytic cracking reaction step S1 are mainly C5 and C6 paraffins.
  • the weight per time of each substance shown by FIG. 1 describes the result of the experiment and simulation which are demonstrated in the below-mentioned Example.
  • C6 paraffins are described as undecomposed naphtha, but in the experiment in the examples, n-hexane (n is used as a representative component of light naphtha which is a light paraffinic hydrocarbon raw material. -C6H14) is used, and undecomposed components are C6 paraffins, but when light naphtha is used as a raw material, C5 and C6 paraffins are undecomposed components.
  • FIG. 2 shows the production process of a lower olefin by catalytic cracking similar to FIG. 1, but steam is supplied in addition to the raw material in the catalytic cracking reaction. In this case, the production amount of propylene is increased, and details will be described in Examples described later.
  • the light naphtha catalytic cracking reaction using the zeolite catalyst shown in FIG. 1 and the thermal cracking reaction by steam cracking are combined.
  • the production ratio of ethylene and propylene can be changed by adjusting the feed rate of the raw materials for the catalytic cracking reaction and the thermal cracking reaction.
  • the catalytic cracking reaction / quenching step S11 and the steam cracking step S13 are performed in parallel.
  • quenching is performed, and the cracked mixture after catalytic cracking reaction is used for re-cracking with C4 or lower hydrocarbon components and C5 or higher paraffins as main components in a state in which heavy components are removed.
  • the lower hydrocarbon component is sent to a separation and purification apparatus shared with steam cracking, and the re-cracking component is sent to a catalytic cracking reactor.
  • the quenching / gas pressurization / dehydration step S2 and the separation / purification step S3 shown in FIGS. 1 and 2 are not performed, but after the pyrolysis for steam cracking.
  • a lower hydrocarbon separation step S12 for separating the lower hydrocarbon component from the quenched cracked mixture after the catalytic cracking reaction is performed. .
  • the above-described zeolite catalyst is used, and the catalytic cracking reaction using light naphtha as a raw material and the quenching of the cracked mixture through the catalytic cracking reaction And the catalytic cracking reaction / quenching step (catalytic cracking reaction step) S11, and the cooled cracked mixture after quenching with the above-mentioned lower hydrocarbon component and the re-cracking component (residue) containing the undecomposed component
  • the lower hydrocarbon separation step S12 is separated into steam, the steam cracking step S13 in which ethylene and propylene are produced using light naphtha as a raw material by steam cracking (pyrolysis), the cracked mixture after pyrolysis and the lower hydrocarbon component.
  • the catalytic cracking reaction in the catalytic cracking reaction / quenching step S11 is performed by the same method as in the above catalytic cracking reaction step S1. Moreover, quenching is performed in the same manner as the quenching in the above-described quench / gas pressurization / dehydration step S2 for the decomposition mixture after the catalytic cracking reaction. In quenching, heavy components and moisture liquefied from the decomposition mixture after catalytic decomposition are removed.
  • a distillation column is basically used to separate the lower hydrocarbon component of C4 or lower and the residue mainly containing undecomposed components of C5 and C6.
  • an aromatic compound for example, BTX
  • BTX BTX
  • steam and raw materials are supplied to the cracking furnace and heated to 800 ° C. or higher, and the raw materials are pyrolyzed in the presence of steam to produce ethylene and propylene.
  • gas pressurization, acid gas removal, dehydration step (post-thermal decomposition treatment step) S14 quenching is performed to cool the gaseous decomposition mixture (reaction mixture) flowing out from the decomposition furnace and stop the thermal decomposition reaction. Is called.
  • the quench heavy components that are liquefied by cooling are separated, and liquefied water is separated from steam.
  • the pressure of the gas is increased to compress the gas.
  • the acid gas is mainly hydrogen sulfide.
  • DMDS dimethyl disulphide
  • DMDS becomes hydrogen sulfide in the thermal decomposition reaction and prevents adhesion of coke, but hydrogen sulfide is included as an acidic gas in the outflowing gas.
  • gas pressurization, acidic gas removal, dehydration step S14 Hydrogen sulfide gas is removed as an acid gas.
  • the separation and purification step S15 the temperature is lowered to separate methane and the like. As a result, the water may freeze and the pipes may be clogged. Therefore, it is necessary to sufficiently remove the water.
  • Separation and purification step S15 is performed by a method substantially similar to separation and purification step S3 after the catalytic cracking reaction described above.
  • the gas pressurized in the previous step is first cooled to liquefy the gas.
  • the compressor of this cooler is generated using the heat of the cracking furnace. It is designed to work with the steam generated.
  • ethane and propane are separated as lighter (C1 to C3) lower paraffin than C4 and returned to the steam cracking step S13.
  • ethane and propane returned from the separation and purification step S15 are not returned to the main cracking furnace, but a small sub cracking furnace is provided for the main cracking furnace, and the cracking is performed.
  • Lighter (C1-C3) lower paraffins such as ethane and propane returned in the furnace are decomposed.
  • ethane and propane separated in the separation / purification step S15 as the common separation step are supplied to the sub-cracking furnace.
  • the pyrolysis content of the undecomposed component supplied to the steam cracking step S13 is 0%, ethane, propane, etc. can be pyrolyzed by starting the sub-decomposition furnace. In this case, it is preferable to operate the process after the steam cracking process S13.
  • lighter (C1 to C3) lower paraffin than C4 may be stored and supplied to the main cracking furnace when the main cracking furnace is operated.
  • light naphtha is supplied as a raw material to the catalytic cracking reaction / quenching step S11 and the steam cracking step S13.
  • the raw material supplied at this time is distributed to the catalytic cracking portion to be sent to the catalytic cracking reaction / quenching step S11 and the thermal cracking portion to be sent to the steam cracking step S13.
  • the distribution ratio at this time can be adjusted.
  • the ratio of the catalytically decomposed portion and the thermally decomposed portion of the raw material can be changed, for example, from 0% to 100% of the proportion of the catalytically decomposed portion of the raw material. It can be changed from% to 0%.
  • the catalytic cracking of the raw material is 0%
  • the thermal cracking is 100%
  • the catalytic cracking is 50% and the thermal cracking is 50%, as shown in FIG.
  • the catalytic decomposition is 80%
  • the thermal decomposition is 20%
  • the catalytic decomposition is 100% and the thermal decomposition is 0%.
  • the amount of ethylene, propylene, etc. produced in the state where the ratio of the pyrolysis component and the catalytic decomposition component is changed will be described as a result of experiments and simulations in the examples described later.
  • the main cracking furnace for steam cracking is stopped (the sub cracking furnace is activated).
  • the steam for operating the compressor of the refrigerating machine in the separation and purification step S15 cannot be supplied from the main cracking furnace, but the steam cracking equipment is in a state where the temperature of the cracking furnace has not yet been raised at the start of operation.
  • a start-up boiler that supplies steam to the cracking furnace is provided, and steam can be supplied from the start-up boiler to the compressor of the cooler.
  • the production ratio of propylene is higher than that of ethylene
  • the production ratio of ethylene is higher than that of propylene.
  • the thermal decomposition reaction by steam cracking the production ratio of propylene can be improved and the production amount of propylene can be improved.
  • the catalytic cracking reaction requires a lower temperature than the thermal cracking reaction, and energy efficiency is achieved by combining the catalytic cracking reaction and the thermal cracking reaction by steam cracking rather than producing ethylene and propylene by steam cracking alone. And energy saving is possible.
  • the common post-treatment means 15 for performing the gas removal / dehydration step (common post-treatment step) S14, the decomposition mixture after thermal decomposition, and the lower hydrocarbon component are described above.
  • a common separation and purification means 16 for separation and purification step S15 are described above.
  • the catalytic cracking cooling means 11 rapidly cools the reactor filled with the above-mentioned zeolite catalyst in a fixed bed system, a heating device for heating the reactor to the above-mentioned predetermined temperature, and the cracked mixture after catalytic cracking. And a quenching quenching device for stopping the reaction.
  • the lower hydrocarbon separation means 12 removes aromatic hydrocarbons such as BTX as heavy components from the cracked mixture using, for example, about two distillation columns, and then regenerates C4 or lower hydrocarbon components and C5 or higher recycle components. Fractionated into components for decomposition (undecomposed components). A facility that is simple in comparison with a facility that has many distillation columns corresponding to each component to be separated, such as the shared separation and purification means 16.
  • the distribution unit 13 distributes the light paraffinic hydrocarbon raw material into the above-described pyrolysis component and the catalytic cracking component and adjusts the distribution ratio, and supplies the pyrolysis component to the reactor of the catalytic cracking cooling unit 11.
  • the pyrolyzed component is supplied to the cracking furnace of the pyrolyzing means 14.
  • the thermal decomposition means 14 includes the above-described main cracking furnace for steam cracking, a sub-decomposing furnace, a startup boiler, and the like.
  • the shared post-processing means 15 includes a quenching quenching device (quenching tower), a gas booster, a dehydrating device, an acid gas removing device, and the like.
  • the common separation and purification means 16 includes the above-described refrigerator and a plurality of distillation columns for separation of methane, hydrogen, etc., separation of ethane and ethylene, separation of propane and propylene, and the like. For example, a plurality of distillation columns such as a distillation column for separating ethane and ethylene together as a C2 hydrocarbon and a distillation column for separating ethane and ethylene separated separately are provided.
  • a lower olefin can be produced by the above-described production method of lower olefin. That is, according to the lower olefin production apparatus, the quenching quenching apparatus is provided downstream of the catalytic cracking reactor, and the lower hydrocarbon separation means 12 is provided downstream thereof to simplify separation and purification after catalytic cracking. In other words, it is only separated into a lower hydrocarbon component and a re-cracking component. Final separation of ethylene, propylene, and the like is performed by the shared separation and purification means 16 together with the decomposition mixture after thermal decomposition.
  • the construction method of such a lower olefin production apparatus is the above-mentioned catalytic cracking cooling means 11 (catalytic cracking reaction equipment) in the site of the steam cracker (cracking furnace: steam cracking equipment) or in the site adjacent to or adjacent thereto. : Reactor, quench quenching device), lower hydrocarbon separation means 12 and distribution means 13.
  • the common post-treatment means 15 and the common separation / purification means (separation purification equipment) 16 are not only the post-treatment and separation / purification of the cracked mixture after pyrolysis, but also the lower hydrocarbons separated from the cracked mixture after catalytic cracking. It will also be used for work-up of components and separation and purification.
  • shared post-processing means 15 and shared separation purification means 16 are existing facilities of a steam cracker, and do not need to be newly provided when constructing the lower olefin production apparatus of the present embodiment. Although there is a possibility that a change or replacement of some devices may be required, the construction cost can be greatly reduced.
  • a light olefin which is a light paraffinic hydrocarbon raw material
  • a method for producing a lower olefin mainly producing ethylene and propylene, a lower olefin The manufacturing apparatus of this and the construction method of the manufacturing facility of a lower olefin are demonstrated.
  • ethylene and propylene are produced by combining production of ethylene and propylene by a catalytic cracking reaction using a zeolite catalyst and production of ethylene and propylene by steam cracking. This makes it possible to adjust the production ratio of ethylene and propylene in the same manner as in the first embodiment.
  • the method for producing the lower olefin by the catalytic cracking reaction is the same as in the first embodiment.
  • the light naphtha catalytic cracking reaction using the zeolite catalyst shown in FIG. 1 and the thermal cracking reaction by steam cracking are combined.
  • the production ratio of ethylene and propylene can be changed by adjusting the feed rate of the raw materials for the catalytic cracking reaction and the thermal cracking reaction.
  • the raw material for the thermal decomposition reaction is mainly an undecomposed component in the catalytic decomposition reaction.
  • the catalytic cracking reaction step S1 is performed prior to the steam cracking step S4, and undecomposed components (mainly C5 and C6 paraffins) in the cracked mixture flowing out from the catalytic cracking reaction step S1.
  • the total amount is not returned to the catalytic cracking reaction step S1 as shown in FIG. 1, but undecomposed components are supplied to the steam cracking step S4 as shown in FIG.
  • what is supplied to the steam cracking step S4 is not limited to undecomposed components, and is not particularly limited to C5 and C6 paraffins, and may include C2 to C4 hydrocarbons. .
  • ethane and propane as lower paraffin of C3 or less separated in the separation and purification step S3 are supplied to the steam cracking step S4.
  • the catalytic cracking reaction step S1 the quench gas pressurization / dehydration step S2, and the separation and purification step (catalytic cracking separation step) S3 for catalytic cracking reaction are performed.
  • the steam cracking step S4 is performed. After pyrolysis in the steam cracking step S4, quench, gas pressurization, acid gas removal, dehydration step (post-thermal decomposition treatment step) S5, and separation and purification step (thermal decomposition separation step) S6 after the thermal decomposition reaction are performed. Is called.
  • steam and raw materials are supplied to the cracking furnace and heated to 800 ° C. or higher, and the raw materials are pyrolyzed in the presence of steam to produce ethylene and propylene.
  • gas pressurization, acid gas removal, dehydration step (thermal decomposition post-processing step) S5 quenching is performed to cool the gaseous decomposition mixture (reaction mixture) flowing out from the decomposition furnace and stop the thermal decomposition reaction. Is called.
  • the quench heavy components that are liquefied by cooling are separated, and liquefied water is separated from steam.
  • the gas is pressurized to compress the gas.
  • the acid gas is mainly hydrogen sulfide.
  • DMDS dimethyl disulphide
  • DMDS becomes hydrogen sulfide in the thermal decomposition reaction and prevents the adhesion of coke, but hydrogen sulfide is included as an acidic gas in the outflow gas.
  • gas pressurization, acidic gas removal, dehydration step S5 Hydrogen sulfide gas is removed as an acid gas.
  • the separation and purification step S6 the temperature is lowered to separate methane and the like. As a result, the water may freeze and the pipes may be clogged. Therefore, it is necessary to sufficiently remove the water.
  • the separation / purification step S6 is basically performed by a method substantially the same as the separation / purification step S3 after the catalytic cracking reaction.
  • the gas pressurized in the previous step is first cooled in order to liquefy the gas.
  • the compressor of this cooler is generated using the heat of the cracking furnace. It is designed to work with the steam generated.
  • ethane and propane are separated as lighter (C1 to C3) lower paraffin than C4 and returned to the steam cracking step S4.
  • ethane and propane returned from the separation and purification step S6 are not returned to the main cracking furnace, but a small sub-cracking furnace is provided for the main cracking furnace, and the cracking is performed.
  • Lighter (C1-C3) lower paraffins such as ethane and propane returned in the furnace are decomposed.
  • ethane and propane separated in the separation / purification step S3 as the catalytic cracking separation step and the separation / purification step S6 as the thermal cracking / separation step are supplied to the sub-cracking furnace.
  • the sub-decomposition furnace is activated to thermally decompose ethane, propane and the like. In this case, it is preferable to operate the process after the steam cracking process S4.
  • the lower paraffin that is lighter (C1 to C3) than C4 separated in the separation and purification step S3 and supplied to the steam cracking step S4 may be returned to the main cracking furnace.
  • lower paraffin that is lighter than C4 (C1 to C3) is stored and supplied to the main cracking furnace when the main cracking furnace is activated It is good.
  • ethylene and propylene are produced by a catalytic cracking reaction using a zeolite catalyst.
  • the undecomposed component in the catalytic cracking reaction is divided into a reflux component that returns to the reactor that performs the catalytic cracking reaction, and a forward flow component that is sent to the cracking furnace that performs steam cracking. Produces ethylene and propylene by steam cracking from the forward flow.
  • the ratio of the reflux portion of the undecomposed component to the forward flow portion can be changed, for example, from 0% to 100% of the reflux portion of the undecomposed component, and the ratio of the forward flow portion corresponding to the change is 100. It can be changed from% to 0%.
  • the reflux of the undecomposed component is 0%
  • the forward flow is 100%
  • the reflux is 50% and the forward flow is 50%.
  • the reflux component is 80% and the forward flow component is 20%.
  • the reflux component is 100% and the forward flow component is 0%.
  • the production ratio of propylene is higher than that of ethylene
  • the production ratio of ethylene is higher than that of propylene.
  • the thermal decomposition reaction by steam cracking the production ratio of propylene can be improved and the production amount of propylene can be improved.
  • the catalytic cracking reaction requires a lower temperature than the thermal cracking reaction, and energy efficiency is achieved by combining the catalytic cracking reaction and the thermal cracking reaction by steam cracking rather than producing ethylene and propylene by steam cracking alone. And energy saving is possible.
  • the lower olefin production apparatus includes a catalytic cracking means (catalytic cracking reaction facility) 10 for performing the above-described catalytic cracking reaction step S1, and the above-described quench gas pressurization / dehydration step (after catalytic cracking).
  • a catalytic cracking means catalytic cracking reaction facility 10 for performing the above-described catalytic cracking reaction step S1
  • the above-described quench gas pressurization / dehydration step after catalytic cracking
  • the post-pyrolysis treatment means 50 for performing S5 and the pyrolysis separation and purification means 60 for carrying out the separation and purification step S6 described above are provided.
  • the catalytic cracking means 10 includes a reactor filled with the above-mentioned zeolite catalyst in a fixed bed system, and a heating device for heating the reactor to the above-mentioned predetermined temperature.
  • the catalytic cracking post-treatment means 20 includes a quenching quenching device (quenching tower), a gas booster, a dehydrating device, and the like.
  • quenching quenching device quenching tower
  • gas booster gas booster
  • dehydrating device a dehydrating device that further removes moisture.
  • water is hardly contained in the cracked mixture after the catalytic cracking treatment unless steam is added.
  • the separation and purification means 30 for catalytic cracking includes the above-described refrigerator and a plurality of distillation columns for separation of methane, hydrogen, etc., separation of ethane and ethylene, separation of propane and propylene, and the like.
  • a plurality of distillation columns such as a distillation column for separating ethane and ethylene together as a C2 hydrocarbon and a distillation column for separating ethane and ethylene separated separately are provided.
  • the distribution means 35 distributes undecomposed components (redecomposition components) mainly composed of C5 and C6 paraffin, and is composed of a pipe, a pump, a valve, and the like. It separates into minutes. In addition, the distribution ratio between the forward flow portion and the reflux portion can be adjusted.
  • undecomposed components mainly composed of C5 and C6 paraffin
  • the thermal decomposition means 40 includes the above-described main cracking furnace for steam cracking, a sub-decomposing furnace, a startup boiler, and the like.
  • the thermal decomposition post-treatment means 50 includes a quenching quenching device (quenching tower), a gas pressure raising device, a dehydration device, an acid gas removal device, and the like. It has the structure which added the removal apparatus.
  • the pyrolysis separation / purification means 60 basically includes a cooling device and various distillation towers in the same manner as the catalytic cracking separation / purification means 30.
  • a lower olefin can be produced by the above-described production method of lower olefin.
  • the catalytic cracking separation / purification means 30 and the thermal cracking separation / purification means 60 are separately provided.
  • the decomposition mixture flowing out from the thermal decomposition post-treatment means 50 may be combined and separated and purified by the separation and purification means.
  • the undecomposed component separated from the separation and purification means is separated into a forward flow component and a reflux component by the distribution means 35.
  • a catalytic cracking reaction means (reactor: catalytic cracking reaction facility) 10 using a zeolite catalyst is additionally provided in an existing steam cracker.
  • the catalytic cracking means 10 the catalytic cracking post-processing means 20, the catalytic cracking separation and purification means 30, and the distributing means 35 are provided in the site of the steam cracker or adjacent or close to the site, as described above.
  • facilities such as a pump, piping and valves for sending C3 or lower lower paraffin from the catalytic cracking separation and purification means 30 to the thermal cracking means 40.
  • the steam cracker is a product whose main products are the above-mentioned ethylene and propylene.
  • the production amount of propylene is low and the energy efficiency is low as described above.
  • the production facility for ethylene and propylene by the catalytic cracking reaction using the zeolite catalyst as described above or the production facility for ethylene or propylene by other methods may be replaced.
  • ethylene and propylene are currently produced by steam crackers, and in the current situation, it is costly to dispose of equipment and to construct new equipment to break down the steam cracking equipment. There is.
  • the equipment for catalytic cracking reaction to the existing steam cracker as described above, the cost for disposal of equipment is not required, and part of the existing equipment can be used for the production of lower olefins by catalytic cracking reaction. By diverting, etc., it is possible to increase the production amount of propylene and improve the energy efficiency while suppressing the construction cost.
  • both steam cracking and catalytic cracking reactions can basically produce ethylene and propylene from the same raw material, and the production and separation methods after decomposition are similar, and separation and purification of ethylene and propylene using substantially the same equipment. Therefore, if the separation and purification equipment can be used together by remodeling a part of the separation and purification equipment, the construction cost can be further reduced and the space efficiency can be increased.
  • the reaction is stopped by cooling after catalytic cracking, and then the cooled cracked mixture mainly contains ethylene and propylene.
  • the lower hydrocarbon component is separated into a residue containing mainly undecomposed components (C5, C6 paraffin), and the lower hydrocarbon components are sent to the post-pyrolysis treatment and heated using a separation and purification facility for thermal decomposition. It is processed with the decomposition mixture after decomposition, and ethylene and propylene are separated.
  • the residue is distributed as a re-decomposition component into the above-mentioned forward flow and reflux components, and is used to produce ethylene and propylene by catalytic cracking reaction or thermal cracking reaction.
  • the method for producing a lower olefin according to the present embodiment is a catalytic cracking reaction / quenching step in which a catalytic cracking reaction using a zeolite catalyst similar to that of the first embodiment and a quenching of the cracked mixture through the catalytic cracking reaction are performed.
  • Catalytic cracking reaction step S21 and a lower hydrocarbon separation step S22 for separating the cooled cracked cracked mixture into the above-mentioned lower hydrocarbon component and a re-cracking component (residual component) containing an undecomposed component;
  • a steam cracking step S24 in which the components for re-cracking including the undecomposed components separated in the lower hydrocarbon separation step S22 are supplied to produce ethylene and propylene by steam cracking (pyrolysis), and a cracked mixture after pyrolysis, Quench, gas pressurization, acid gas removal, dehydration step (thermal decomposition post-treatment step) S25 for performing post-treatment on the lower hydrocarbon component Provided from the decomposition mixture and lower hydrocarbon components after pyrolysis of ethylene, and a common separation and purification process for separating propylene and the like (shared separation step) S26.
  • the catalytic cracking reaction in the catalytic cracking reaction / quenching step S21 is performed by the same method as in the first embodiment.
  • the quench is performed in the same manner as the quench described in the second embodiment for the decomposition mixture after the catalytic decomposition reaction. In quenching, heavy components and moisture liquefied from the decomposition mixture after catalytic decomposition are removed.
  • the lower hydrocarbon separation step S22 basically, a distillation column is used to separate a lower hydrocarbon component of C4 or less and a residual component mainly containing undecomposed components of C5 and C6.
  • an aromatic compound for example, BTX
  • ethane, propane, butane as paraffin and ethylene, propylene, butene, butadiene, etc. as olefins.
  • the steam cracking step S24 is the same as the steam cracking step S4 of the second embodiment.
  • the quenching / gas boosting / acid gas removal / dehydration step S25 is the same as the quenching / gas boosting / acid gas removal / dehydration step S5 of the second embodiment, but in this embodiment, after the thermal decomposition, In addition to the cracked mixture, the above-mentioned lower hydrocarbon component is treated.
  • the future reaction product after pyrolysis and the lower hydrocarbon component may be mixed and supplied to the quench / gas pressurization / acid gas removal / dehydration step S25. Since the quenching previously performed in the gas pressurization / acid gas removal / dehydration step S25 is completed, the lower hydrocarbon component may be introduced after the quench in the quench / gas pressurization / acid gas removal / dehydration step S25. Good.
  • the common separation / purification step S26 is basically the same as the separation / purification step S3 for catalytic cracking and the separation / purification step S6 for thermal cracking according to the second embodiment.
  • -Ethylene and propylene are isolate
  • the method for producing a lower olefin of the third embodiment not only can the same effects as those of the first embodiment be obtained, but also the catalytic cracking reaction and the thermal cracking reaction
  • the post-treatment process for example, quenching, gas pressurization, acid gas removal, dehydration process S25
  • separation and purification process S26 using the same equipment for the thermal decomposition reaction and the catalytic decomposition reaction. Costs related to the equipment can be reduced.
  • the existing steam cracking equipment is used as post-treatment equipment after the catalytic cracking (quenching device, gas booster, dehydrator).
  • existing steam cracking equipment such as various distillation towers) can be used for separation and purification of the cracked mixture after catalytic cracking.
  • the lower olefin production apparatus for producing the lower olefin by the lower olefin production method of the third embodiment performs the above-described catalytic cracking reaction / quenching step S21 as shown in FIG.
  • Catalytic cracking cooling means catalytic cracking means 110 for separating the lower hydrocarbon component from the cracked mixture generated by the catalytic cracking reaction and separating the re-cracking component including the undecomposed component from the lower hydrocarbon separation step S22
  • the lower hydrocarbon separation means 120 for performing the separation and the separated undecomposed component are separated into the above-mentioned reflux component and the forward flow component, and the distribution ratio of the reflux component and the forward flow component is adjusted.
  • the distribution means 130, the thermal cracking means 140 for performing the above-described steam cracking step S24, the cracked mixture and the lower hydrocarbon component after the thermal cracking The post-treatment unit 150 for performing the quench, gas pressurization, acid gas removal, dehydration step (common post-treatment step) S5, and the above-described separation and purification step S26 for the pyrolysis decomposition mixture and lower hydrocarbon components. And a common separation and purification means 160 for performing.
  • the catalytic cracking cooling means 110 includes the quenching quenching device (quenching tower) described above in addition to the catalytic cracking means 10 including the reactor of the second embodiment. After the cracked mixture after the catalytic cracking reaction flowing out from the reactor is quenched, it is supplied to the lower hydrocarbon separation means 120. In addition, when supplying steam to a reactor, water is removed by quenching.
  • quenching quenching device quenching tower
  • the lower hydrocarbon separation means 120 removes aromatic hydrocarbons such as BTX as heavy components from the cracked mixture by using, for example, about two distillation columns, and then regenerates C4 or lower hydrocarbon components and C5 or higher recycle components. Fractionated into components for decomposition (undecomposed components). It becomes a simple installation with respect to the installation provided with many distillation columns corresponding to each component isolate
  • the distribution unit 130 distributes the re-decomposition component to the above-mentioned forward flow component and the reflux component and can adjust the distribution ratio, and the forward flow component is catalytically decomposed.
  • the cooling unit 110 is supplied to the reactor, and the forward flow is supplied to the cracking furnace of the thermal decomposition unit 140.
  • the thermal decomposition means 140 is the same as the thermal decomposition means 40 of the second embodiment.
  • the shared post-processing means 150 is the same as the thermal decomposition post-processing means 50 of the second embodiment, and the shared separation and purification means 160 is the thermal decomposition separation and purification means 60 of the second embodiment. Is the same. However, the common post-treatment means 150 and the common separation and purification means 160 are supplied with a lower hydrocarbon component in addition to the decomposition mixture after the thermal decomposition reaction.
  • the downstream side of the catalytic cracking reactor instead of including the catalytic cracking post-treatment means 20 and the catalytic cracking separation and purification means 30 as in the second embodiment, the downstream side of the catalytic cracking reactor. Is equipped with a quenching quenching device, and a lower hydrocarbon separation means 120 is provided downstream thereof to simplify separation and purification after catalytic cracking, and only separates into a lower hydrocarbon component and a recracking component. Final separation of ethylene, propylene, and the like is performed by the shared separation and purification means 160 together with the decomposition mixture after thermal decomposition.
  • Such a low olefin production apparatus is constructed by the above-described catalytic cracking cooling means 110 (catalytic cracking means: in a site adjacent to or adjacent to a steam cracker (cracking furnace: steam cracking facility)). Reactor, quench quenching device), lower hydrocarbon separation means 120, and distribution means 130.
  • the common post-treatment means 150 and the common separation / purification means (separation purification equipment) 160 are not only post-treatment and separation / purification of the cracked mixture after pyrolysis, but also lower hydrocarbons separated from the cracked mixture after catalytic cracking. It will also be used for work-up of components and separation and purification.
  • shared post-processing means 150 and shared separation and purification means 160 are existing facilities of a steam cracker, and do not need to be newly provided when constructing the lower olefin production apparatus of the present embodiment. Although it may be necessary to change or replace some devices, the construction cost can be greatly reduced.
  • n-hexane (n-C6H14) was used as a representative component of light naphtha which is a light paraffinic hydrocarbon raw material.
  • MFI type crystalline aluminosilicate containing iron and gallium was used as the zeolite of the zeolite catalyst.
  • the zeolite catalyst used was a composite catalyst obtained by molding the above-mentioned zeolite powder with a binder, and silica (SiO 2) was used as the binder.
  • the mixing ratio of zeolite and silica, that is, the zeolite / SiO 2 mixing ratio is 90 wt% / 10 wt%.
  • the reaction conditions for the catalytic cracking reaction were a reaction temperature of 565 ° C., a total pressure of 0.1 MPa, n-hexane LHSV of 6.0 h-1, and a zeolite catalyst amount of 1.8 ml.
  • concentration of each product after reacting n-hexane only once (one pass) and unreacted n-hexane was measured by gas chromatography without returning the undecomposed component (redecomposition component).
  • the yield of each component was determined. Based on the result (yield), the yield of each component (Overall yield) when it was assumed that the undecomposed component was refluxed and continuously reacted (FIG. 1) was calculated.
  • FIG. 9 shows the one-pass yield of each component as an experimental result and the overall yield in the case of continuous reaction.
  • the yield of ethylene (C2H4) is 10.0 wt%
  • the yield of propylene (C3H6) is 22.6 wt%
  • the production ratio of ethylene and propylene is about 1: 2
  • the yield varies depending on the molar composition ratio of each element of the zeolite, the kind of the binder, the reaction conditions, and the like.
  • reaction conditions when the raw material is diluted by introducing steam in addition to the raw material during the catalytic cracking reaction, the yield of propylene may be increased by about 1.5 times, for example, depending on the amount of steam introduced. Is possible.
  • n-hexane n-C6H14
  • naphtha a representative component of light naphtha, which is a light paraffinic hydrocarbon raw material, as in the above-described experiment.
  • MFI type crystalline aluminosilicate containing iron not containing gallium
  • Ga is included in the denominator, but the number of moles of Ga is zero.
  • the zeolite catalyst used is a composite catalyst obtained by molding the above-mentioned zeolite powder with a binder, and alumina (Al 2 O 3) was used as the binder.
  • the mixing ratio of zeolite and alumina, that is, the Zeolite / Al2O3 mixing ratio is 71 wt% / 29 wt%.
  • the reaction conditions for the catalytic cracking reaction were a reaction temperature of 565 ° C., a total pressure of 0.1 MPa, n-hexane LHSV of 1.0 h-1, and a zeolite catalyst amount of 9.3 ml. Moreover, although the raw material and steam were mixed, the amount of steam was 27% with respect to the total amount of gas flowing into the reactor.
  • each product after reacting n-hexane only once (one pass) without returning the undecomposed component (redecomposition component) and unreacted n-hexane The concentration was measured by gas chromatography, and the yield of each component was determined.
  • FIG. 10 shows the one pass yield of each component and the overall yield in the case of continuous reaction.
  • the yield of ethylene (C2H4) is 10.6 wt%
  • the yield of propylene (C3H6) is 29.4 wt%
  • the production ratio of ethylene and propylene is about 1: It was 2.8.
  • the yield of ethylene was 31.1 wt% and the yield of propylene was 17.1 wt%, as shown in Comparative Example 1 in FIG. It was. Therefore, the production ratio of ethylene and propylene was about 1: 0.5.
  • the comparative example 1 is the yield of ethylene and propylene in the existing steam cracker.
  • Examples 1 to 4 corresponding to the first embodiment will be described with reference to FIGS. 3 to 7 and FIG.
  • the yields of ethylene and propylene in the catalytic cracking reactions of Examples 1 to 3 were obtained by using the one-pass experimental results (FIG. 9) in the n-hexane catalytic cracking reaction test without dilution.
  • This is a calculation result when the distribution ratio of the raw material supplied to the catalytic cracking reactor is 0%, 50%, 80%, and 100%.
  • the yield of ethylene and propylene in the catalytic cracking reaction of Example 4 is 100% based on the distribution ratio of the raw material supplied to the catalytic cracking reactor using the one pass experimental result (FIG. 10) under the steam dilution condition.
  • the process diagram shown in FIG. 3 is assumed to be Example 0, and the yields of ethylene and propylene are the same as those of Comparative Example 1. That is, the yield of ethylene is 31.1%, the yield of propylene is 17.1%, and the combined yield of these ethylene and propylene is 48.2%.
  • Example 1 as shown in FIG. 4 and FIG. 11, the thermal decomposition amount of the raw material (n-hexane) sent to the thermal decomposition reaction is 50%, and the catalytic decomposition amount sent to the catalytic decomposition reaction is 50%. ing.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 26.2%
  • the yield of propylene was 21.0%
  • the combined yield of ethylene and propylene was 47. .2%.
  • Example 2 as shown in FIG. 5 and FIG. 11, the pyrolysis component sent to the pyrolysis reaction of the raw material is 20%, and the catalytic cracking component sent to the catalytic cracking reaction is 80%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction is 23.3%
  • the yield of propylene is 23.3%
  • the combined yield of these ethylene and propylene is 46. .6%.
  • Example 3 as shown in FIGS. 6 and 11, the pyrolysis component sent to the pyrolysis reaction of the raw material is 0%, and the catalytic cracking component sent to the catalytic cracking reaction is 100%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 21.4%
  • the yield of propylene was 24.9%
  • the combined yield of ethylene and propylene was 46. .2%.
  • Example 4 as shown in FIG. 7 and FIG. 11, the pyrolysis component sent to the pyrolysis reaction of the raw material is 0%, and the catalytic cracking component sent to the catalytic cracking reaction is 100%.
  • steam that is 27% of the total supply amount of the raw material and steam is introduced into the reaction vessel.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction is 21.9%
  • the yield of propylene is 31.6%
  • the combined yield of ethylene and propylene is 53. .5%.
  • Comparative Example 1 since the yield of ethylene by steam cracking is high, the combined yield of ethylene and propylene is slightly higher than in Examples 1 to 3. In addition, it is possible to increase the combined yield of ethylene and propylene in the catalytic cracking reaction, as shown in Example 4, by changing the experimental conditions, for example, by introducing steam into the catalytic cracking reaction, etc. The difference in the combined yield of ethylene and propylene of Comparative Example 1 and Examples 1 to 3 is not so great as to be a problem.
  • the difference in the combined yield of ethylene and propylene in Examples 1 to 3 is an error level.
  • the proportion of catalytic cracking in the feedstock is increased to 0%, 50%, 80% and 100%, the yield of propylene will increase from 17.1 wt% to 24.9 wt%.
  • the yield of ethylene will drop to 31.1 wt% to 21.4 Wt%. That is, it is possible to adjust the production amounts of ethylene and propylene.
  • the production ratio of propylene / ethylene can be adjusted from 0.55 to about 1.16. In this case, it becomes possible to increase the production ratio of propylene to ethylene as compared with the case where the OCT process is combined with steam cracking.
  • the production ratio of propylene / ethylene is 1.44, and the production ratio of propylene can be further increased. Even if the raw material supplied to the steam cracking is 0%, ethane and propane separated from the cracked mixture after the catalytic cracking reaction are supplied to the steam cracking, so the yield of ethylene and propylene in the steam cracking is Not 0%.
  • the yield of ethylene is 31.1 wt% and the yield of propylene is 17.1 wt as shown in Comparative Example 1 in FIGS. %Met. Therefore, the production ratio of ethylene and propylene was about 1: 0.5.
  • the comparative example 1 is the yield of ethylene and propylene in the existing steam cracker.
  • Examples 5 to 8 corresponding to the second embodiment will be described with reference to FIGS. 12 to 15 and FIG.
  • the yields of ethylene and propylene in the catalytic cracking reactions in Examples 5 to 8 were determined based on the experimental results (one-pass yield) in FIG. It is a calculation result when the amount is 0%, 50%, 80%, and 100%.
  • the yields of ethylene and propylene in the thermal decomposition reaction of each example are the undecomposed components (redecomposition components), ethane and propane yields in the above-described one-pass, It was obtained by calculation based on the yield of Comparative Example 1 from the distribution amount (0%, 20%, 50%, 100%) of the reflux / recycled use.
  • Example 5 as shown in FIG. 12 and FIG. 22, the re-decomposition component sent to the thermal decomposition reaction side is 100%, and the reflux amount returned to the catalytic decomposition reaction side is 0%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 25.4%, and the yield of propylene was 21.7%.
  • the combined yield of these ethylene and propylene was 47. 1%.
  • Example 6 As shown in FIG. 13 and FIG. 22, 50% of the re-decomposition component is sent to the thermal decomposition reaction side, and 50% of the reflux component is returned to the catalytic decomposition reaction side.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 23.4%
  • the yield of propylene was 23.3%
  • the combined ratio of these ethylene and propylene was 46.6. %.
  • Example 7 as shown in FIG. 14 and FIG. 22, the re-decomposition component sent to the thermal decomposition reaction side is 20%, and the reflux amount returned to the catalytic decomposition reaction side is 80%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 22.2%, and the yield of propylene was 24.2%.
  • the combined yield of these ethylene and propylene was 46. 4%.
  • Example 8 as shown in FIG. 15 and FIG. 22, the amount sent to the thermal decomposition reaction side of the re-decomposition component is 0%, and the reflux amount returned to the catalytic decomposition reaction side is 100%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 21.4%, and the yield of propylene was 24.9%.
  • the combined yield of these ethylene and propylene was 46. 2%.
  • Comparative Example 1 since the yield of ethylene by steam cracking is high, the combined yield of ethylene and propylene is slightly higher than in Examples 5 to 8. It is possible to increase the combined yield of ethylene and propylene in the catalytic cracking reaction by changing the experimental conditions, for example, by introducing steam into the catalytic cracking reaction. Comparative Example 1 and Example 5 The difference in the combined yield of ethylene and propylene in Example 8 is not so great as to be a problem.
  • the difference in the combined yield of ethylene and propylene in Examples 5 to 8 is an error level.
  • the ratio of the re-decomposition component reflux is increased to 0%, 50%, 80%, and 100%
  • the yield of propylene increases from 21.7 wt% to 24.9 wt%.
  • the yield of ethylene falls to 25.4 wt% to 21.4 Wt%. That is, it is possible to adjust the production amounts of ethylene and propylene.
  • the production ratio (weight) of propylene / ethylene can be adjusted from 0.85 to 1.16. Therefore, the production ratio of propylene can be increased as compared with the case where steam cracking and the OCT process are combined. Even if the re-cracking component supplied to the steam cracking is 0%, ethane and propane separated from the cracked mixture after the catalytic cracking reaction are supplied to the steam cracking. The yield is not 0%.
  • Examples 9 to 12 corresponding to the method for producing a lower olefin of the third embodiment will be described with reference to FIGS. 17 to 20 and FIG.
  • the yield is obtained by calculation based on the one-pass experimental result of the catalytic cracking reaction shown in FIG. That is, as shown in FIGS. 17 to 20, the concentration of each product of the cracked mixture after steam cracking and the lower hydrocarbon separated after the catalytic cracking reaction is not measured by gas chromatography or the like.
  • the yields of ethylene and propylene are obtained by the same calculation as in Examples 5 to 8, and the distribution ratio of the forward flow and the reflux of the undecomposed component (redecomposition component) is the same. Then, the yields of ethylene and propylene are the same in Examples 5 to 8 and Examples 9 to 12.
  • Example 9 the results of Examples 5 to 8 corresponding to the second embodiment shown in FIG. 22 are the same as the results of Examples 9 to 12 corresponding to the third embodiment shown in FIG. It has become. That is, in Example 9, as shown in FIGS. 17 and 23, the forward flow sent to the thermal decomposition reaction among the components for re-decomposition is 100%, and the reflux returned to the catalytic decomposition reaction is 0%. . In this case, the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 25.4%, the yield of propylene was 21.7%, and the combined yield of ethylene and propylene was 47. .1%.
  • Example 10 as shown in FIGS. 18 and 22, the forward flow sent to the thermal decomposition reaction among the components for re-decomposition is 50%, and the reflux returned to the catalytic decomposition reaction is 50%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 23.4%
  • the yield of propylene was 23.3%
  • the combined yield of these ethylene and propylene was 46. .6%.
  • Example 11 as shown in FIG. 19 and FIG. 22, the forward flow sent to the thermal decomposition reaction among the components for re-decomposition is 20%, and the reflux flow returned to the catalytic decomposition reaction is 80%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction is 22.2%
  • the yield of propylene is 24.2%
  • the combined yield of ethylene and propylene is 46. 4%.
  • Example 12 as shown in FIG. 20 and FIG. 22, the forward flow sent to the thermal decomposition reaction among the components for re-decomposition is 0%, and the reflux amount returned to the catalytic decomposition reaction is 100%.
  • the combined yield of the catalytic cracking reaction and the thermal cracking reaction was 21.4%
  • the yield of propylene was 24.9%
  • the combined yield of ethylene and propylene was 46. .2%.
  • the method for producing the lower olefin of the second embodiment and the method for producing the lower olefin of the third embodiment differ in the separation method of the components for re-decomposition, but basically the same raw materials are used. Since the re-decomposition component can be distributed in the same manner, the yields of ethylene and propylene are likely to be substantially the same in the second embodiment and the third embodiment.
  • catalytic cracking means (reactor: catalytic cracking reactor) 11 catalytic cracking cooling means (catalytic cracking means: reactor, quench quenching device) 12 Lower hydrocarbon separation means 13 Distribution means 14 Pyrolysis means (cracking furnace, steam cracking equipment) 16 Common separation and purification means (Separation and purification equipment: Steam cracking equipment) 30 Separation and purification means for catalytic cracking 35 Distributing means 40 Thermal decomposition means (cracking furnace, steam cracking equipment) 60 Separation and purification means for pyrolysis (separation and purification equipment: steam cracking equipment) 110 catalytic cracking cooling means (catalytic cracking means: reactor, quench quenching device) 120 Lower hydrocarbon separation means 130 Distribution means 140 Pyrolysis means (cracking furnace, steam cracking equipment) 160 Common separation and purification means (Separation and purification equipment: Steam cracking equipment) S1 catalytic cracking reaction process S3 separation and purification process (separation process for catalytic cracking) S4

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Abstract

Cette invention concerne un procédé et un dispositif de production d'oléfines inférieures, un procédé de construction pour équipement de production d'oléfines inférieures, et un catalyseur de type zéolithe qui permettent de modifier facilement les taux de production d'éthylène et de propylène et de réduire les coûts d'équipement, lors de la production d'éthylène et de propylène à partir d'un matériau de départ hydrocarboné à base de paraffine légère tel qu'un naphta léger. Le procédé de production comprend : une étape S21 de réaction de craquage catalytique qui consiste à générer de l'éthylène et du propylène à partir d'un matériau de départ hydrocarboné à base de paraffine légère par une réaction de craquage catalytique faisant appel à un catalyseur de type zéolithe ; et une étape S13 de vapocraquage qui consiste à produire de l'éthylène et du propylène à partir d'un matériau de départ hydrocarboné à base de paraffine légère par vapocraquage.
PCT/JP2015/085649 2014-12-19 2015-12-21 Procédé et dispositif de production d'oléfines inférieures, procédé de construction pour équipement de production d'oléfines inférieures, et catalyseur de type zéolithe Ceased WO2016098909A1 (fr)

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WO2019036291A1 (fr) * 2017-08-15 2019-02-21 Sabic Global Technologies B.V. Gaz de schiste et condensat donnant des produits chimiques
WO2020021356A1 (fr) * 2018-07-27 2020-01-30 Sabic Global Technologies B.V. Procédé de production d'oléfines légères et de composés aromatiques à partir de naphta à point d'ébullition à coupe large
WO2021019326A1 (fr) * 2019-07-31 2021-02-04 Sabic Global Technologies B.V. Procédé de craquage catalytique de naphta
WO2021019343A1 (fr) * 2019-07-31 2021-02-04 Sabic Global Technologies B.V. Procédé de craquage catalytique de naphta
WO2021019344A1 (fr) * 2019-07-31 2021-02-04 Sabic Global Technologies B.V. Procédé de craquage catalytique de naphta
FR3104604A1 (fr) * 2019-12-16 2021-06-18 IFP Energies Nouvelles Dispositif et procédé de production d’oléfines légères et d’aromatiques par craquage catalytique.
FR3104605A1 (fr) * 2019-12-16 2021-06-18 IFP Energies Nouvelles Dispositif et procédé de production d’oléfines légères par craquage catalytique et vapocraquage.
WO2021236149A1 (fr) * 2020-05-21 2021-11-25 Saudi Arabian Oil Company Conversion de naphta léger en produits à valeur améliorée dans un procédé intégré avec réacteur à deux zones
WO2024145448A1 (fr) * 2022-12-29 2024-07-04 Uop Llc Procédés de craquage de paraffine

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WO2019036291A1 (fr) * 2017-08-15 2019-02-21 Sabic Global Technologies B.V. Gaz de schiste et condensat donnant des produits chimiques
WO2020021356A1 (fr) * 2018-07-27 2020-01-30 Sabic Global Technologies B.V. Procédé de production d'oléfines légères et de composés aromatiques à partir de naphta à point d'ébullition à coupe large
US11807819B2 (en) 2018-07-27 2023-11-07 Sabic Global Technologies B.V. Process of producing light olefins and aromatics from wide range boiling point naphtha
WO2021019344A1 (fr) * 2019-07-31 2021-02-04 Sabic Global Technologies B.V. Procédé de craquage catalytique de naphta
WO2021019343A1 (fr) * 2019-07-31 2021-02-04 Sabic Global Technologies B.V. Procédé de craquage catalytique de naphta
US12234415B2 (en) 2019-07-31 2025-02-25 Sabic Global Technologies B.V. Naphtha catalytic cracking process
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US11851621B2 (en) 2019-07-31 2023-12-26 Sabic Global Technologies B.V. Naphtha catalytic cracking process
WO2021019326A1 (fr) * 2019-07-31 2021-02-04 Sabic Global Technologies B.V. Procédé de craquage catalytique de naphta
CN114207093A (zh) * 2019-07-31 2022-03-18 沙特基础全球技术有限公司 石脑油催化裂化方法
CN114466916A (zh) * 2019-07-31 2022-05-10 沙特基础全球技术有限公司 石脑油催化裂化方法
US11866396B2 (en) 2019-12-16 2024-01-09 IFP Energies Nouvelles Apparatus and process for producing light olefins and aromatics by catalytic cracking
US11702377B2 (en) 2019-12-16 2023-07-18 IFP Energies Nouvelles Apparatus and process for producing light olefins by catalytic and steam cracking
EP3839012A1 (fr) * 2019-12-16 2021-06-23 IFP Energies nouvelles Dispositif et procédé de production d oléfines légères par craquage catalytique et vapocraquage
FR3104605A1 (fr) * 2019-12-16 2021-06-18 IFP Energies Nouvelles Dispositif et procédé de production d’oléfines légères par craquage catalytique et vapocraquage.
EP3839013A1 (fr) * 2019-12-16 2021-06-23 IFP Energies nouvelles Dispositif et procédé de production d'oléfines légères et d'aromatiques par craquage catalytique
FR3104604A1 (fr) * 2019-12-16 2021-06-18 IFP Energies Nouvelles Dispositif et procédé de production d’oléfines légères et d’aromatiques par craquage catalytique.
US11365358B2 (en) 2020-05-21 2022-06-21 Saudi Arabian Oil Company Conversion of light naphtha to enhanced value products in an integrated two-zone reactor process
WO2021236149A1 (fr) * 2020-05-21 2021-11-25 Saudi Arabian Oil Company Conversion de naphta léger en produits à valeur améliorée dans un procédé intégré avec réacteur à deux zones
WO2024145448A1 (fr) * 2022-12-29 2024-07-04 Uop Llc Procédés de craquage de paraffine

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