WO2008035743A1 - Procédé de production de propylène - Google Patents

Procédé de production de propylène Download PDF

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Publication number
WO2008035743A1
WO2008035743A1 PCT/JP2007/068299 JP2007068299W WO2008035743A1 WO 2008035743 A1 WO2008035743 A1 WO 2008035743A1 JP 2007068299 W JP2007068299 W JP 2007068299W WO 2008035743 A1 WO2008035743 A1 WO 2008035743A1
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Prior art keywords
fluid
carbon atoms
reactor
rich
hydrocarbon
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PCT/JP2007/068299
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English (en)
Japanese (ja)
Inventor
Masashi Yamaguchi
Tohru Setoyama
Kagoto Nakagawa
Fumitaka Utsumi
Shinji Iwade
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Mitsubishi Chemical Corporation
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Priority to KR1020097005802A priority Critical patent/KR101435230B1/ko
Publication of WO2008035743A1 publication Critical patent/WO2008035743A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • C07C4/04—Thermal processes
    • 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
    • C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing propylene from a raw material mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether.
  • Patent Document 1 U.S. Pat.No. 6888038
  • a first object of the present invention is to provide a novel and economical process for producing propylene by reacting olefin having 4 or more carbon atoms with at least one of methanol and dimethyl ether.
  • the second object of the present invention is to provide a new and economical process that integrates this process and steam cracking.
  • the inventors of the present invention examined the reaction of obtaining propylene by reacting olefins having 4 or more carbon atoms with at least one of methanol and dimethyl ether, and obtained the following findings.
  • aromatic compounds and paraffins are also produced in trace amounts, and are contained in the reactor outlet fluid.
  • the concentration of paraffin in the reactor outlet fluid increases. Since noraffins hardly react in the reactor, paraffin concentrates and accumulates in the system when recycled to the reactor together with olefins having 4 or more carbon atoms. For this reason, it is preferable to extract a part of the fluid containing paraffins from the system.
  • the fluid to be extracted is preferably a fluid having a composition that can be effectively used.
  • the fluid to be extracted is preferably a fluid having a composition that can be used effectively.
  • the present inventors have found various problems in a method for producing propylene using olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether as raw materials, and solved these problems.
  • a process capable of producing propylene it was found that propylene could be produced in a high yield while suppressing deterioration of the catalyst using a small amount of raw materials.
  • the present invention has been achieved based on such findings, and the gist thereof is as follows.
  • At least a part of the aromatic compound contained in the reactor outlet effluent gas is withdrawn and contained in the reactor outlet effluent gas (reactor outlet gas)!
  • the total amount of aromatic compounds contained in all raw materials fed to the reactor is the total of olefins having 4 or more carbon atoms contained in all the raw materials.
  • the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in all raw materials fed to the reactor is 20 vol% or more.
  • Propylene production method characterized by controlling to volume% or less.
  • step (1) In a method for producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following step (1) , (2) and a process comprising (3A), characterized in that it comprises a process for producing propylene.
  • Step (1) olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (D) recycled from step (3A), and at least one of methanol and dimethyl ether are supplied to the reactor, and carbon at the outlet of the reactor is supplied.
  • the molar flow rate of olefins of 4 or more is contacted with the catalyst under reaction conditions such that the molar flow rate of the olefins at the inlet of the reactor is 20% or more and less than 90%.
  • gas reactor outlet gas
  • Step (2) Reactor outlet gas from step (1) above is rich in hydrocarbons rich in hydrocarbons having 3 or less carbon atoms, fluids rich in hydrocarbons having 4 or more carbon atoms (A), and rich in water. Separating into fluid
  • the following steps (1 ), (2) and (3A) In a method for producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1 ), (2) and (3A).
  • Step (1) olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (D) recycled from step (3A), and at least one of methanol and dimethyl ether are supplied to the reactor, and carbon at the outlet of the reactor is supplied.
  • the molar flow rate of olefins of 4 or more is contacted with the catalyst under reaction conditions such that the molar flow rate of the olefins at the inlet of the reactor is 20% or more and less than 90%.
  • gas reactor outlet gas
  • Step (2) Reactor outlet gas from step (1) above is rich in hydrocarbons rich in hydrocarbons having 3 or less carbon atoms, fluids rich in hydrocarbons having 4 or more carbon atoms (A), and rich in water. Separating into fluid
  • the reactor is composed of two or more reaction forces connected in series, the olefin raw material having 4 or more carbon atoms supplied to the reactor; methanol and dimethyl ether At least one of them; and at least one of the recycled hydrocarbon-containing fluid (D) is divided and supplied to the first-stage reaction section and the second-stage and subsequent reaction sections.
  • Propylene production method is composed of two or more reaction forces connected in series, the olefin raw material having 4 or more carbon atoms supplied to the reactor; methanol and dimethyl ether At least one of them; and at least one of the recycled hydrocarbon-containing fluid (D) is divided and supplied to the first-stage reaction section and the second-stage and subsequent reaction sections.
  • Step (1) olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (I) recycled from step (3B), and at least one of methanol and dimethyl ether are supplied to the reactor, and the number of carbons at the outlet of the reactor Contact with the catalyst under reaction conditions such that the molar flow rate of 4 or more olefins is 20% or more and less than 90% of the molar flow rate of the olefins at the inlet of the reactor.
  • Step (2) The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, a fluid rich in hydrocarbons having 4 or more carbon atoms (A), and a fluid rich in water
  • Step (3) In the step (2), the fluid (A) has an aromatic concentration lower than that of the fluid (A) !, and the fluid (G) and the hydrocarbon concentration of 4 carbon atoms are fluid ( A) is separated into a fluid (F), at least a part (I) of the fluid (G) is recycled to the reactor, and the remaining fluid (H) is extracted from the process.
  • Propylene is produced by contacting a mixture of olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst.
  • a process for producing propylene characterized by comprising a process comprising the following steps (1), (2) and (3B):
  • Step (1) olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (I) recycled from step (3B), and at least one of methanol and dimethyl ether are supplied to the reactor, and the number of carbons at the outlet of the reactor Contact with the catalyst under reaction conditions such that the molar flow rate of 4 or more olefins is 20% or more and less than 90% with respect to the molar flow rate of the olefins at the inlet of the reactor, and propylene and other olefins from the reactor outlet.
  • gas containing gas, paraffins, aromatic compounds and water reactor outlet gas
  • Step (2) The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, a fluid rich in hydrocarbons having 4 or more carbon atoms (A), and a fluid rich in water Step (3B):
  • the fluid (A) has an aromatic concentration lower than that of the fluid (A) !, and the fluid (G) and the hydrocarbon concentration of 4 carbon atoms are fluid ( A) is separated into a fluid (F), and the fluid (F) is withdrawn from the process, and a part (I) of the fluid (G) is recycled to the reactor, and the remaining fluid Step of extracting (H) from the process
  • the reactor comprises two or more reaction parts connected in series, and the olefin raw material having 4 or more carbon atoms to be supplied to the reactor; methanol and dimethyl ether At least one of them; and at least one of the recycled hydrocarbon-containing fluid (I) is divided into a first-stage reaction section and a second-stage reaction section to be supplied.
  • a method for producing propylene which is characterized.
  • the total raw material supplied to the reactor has 4 or more carbon atoms.
  • a method for producing propylene characterized in that the total concentration (substrate concentration) of olefin, methanol, and dimethyl ether is controlled to 20 volume% or more and 80 volume% or less.
  • step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step
  • carbonization having 2 or less carbon atoms is performed by distillation.
  • a fluid rich in hydrogen and a fluid rich in hydrocarbons having 3 or more carbon atoms are separated, and the fluid rich in hydrocarbons having 3 or more carbon atoms is separated from the fluid rich in hydrocarbons and carbon atoms containing 3 carbon atoms by distillation.
  • a method for producing propylene comprising a step of separating the fluid into a hydrocarbon-rich fluid having a number of 4 or more.
  • step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step
  • carbonization of 3 or less carbon atoms is performed by distillation.
  • a fluid rich in hydrogen and a fluid rich in hydrocarbons having 4 or more carbon atoms are separated into a fluid rich in hydrocarbons having 3 or less carbon atoms, and a fluid rich in hydrocarbons having 2 or less carbon atoms by distillation.
  • step 1 condenses and removes moisture from the reactor outlet gas by a cooling and compression step, and then the number of carbon atoms by distillation.
  • a fluid containing a hydrocarbon having 2 or less hydrocarbons and a hydrocarbon having 3 carbon atoms is separated into a fluid rich in hydrocarbons having 3 or more carbon atoms, and the fluid rich in hydrocarbons having 3 or more carbon atoms is distilled by distillation.
  • a method for producing propylene comprising a step of separating a fluid rich in hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms.
  • the distillation has a carbon number of 3 or less.
  • a fluid rich in hydrocarbons and a fluid rich in hydrocarbons having 4 or more carbon atoms are separated, and the fluid rich in hydrocarbons having 3 or less carbon atoms is separated into hydrocarbons having 2 or less carbon atoms by distillation.
  • a process for producing propylene comprising a step of separating a fluid containing elemental hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms.
  • the total amount of aromatic compounds contained in all the raw materials fed to the reactor is olefin having 4 or more carbon atoms contained in all the raw materials.
  • Propylene production method characterized in that the molar ratio is less than 0.05 with respect to the total amount of
  • the catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefins having 4 or more carbon atoms is 20% or more and less than 90% with respect to the molar flow rate of the olefins at the inlet of the reactor, and propylene and other components are discharged from the reactor outlet.
  • the catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefins having 4 or more carbon atoms is 20% or more and less than 90% with respect to the molar flow rate of the olefins at the inlet of the reactor, and propylene and other components are discharged from the reactor outlet Of obtaining gas (reactor outlet gas) containing olefins, paraffins, aromatic compounds and water
  • the liquid fluid (M) has an aromatic concentration lower than that in the liquid fluid (M) by distillation! /,
  • the fluid (R) and the carbon number of 4 A method for producing propylene, characterized in that the hydrocarbon concentration is separated into a fluid (S) lower than the liquid fluid (M).
  • the fluid (R) may be any force selected from the fluids (K), (L), (M), (P), and (Q), and one or more fluids A method for producing propylene, which is returned to the distribution location.
  • the gas fluid (L) is obtained by distilling the fluid rich in hydrocarbons having 2 or less carbon atoms and 3 or more carbon atoms by distillation. It is separated into a fluid rich in hydrocarbons, and a fluid rich in hydrocarbons with 3 or more carbon atoms is distilled to enrich a fluid rich in hydrocarbons with 3 carbon atoms and rich in hydrocarbons with 4 or more carbon atoms.
  • a process for producing propylene which comprises a step of separating into a fluid (N).
  • the gas fluid (L) is obtained by distilling the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms.
  • the hydrocarbon-rich fluid (N) is separated into the above-mentioned hydrocarbon-rich fluid, and further, the hydrocarbon-rich fluid having 3 or less carbon atoms is distilled, and the hydrocarbon-rich fluid having 3 or less carbon atoms and carbon 3 or less are obtained by distillation.
  • a process for producing propylene, comprising the step of separating into a hydrocarbon-rich fluid.
  • step 3C) includes distilling the gas fluid (L) into a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms. Is separated into a fluid rich in hydrocarbons containing 3 or more carbon atoms, and a fluid rich in hydrocarbons containing 3 or more carbon atoms is distilled into a fluid rich in hydrocarbons containing 3 carbon atoms. And a fluid rich in hydrocarbons (N) having 4 or more carbon atoms, and a process for producing propylene.
  • the gas fluid (L) is obtained by distilling the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms and the carbon number. It is separated into a hydrocarbon-rich fluid (N) having 4 or more hydrocarbons, and a fluid rich in hydrocarbons having 3 or less carbon atoms is distilled by distillation to produce hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms.
  • a process for producing propylene comprising a step of separating the fluid into a fluid rich in hydrocarbons containing 3 carbon atoms.
  • the olefin raw material having 4 or more carbon atoms which is composed of two or more reaction parts connected in series with each other and fed to the reactor; At least one of methanol and dimethyl ether; and recycled charcoal
  • a method for producing propylene characterized in that at least one of the hydride-containing fluids is divided and supplied to a first-stage reaction section and a second-stage reaction section and thereafter.
  • the total amount of aromatic compounds contained in all the raw materials fed to the reactor is olefin having 4 or more carbon atoms contained in all the raw materials.
  • Propylene production method characterized in that the molar ratio is less than 0.05 with respect to the total amount of
  • the total concentration of aromatic compounds contained in at least one of the fluid (M) and the fluid (P) is less than 5.0% by volume.
  • [55] A method for producing propylene according to any one of [38] to [54], wherein the fluid (R) is supplied to a steam cracking process and used as a cracker raw material.
  • [56] A method for producing propylene according to [55], wherein at least a part of the fluid (R) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.
  • the total amount of fluid supplied to the reactor is controlled by controlling the flow rates of the fluid (P), fluid (R), and fluid (S).
  • a method for producing propylene characterized in that the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in the raw material is controlled to 20 volume% or more and 80 volume% or less.
  • the fluid (R) may be any force selected from the fluids (K), (L), (N), (P), and (Q), When returning to the location of 1 or 2 or more fluids, by controlling the return location and flow rate of the fluid (R), olefin and methanol having 4 or more carbon atoms contained in all the raw materials supplied to the reactor Propylene production method characterized in that the total concentration of dimethyl ether and substrate (substrate concentration) is controlled to 20 vol% or more and 80 vol% or less.
  • the raw material in the method for producing propylene by reacting an olefin raw material having 4 or more carbon atoms with at least one of methanol and dimethyl ether in the presence of a catalyst, the raw material is highly advanced. Utilizing the power S to produce propylene in a high yield while suppressing catalyst deterioration.
  • FIG. 1 is a system diagram showing an example of an embodiment of a method for producing propylene of the present invention.
  • FIG. 2 is a system diagram showing another example of the embodiment of the method for producing propylene of the present invention.
  • FIG. 3 is a system diagram showing another example of the embodiment of the method for producing propylene of the present invention. Explanation of symbols
  • the method for producing propylene of the present invention is different from the method for producing propylene by contacting a olefin having 4 or more carbon atoms and a raw material containing at least one of methanol and dimethyl ether in the presence of a catalyst in a reactor.
  • a catalyst in a reactor.
  • at least a part of the aromatic compound contained in the reactor outlet effluent gas is extracted and at least a part of the olefins having 4 or more carbon atoms contained in the reactor outlet effluent gas.
  • the reactor is again brought into contact with the catalyst.
  • More specific first and second embodiments include those including the three steps (1), (2), (3A) or (1), (2), (3B) as described above, As long as it follows the purpose of solving the problem of the present invention, the force S including the four steps (1C), (2C), (3C) and (4C) as described above as the third embodiment There is no need to exclude the existence of other processes. Other processes may exist before and after the four processes, and other processes may exist between each process.
  • the "rich" in the present invention purity of 50 mol% or more of the desired product, preferably 7 0 mole 0/0 or more, more preferably 90 mol 0/0 or more, more preferably 95 mol 0/0 That means it is above.
  • “fluid rich in hydrocarbons having 4 or more carbon atoms (N)” means “hydrocarbons having 4 or more carbon atoms” of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol%. More preferably, the fluid contains 95 mol% or more.
  • the catalyst used in the reaction according to the present invention is not particularly limited as long as it is a solid having a Bronsted acid point, and a conventionally known catalyst is used.
  • a conventionally known catalyst is used.
  • clay minerals such as kaolin; clay minerals and the like
  • Solid acid catalyst such as mesoporous silica alumina such as A1-MCM41; acidic type ion exchange resin; zeolites; aluminum phosphates;
  • solid acid catalysts those having a molecular sieving effect are preferred, and those having a very high acid strength are preferred.
  • zeolites and aluminum phosphates having a molecular sieve effect As a structure, for example, AEI, AET, AEL, AFI, AFO, AFS, AST, ATN, BEA, CAN, CHA, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON, etc.
  • catalysts with a catalyst framework density of 18. OT / nm 3 or less are preferred.
  • MFI, MEL, MOR, MWW, FAU, BEA, and CHA are preferred.
  • MFI, MEL, MOR, MWW, CHA particularly preferably MFI, MEL, MWW, CHA.
  • the framework density (unit: T / nm 3 ) is the number of T atoms (among the atoms constituting the zeolite skeleton, other than oxygen) present per unit volume of zeolite (lnm 3 ). This value is determined by the structure of the zeolite.
  • the solid acid catalyst more preferably has micropores having a pore diameter of 0.3 to 0.9 nm, a BET specific surface area of 200 to 700 m 2 / g, and a pore volume of 0.3; Crystalline aluminosilicates, metamouth silicates, crystalline aluminum phosphates, etc. that are in the range of ⁇ 0.5 g / ml are preferred.
  • the pore diameter to say, International Zeolite Association (IZA) stipulated crystal 'formic white ladle 7 d Chiyanenore DiL diameter (Crystaliographic free diameter of the channels) and non, shape perfect circular pores (channels) In the case of, the diameter is indicated, and when the pore shape is elliptical, the short diameter is indicated.
  • IZA International Zeolite Association
  • aluminosilicates those having a SiO 2 / Al 2 O molar ratio of 10 or more are preferred.
  • the upper limit of the iO / AlO molar ratio is usually 10,000 or less. This is the molar ratio of Si ⁇ / Al ⁇ .
  • the molar ratio can be determined by conventional methods such as fluorescent X-ray and chemical analysis.
  • the aluminum content in the catalyst can be controlled by the amount of raw material charged during catalyst preparation, and A1 can be reduced by steaming after preparation. Further, a part of A1 may be replaced with another element such as boron or gallium. In particular, it is preferable to replace with boron.
  • the catalytically active component as described above may be used as it is as a catalyst in the reaction, or granulated and molded using a substance or binder that is inert to the reaction, or may be used. These may be mixed for use in the reaction.
  • the substance or binder inert to the reaction include alumina or alumina sol, silica, silica gel, quartz, and a mixture thereof.
  • the catalyst composition described above is a composition of only a catalytically active component that does not contain a substance inactive to these reactions, a binder, and the like.
  • the catalyst according to the present invention includes a substance or binder that is inert to these reactions, the catalyst active component is combined with the substance or binder that is inert to these reactions to form a catalyst. In that case, it does not contain substances or binders that are inert to these reactions.
  • the particle diameter of the catalytically active component used in the present invention varies depending on the conditions during synthesis, but is usually 0.01 m to 500 m as an average particle diameter. If the particle size of the catalyst is too large, the surface area showing the catalytic activity will be small, and if it is too small, the handleability will be inferior, which is not preferable in either case. This average particle size can be determined by SEM observation or the like.
  • the method for preparing the catalyst used in the present invention is not particularly limited, and the catalyst can be prepared by a known method generally called hydrothermal synthesis.
  • the composition can be changed after hydrothermal synthesis by modification such as ion exchange, dealumination treatment, impregnation and loading.
  • the catalyst used in the present invention may be prepared by any method as long as it has the above physical properties or composition when subjected to the reaction.
  • the olefin having 4 or more carbon atoms used as a raw material for the reaction is not particularly limited.
  • oil produced by catalytic cracking or steam cracking, etc. (BB fraction, C4 rough rice toe 1, C4 rough rice toe 2, etc.), hydrogen / CO mixed gas obtained by gasification of coal It is obtained by synthesis of FT (Fischer-Tropsch) as a raw material and obtained by oligomerization reaction including ethylene dimerization reaction.
  • the reaction temperature can be easily controlled because norafine serves as a diluent gas, and the raw material containing paraffin is inexpensive. It is preferable because it is often available. More preferred
  • These preferable raw materials include the above-mentioned BB fraction, C4 rough rice toe 1 and C4 rough rice toe 2. These raw materials usually contain butadiene. Since butadiene is easily converted to an aromatic compound by reaction, it is very important to extract at least a part of the produced aromatic compound without recycling it to the reactor as in the present invention. Since the BB fraction contains a large amount of butadiene, it is preferable to use a fluid that has been brought into contact with a hydrogenation catalyst to lower the butadiene concentration as a raw material.
  • the production origin of at least one of methanol and dimethyl ether used as a reaction raw material is not particularly limited.
  • those obtained by hydrogenation reaction of coal and natural gas, and by-product hydrogen / CO gas mixture in the steel industry those obtained by reforming reaction of plant-derived alcohols, by fermentation method And those obtained from organic materials such as recycled plastic and municipal waste.
  • the reaction between olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether is a gas phase reaction.
  • gas phase reactor There are no particular restrictions on the form of the gas phase reactor, but it is usually selected from continuous fixed bed reactors and fluidized bed reactors. A fixed bed reactor is preferred.
  • the reactor may be composed of two or more reaction units connected in series.
  • one reactor may be divided into a plurality of reaction chambers, or two or more reactors may be connected in series.
  • a heat exchanger may be disposed between the reactors for the purpose of removing heat generated by the reaction.
  • reaction substrate may be divided and supplied for the purpose of dispersing heat generation.
  • reaction substrate reaction raw material
  • at least one of methanol and dimethyl ether is divided and supplied to the first-stage reaction section (reactor or reaction chamber) and the second-stage reaction section (reactor or reaction chamber).
  • the catalyst has little coking and the rate of catalyst deterioration is slow.
  • a fixed bed reactor it is desirable to install at least two reactors in parallel and switch between reaction and regeneration.
  • a multitubular reactor or an adiabatic reactor is selected.
  • examples of the catalyst regeneration operation include a method of regenerating the catalyst deteriorated by coking by treating it with nitrogen gas containing oxygen or water vapor.
  • the regeneration operation in the fixed bed reactor preferably, after removing volatile organic compounds adhering to the catalyst with nitrogen gas, the coke content is burned and removed with nitrogen gas containing a low concentration of oxygen, and thereafter.
  • An example is a method of removing molecular oxygen contained in the catalyst layer by treating with nitrogen gas.
  • the amount of olefin having 4 or more carbon atoms fed to the reactor is 0.2 in terms of a molar ratio to the sum of the number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether. Or more, preferably 0.5 or more, 10 or less, preferably 5 or less
  • Mc4 when the supply molar amount of olefins having 4 or more carbon atoms is Mc4, the supply molar amount of methanol is Mm, and the supply molar amount of dimethyl ether is Mdm, Mc4 is 0.2 to 10 times (Mm + 2Mdm), preferably Is 0.5 to 5 times.
  • this supply concentration ratio is too low or too high, the reaction will be slow, which is preferable. In particular, if this supply concentration ratio is too low, the consumption of olefins as a raw material will be reduced.
  • the supply concentration ratio is obtained by quantifying the composition of each fluid supplied to the reactor or the mixed fluid by a general analytical method such as gas chromatography. .
  • olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether may be supplied separately or after mixing in part or in advance. Also good.
  • the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether in all the feeds fed to the reactor is preferably 20% by volume or more and 80% by volume or less, more preferably 30%.
  • the volume is not less than 70% by volume.
  • the substrate concentration is determined for each fluid supplied to the reactor or after mixing. It can be determined by quantifying the composition using a general analytical method such as gas chromatography.
  • the substrate concentration is too high, aromatic compounds and paraffins are prominently produced, and the propylene selectivity tends to decrease.
  • the substrate concentration is too low, the reaction rate becomes slow, so a large amount of catalyst is required, and the product purification cost and the construction cost of the reaction equipment increase, which is not economical.
  • the reaction substrate is diluted with a diluent gas described below so as to obtain such a substrate concentration.
  • the method for controlling the substrate concentration includes a method for controlling the flow rate of the fluid extracted from the process. That is, by changing the flow rate of the fluid withdrawn from the process, it is possible to change the flow rate of the dilution gas recycled to the reactor and change the substrate concentration.
  • butadiene may be contained in the olefin raw material having 4 or more carbon atoms and / or in the hydrocarbon-containing fluid to be recycled, but butadiene in all the raw materials supplied to the reactor.
  • the concentration of is preferably 2.0% by volume or less. If the concentration of butadiene in the raw material is high, the production of aromatic compounds increases and deterioration due to catalyst coking is accelerated.
  • the butadiene concentration is determined by the force S known by quantifying the composition of each fluid supplied to the reactor or the fluid after mixing by a general analytical method such as gas chromatography.
  • Examples of a method for reducing the concentration of butadiene in the raw material include a partial hydrogenation method in which the fluid is brought into contact with a hydrogenation catalyst and converted into olefins.
  • the hydrocarbon-containing fluid to be recycled to the reactor may contain an aromatic compound! /, But the aromatic compound contained in all raw materials supplied to the reactor Is preferably less than 0.05 in terms of a molar ratio with respect to the total amount of olefins having 4 or more carbon atoms contained in all raw materials fed to the reactor.
  • concentration of the aromatic compound in the raw material is high, the reaction between the aromatic compound and olefin having 4 or more carbon atoms, or the reaction between the aromatic compound and at least one of methanol and dimethyl ether in the reactor becomes remarkable. Therefore, it is not preferable because it consumes at least one of olefins having 4 or more carbon atoms, methanol and dimethyl ether more than necessary.
  • the compound produced by the reaction with the olefin having 4 or more carbon atoms clogs the pores of the catalyst, thereby promoting the deterioration of the catalyst. It is preferable to remove the aromatic compounds present in the reactor outlet fluid from the system as much as possible and reduce the concentration of the aromatic compounds in the fluid recycled to the reactor.
  • the ratio of the total amount of the aromatic compounds and the total amount of olefins having 4 or more carbon atoms depends on the composition of each fluid supplied to the reactor or the fluid after mixing, such as gas chromatography. This can be determined by quantitative analysis using a typical analysis method.
  • An example of a method for reducing the concentration of aromatic compounds in the raw material is a separation method by distillation.
  • paraffins and aromatics are defined as diluting gases because of the small amount of reaction that may react slightly depending on the reaction conditions.
  • impurities contained in the reaction raw material can be used as they are, or a separately prepared dilution gas can be mixed with the reaction raw material.
  • the dilution gas may be mixed with the reaction raw material before entering the reactor, or may be supplied to the reactor separately from the reaction raw material.
  • Preferred diluent gases are paraffins having 4 or more carbon atoms. More preferably, what is contained in the raw material for polyolefin can be used, and since the heat capacity is relatively high and the compound is used, the reaction temperature can be easily controlled.
  • the space velocity mentioned here is the flow rate of olefin having 4 or more carbon atoms as the reaction raw material per weight of the catalyst (catalytic active component).
  • the weight of the catalyst is used for granulating and molding the catalyst. It is the weight of the catalytically active component which does not contain an inactive component or a binder.
  • the flow rate is the flow rate (weight / hour) of olefins with 4 or more carbon atoms.
  • the space velocity is preferably between 0.1 lHr- 1 and 500Hr- 1. 1. More preferably between OHr- 1 and lOOHr- 1 . If the space velocity is too high, the conversion of at least one of the raw materials olefin and methanol and dimethyl ether is low, and sufficient propylene selectivity cannot be obtained. On the other hand, if the space velocity is too low, the amount of catalyst required to obtain a certain production amount increases, the reactor becomes too large, and preferable residues and by-products such as aromatic compounds and paraffin are produced. Since propylene selectivity decreases, it is not preferable.
  • the lower limit of the reaction temperature is usually about 300 ° C or higher, preferably 400 ° C or higher as the gas temperature at the reactor inlet, and the upper limit of the reaction temperature is usually 700 ° C or lower, preferably 600 ° C. It is as follows. If the reaction temperature is too low, a large amount of unreacted raw material with a low reaction rate tends to remain, and the yield of propylene also decreases. On the other hand, if the reaction temperature is too high, the yield of propylene is significantly reduced.
  • the upper limit of the reaction pressure is usually 2 MPa (absolute pressure, the same applies hereinafter) or less, preferably IMPa or less, more preferably 0.7 MPa or less.
  • the lower limit of the reaction pressure is not particularly limited, but is usually 1 kPa or more, preferably 50 kPa or more. If the reaction pressure is too high, the amount of preferable les and by-products such as paraffins and aromatic compounds increases, and the yield of propylene tends to decrease. If the reaction pressure is too low, the reaction rate tends to be slow.
  • the total of the molar flow rate of methanol fed to the reactor and twice the molar flow rate of dimethyl ether is preferably less than 1%. More preferably, it is less than 0.1%.
  • Methods for increasing the consumption of methanol and dimethyl ether include increasing the reaction temperature and decreasing the space velocity.
  • the molar flow rate of olefins having 4 or more carbon atoms at the outlet of the reactor is set to 20% or more and less than 90% with respect to the molar flow rate of olefins having 4 or more carbon atoms supplied to the reactor.
  • the molar flow rate is preferably 20% or more and less than 70%, more preferably 25% or more and less than 60%. If the consumption of olefins having 4 or more carbon atoms in the reactor is too small, the amount of unreacted olefins increases, and the flow rate of the fluid recycled to the reactor becomes too large. On the other hand, if the amount of consumption is too large, paraffin and aromatic compounds are not desirable! /, Which is preferable because the compounds are by-produced and the propylene yield is reduced! /.
  • Examples of the method for adjusting the consumption of olefins having 4 or more carbon atoms in the reactor include a method of appropriately setting the reaction temperature and space velocity.
  • the flow rates of methanol and dimethyl ether and olefins having 4 or more carbon atoms to be supplied to the reactor are different from those of each fluid supplied to the reactor or the composition of the fluid after mixing such as gas chromatography. It is possible to know by measuring the flow rate of each fluid and measuring the flow rate of each fluid.
  • the flow rate of methanol and dimethyl ether and olefins having 4 or more carbon atoms at the outlet of the reactor determines the composition of the outlet fluid of the reactor by gas chromatography. Quantify using a general technique such as graphing, and measure or calculate the flow rate of the reactor outlet fluid.
  • reactor effluent a mixed gas containing the reaction product, propylene, unreacted raw materials, by-products and a diluent is obtained.
  • the propylene concentration in the mixed gas is usually 5 to 95% by weight.
  • the unreacted raw material is usually olefin having 4 or more carbon atoms.
  • By-products include ethylene, olefins with 4 or more carbon atoms, paraffins, and aromatics. Compounds and water are mentioned.
  • the reactor outlet gas is separated into a hydrocarbon-rich fluid having 3 or less carbon atoms, a fluid rich in hydrocarbons having 4 or more carbon atoms (A), and water by a general separation process such as cooling, compression and distillation. Separated into rich fluid.
  • a fluid rich in hydrocarbons having 2 or less carbon atoms and carbonization having 3 or more carbon atoms by distillation is separated into a fluid rich in hydrocarbons, and a fluid rich in hydrocarbons containing 3 or more carbon atoms and a fluid rich in hydrocarbons containing 4 or more carbon atoms (A)
  • a method including a step of separating into two is applied.
  • a fluid rich in hydrocarbons having 3 or less carbon atoms and hydrocarbons having 4 or more carbon atoms by distillation After condensing and removing moisture by a cooling and compression step, a fluid rich in hydrocarbons having 3 or less carbon atoms and hydrocarbons having 4 or more carbon atoms by distillation. And a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms by distillation.
  • a method including a step of separating is applied.
  • a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms by distillation and carbon number Separation into a fluid rich in hydrocarbons with 3 or more hydrocarbons, and a fluid rich in hydrocarbons with 3 or more carbon atoms by distillation, fluids rich in hydrocarbons with 3 carbon atoms and fluids rich in hydrocarbons with 4 or more carbon atoms A method including the step of separating into (A) is applied.
  • a fluid rich in hydrocarbons having 3 or less carbon atoms and hydrocarbons having 4 or more carbon atoms are obtained by distillation.
  • a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms and carbon having 3 carbon atoms by distillation is applied.
  • a method is applied that includes the step of separating into a hydrofluoric fluid.
  • Separation of water is possible mainly by condensation through compression and cooling. It is preferable to remove the remaining water with an adsorbent such as molecular sieve.
  • the water removed by condensation and / or adsorption may be used for wastewater treatment processes such as activated sludge, but it can be used for process water.
  • the process of the present invention (hereinafter sometimes referred to as “the process”) is in the vicinity of a steam cracking process, the water recovered from the reactor outlet gas is preferably utilized as a steamer steam source. . It may be recycled to the reactor of this process and used as a diluted gas.
  • hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms obtained from the reactor outlet gas can be further purified to ethylene and propylene with high purity by a purification process such as distillation.
  • ethylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.
  • the purity of propylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.
  • the ethylene and propylene thus obtained can be used as raw materials for ethylene and propylene derivatives that are generally produced from the viewpoint of quality such as the amount of impurities.
  • ethylene glycol, ethanolamine, glycol ethers, etc. for the production of chlorinated butyl monomers, 1, 1, 1 trichloroethane, chlorinated resin, vinylidene chloride by chlorination, and for the polymerization of ethylene, ⁇ -olefin, It can be used for the production of low density or high density polyethylene and for the production of ethylbenzene and the like by benzene ethylation.
  • Polyethylene terephthalate can be further produced from ethylene glycol produced from ethylene power, using ⁇ - olefin as a raw material, and higher alcohol is converted into ethyl benzene by an oxo reaction and subsequent hydrogenation reaction.
  • Acetaldehyde and its derivative ethyl acetate can also be produced by the reaction.
  • Propylene is produced, for example, by ammoxidation for the production of acrylonitrile, by selective oxidation for the production of acrolein, acrylic acid and acrylate esters, and by oxo reaction by oxo-reactions such as cal- butyl alcohol and 2-ethylhexanol. It can be applied to the production of alcohol, the production of polypropylene by polymerization of propylene, and the production of propylene oxide and propylene glycol by the selective oxidation of propylene.
  • acetone can be produced by one reaction, and further, methylisoptyl ketone can be produced from acetone.
  • Acetone can also produce acetone cyanohydrin, which is ultimately converted to methylmethalate.
  • Isopropyl alcohol can also be produced by propylene hydration.
  • phenol, bisphenol A, and polycarbonate resin can be produced from cumene produced by alkylating benzene.
  • the fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms obtained in the third and fourth aspects of the above general separation step! It is preferable to supply it to an ethylene and propylene production process other than this process for purification.
  • ethylene and propylene production processes include steam cracking processes such as naphthaetane. This can significantly reduce the capital investment of this process.
  • the reactor outlet gas is cooled, and the gas fluid (K) after cooling is compressed by gas fluid (L), rich in hydrocarbons having 4 or more carbon atoms, and liquid fluid (M) containing aromatic compounds. And a fluid rich in water (process (2C)), and then a gas fluid (U is separated by a general separation process such as distillation and a fluid rich in hydrocarbons having 3 or less carbon atoms and 4 or more carbon atoms). hydrocarbon Into a rich fluid (N) (step (3C)).
  • the reactor outlet gas is usually at a temperature of about 300 to 600 ° C.
  • the reactor outlet gas is cooled to about 20 to 200 ° C. This cooling may be performed directly by mixing with a fluid usually performed in a heat exchanger or a fluid having a temperature lower than that of the gas.
  • the cooled fluid (K) is compressed into a hydrocarbon-rich gas fluid (L) and hydrocarbons with 4 or more carbon atoms by compression using a compressor, knockout drum or oil-water separator. It is separated into a rich fluid (M) containing aromatics and a fluid rich in water.
  • the partner fluid that exchanges heat with the reactor outlet gas is not particularly limited! /, But is preferably one or more fluids supplied to the reactor! / ,.
  • the gas fluid (L) rich in hydrocarbons having 6 or less carbon atoms separated in this step (2C) contains hydrocarbons.
  • step (3C) general separation such as distillation is performed. The process separates the fluid rich in hydrocarbons with 3 or less carbon atoms and the fluid (N) rich in hydrocarbons with 4 or more carbon atoms.
  • the separation is performed by distillation into a hydrocarbon-rich fluid having 2 or less carbon atoms and a hydrocarbon-rich fluid having 3 or more carbon atoms.
  • a method including a step of separating a fluid rich in hydrocarbons having 3 or more hydrocarbons into a fluid rich in hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms (N) by distillation is applied.
  • a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid (N) rich in hydrocarbons having 4 or more carbon atoms are separated into 3 or less carbon atoms.
  • a method including a step of separating a fluid rich in hydrocarbons into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms by distillation is applied.
  • separation is performed by distillation into a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms
  • a method including a step of separating a fluid rich in hydrocarbons having 3 or more carbon atoms into a fluid rich in hydrocarbons having 3 or more carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms (N) by distillation is applied.
  • a hydrocarbon-rich fluid having a carbon number of 3 or less and a fluid (N) rich in a hydrocarbon having a carbon number of 4 or more are separated by distillation to obtain a hydrocarbon having a carbon number of 3 or less.
  • a method including a step of separating a rich fluid into a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms and a fluid rich in a hydrocarbon having 3 carbon atoms by distillation is applied.
  • Separation of water is possible mainly by condensation through compression and cooling. It is preferable to remove the remaining water with an adsorbent such as molecular sieve.
  • the water removed by condensation and / or adsorption may be used for wastewater treatment processes such as activated sludge, but it can be used for process water.
  • the process of the present invention (hereinafter sometimes referred to as “the process”) is in the vicinity of a steam cracking process, the water recovered from the reactor outlet gas is preferably utilized as a steamer steam source. . It may be recycled to the reactor of this process and used as a diluted gas.
  • hydrocarbons having 2 or less carbon atoms or hydrocarbons having 3 carbon atoms obtained from the reactor outlet gas can be further purified to ethylene and propylene with high purity by a purification process such as distillation.
  • ethylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.
  • the purity of propylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.
  • the ethylene and propylene thus obtained can be used for all of the generally produced ethylene and propylene derivatives.
  • ethylene is produced by the oxidation reaction to produce ethylene oxide, ethylene glycol, ethanolamine, glycol ether, etc.
  • ethylene is produced by the oxidation reaction to produce ethylene oxide, ethylene glycol, ethanolamine, glycol ether, etc.
  • Benzyl chloride, 1, 1, 1 trichloroethane chlorinated resin
  • vinylidene chloride by chlorination
  • ⁇ - olefin low density or high density polyethylene by polymerization of ethylene.
  • Polyethylene from ethylene glycol produced from ethylene power Terephthalate can be produced, and styrene monomer, ABS resin, etc. can be produced from higher alcohol ethylbenzene as a raw material by the oxo reaction using a-olefin and the subsequent hydrogenation reaction.
  • butyl acetate can be produced by reaction with acetic acid
  • cetyl acetate and its derivatives, such as acetoaldehyde can be produced by the reaction of Zucker.
  • propylene is produced by, for example, ammoxidation for the production of acrylonitrile, by selective oxidation for the production of acrolein, acrylic acid and acrylate esters, and by oxo reaction by oxo-reactions such as cal- butyl alcohol and 2-ethylhexanol. It can be applied to the production of alcohol, the production of polypropylene by polymerization of propylene, and the production of propylene oxide and propylene glycol by the selective oxidation of propylene.
  • acetone can be produced by one reaction, and further, methylisoptyl ketone can be produced from acetone.
  • Acetone can also produce acetone cyanohydrin, which is ultimately converted to methylmethalate.
  • Isopropyl alcohol can also be produced by propylene hydration.
  • phenol, bisphenol A, and polycarbonate resin can be produced from cumene produced by alkylating benzene.
  • the fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms obtained in the third and fourth aspects of the separation step described above is a mixture of ethylene and propylene other than this process. It is preferably supplied to the production process for purification.
  • Other processes for producing ethylene and propylene include steam cracking processes such as naphthaetane. This can significantly reduce the capital investment of this process.
  • hydrocarbon-rich fluid (A) separated from the reactor outlet gas (A) (hereinafter referred to as hydrocarbon fluid (A) having 4 or more carbon atoms) is recycled to the reactor.
  • hydrocarbon fluid (A) having 4 or more carbon atoms) is recycled to the reactor.
  • the remaining fluid is withdrawn from the process.
  • extracted from this process means that it is not recycled to the reactor of this process, and it may be supplied directly to other processes through piping or through piping. Once stored in the tank, it may be supplied to another process. It may also be used as fuel without being supplied to other processes.
  • a part (B) of the hydrocarbon fluid (A) having 4 or more carbon atoms is removed from the process. Extract the remaining fluid (C) using a general separation method such as distillation. The concentration of aromatic compounds (% by weight) is lower than that of fluid (C)! /, And the concentration of fluid (D) and hydrocarbons with 4 carbon atoms is fluid. Lower than (C)! /, Fluid (E) is separated, fluid (D) is recycled to the reactor, and a method including the step of withdrawing fluid (E) from the process is applied.
  • the concentration of aromatic compounds is lower than that of fluid (A) by using a general separation method such as distillation of hydrocarbon fluid (A) having 4 or more carbon atoms! /, Fluid (G) And the hydrocarbon concentration of carbon number 4 is lower than that of the fluid (A)! /, And the fluid (F) is separated, and at least a part of the fluid (F) is extracted from the process, and at least the fluid (G) A method including a step of recycling a part of the fluid (I) to the reactor and extracting the remaining fluid (H) from the process is applied.
  • a general separation method such as distillation of hydrocarbon fluid (A) having 4 or more carbon atoms! /
  • Fluid (G) And the hydrocarbon concentration of carbon number 4 is lower than that of the fluid (A)! /
  • the fluid (F) is separated, and at least a part of the fluid (F) is extracted from the process, and at least the fluid (G)
  • the fluid (B) in the first embodiment or the fluid (H) in the second embodiment is a composition fluid containing a lot of paraffin, so it is difficult to separate and purify active ingredients such as butene. Therefore, when the process is in the vicinity of the steam cracking process, it is preferably supplied to the steam cracking process and effectively used as a cracker raw material.
  • these fluids (B) and (H) can be used as raw materials for producing ethylene and propylene in steam cracking.
  • a fluid having a paraffin concentration increased from that of the fluid (B) or fluid (H) is supplied to the steam cracking process.
  • a fluid having a high olefin concentration is supplied to the cracker in the steam cracking process, carbon deposition is likely to occur in the cracker, which is preferable.
  • the total concentration of aromatic compounds contained in fluid (B) or fluid (H) is preferably less than 5.0% by volume, more preferably less than 3.0% by volume. is there. When the aromatic compound concentration is high, there is a large amount of carbon precipitation when fed to the cracker, and the ethylene yield tends to decrease, which is not preferable.
  • the fluid (E) in the first aspect or the fluid (F) in the second aspect is preferably mixed with a cracked gasoline fraction such as a steam cracking process. This makes it possible to effectively use fluid (E) or fluid (F).
  • the cracked gasoline here is a fluid mainly containing paraffin, olefin, gen, and aromatic compounds having 5 to 10 carbon atoms, and the ability to collect active ingredients from the cracked gasoline as required.
  • S can.
  • active ingredients include hydrocarbons having 5 carbon atoms and aromatic compounds such as benzene, toluene and xylene.
  • the cracked gasoline contains hydrocarbons having 4 carbon atoms, it is not preferable because hydrocarbons having 4 carbon atoms are mixed in the hydrocarbon fluid having 5 carbon atoms recovered from the cracked gasoline. Therefore, it is preferable that the C4 hydrocarbon in the fluid (E) or fluid (F) mixed with the cracked gasoline fraction is less than 5% by weight. More preferably, it is less than 2% by weight.
  • the feature of the first aspect is that the load of the separation process such as distillation can be reduced by extracting the fluid (B). More advantageous.
  • fluid (B) is a fluid having the same composition as fluid (A), and the concentration of the aromatic compound is higher than that of fluid (H) obtained in the second mode. Therefore, the process is selected according to the intended use of the fluid to be extracted.
  • Part (P) of the fluid rich in hydrocarbons with 4 or more carbon atoms (N) separated in step (3C) (hereinafter referred to as “hydrocarbon fluids with 4 or more carbon atoms (N)”)
  • the remaining fluid (Q) is withdrawn and recycled to the reactor, and at least one of the liquid fluid (M) rich in hydrocarbons having 4 or more carbons condensed in the compression process and containing aromatic compounds. Departments are extracted from this process.
  • “extracted from the process” is not recycled to the reactor of the process. This means that it may be supplied directly to other processes through piping, or once stored in a tank through piping, it may be supplied to other processes. It may also be used as fuel without being supplied to other processes.
  • Liquid fluid (M) has a lower concentration of aromatic compounds (wt%) than liquid fluid (M) due to distillation!
  • concentration of fluid (R) and hydrocarbons with 4 carbon atoms is higher than liquid fluid (M). It may be separated into lower fluid and fluid (S).
  • the fluid (R) is preferably returned to one or a plurality of fluid circulation locations selected from the fluids (K), (L), (N), (P), and (Q). This distillation operation is particularly preferred when the liquid fluid (M) contains a large amount of hydrocarbons having 4 or less carbon atoms.
  • the fluids (M), (P), and (R) have a composition containing a large amount of paraffin. Since it is a fluid, it is difficult to separate and purify active ingredients such as butene. Therefore, when the process is in the vicinity of the steam cracking process, one of these fluids (M), (P), (R), one or more fluids are supplied to the steam cracking process, and the cracker raw material is supplied. It is preferable to use as effective.
  • This can be a raw material for producing ethylene or propylene in steam cracking.
  • at least a part of the fluids (M), (P), and (R) is brought into contact with the hydrogenation catalyst, and the fluid whose paraffin concentration is increased from the fluids (M), (P), and (R) is steamed. It is preferable to supply it to the cracking process. It is not preferable to feed a fluid with a high olefin concentration to the cracker in the steam cracking process because carbon is likely to precipitate in the cracker.
  • the total concentration of aromatic compounds contained in the fluids (M), (P), and (R) is preferably less than 5.0% by volume. More preferably, it is less than 3.0 volume%.
  • a high concentration of the aromatic compound is not preferable because when it is supplied to the cracker, there is a large amount of carbon precipitation and the ethylene yield tends to decrease.
  • the fluid (S) is preferably mixed with a cracked gasoline fraction such as a steam cracking process. As a result, the fluid (S) can be used effectively. If the concentration of hydrocarbons with 4 or less carbon atoms in the fluid (M) is low, the fluid (M) You may mix with a catalytic cracking gasoline fraction.
  • the cracked gasoline here is a fluid mainly containing paraffin, olefin, gen, and aromatic compounds having 5 to 10 carbon atoms, and has the ability to collect active ingredients from the cracked gasoline as necessary.
  • S can.
  • active ingredients include hydrocarbons having 5 carbon atoms and aromatic compounds such as benzene, toluene and xylene.
  • cracked gasoline contains hydrocarbons having 4 carbon atoms, it is not preferable because hydrocarbons having 4 carbon atoms are mixed in the hydrocarbon fluid having 5 carbon atoms recovered from the cracked gasoline.
  • the C4 hydrocarbon in the fluid (M) or fluid (S) mixed with the cracked gasoline fraction is less than 5% by weight. More preferably, it is less than 2% by weight.
  • the flow rate of the dilution gas such as paraffin contained in the fluid (I) recycled to the reactor is controlled by controlling the flow rates of the fluid (F) and the fluid (H). Is possible.
  • the total concentration (substrate concentration) of olefins, methanol and dimethyl ether having 4 or more carbon atoms in all the feeds supplied to the reactor is preferable to control the total concentration (substrate concentration) of olefins, methanol and dimethyl ether having 4 or more carbon atoms in all the feeds supplied to the reactor to 20 vol% or more and 80 vol% or less.
  • FIG. 1 shows a first embodiment of the process of the present invention
  • FIG. 2 shows a second embodiment.
  • 10 is a reactor
  • 20 is a first separation and purification system
  • 30A and 30B are second separation and purification systems.
  • At least one of the olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (D) having 4 or more carbon atoms from the second separation and purification system 30A, methanol and dimethyl ether is connected to pipes 101, 102, 103 and 104, respectively. Then, it is supplied to the reactor 10.
  • the olefin raw material having 4 or more carbon atoms supplied to the reactor 10 may contain paraffins having 4 or more carbon atoms, such as calalebutane and isobutane.
  • the raw material fluid supplied to the reactor 10 via the pipe 104 may contain butadiene or an aromatic compound.
  • the butadiene concentration in the raw material fluid as described above is usually 2.0% by volume or less, and the total amount of aromatic compounds is moles relative to the total amount of olefins having 4 or more carbon atoms contained in the raw material fluid in the pipe 104.
  • the ratio is usually less than 0.05.
  • the feed fluid is a force S, which means the sum of the fluids supplied via pipes 101, 102 and 103, which do not necessarily have to be joined before entering reactor 10, 10 may be supplied.
  • the raw material gas supplied to the reactor 10 reacts in contact with the catalyst in the reactor 10 to obtain a reactor outlet gas containing propylene, other olefins, paraffins, aromatic compounds and water.
  • the reactor outlet gas is sent to a general separation and purification system 20 such as cooling, compression, and distillation through a pipe 105, and in this separation and purification system 20, a fluid rich in hydrocarbons having 3 or less carbon atoms, They are separated into a hydrocarbon-rich fluid (A) and water-rich fluid with 4 or more carbon atoms, and taken out through pipes 106, 108, and 107, respectively.
  • a hydrocarbon-rich fluid having 3 or less carbon atoms indicates one or more fluids.
  • One fluid may be used, a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms, or a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms.
  • Two fluids such as a fluid rich in 3 carbon atoms, may be used.
  • three or more fluids may be used.
  • a part of the hydrocarbon-rich fluid (A) with 4 or more carbon atoms is withdrawn out of the process through the pipe 109, and the remaining fluid (C) is separated through the pipe 110 through general separation such as distillation. Supplied to purification system 30A.
  • a part of the fluid (A) (B) may be extracted out of the process.
  • the extracted fluid (B) may be used as a cracker raw material for the steam cracking process.
  • the total concentration of aromatic compounds in the extracted fluid (B) is preferably less than 5.0% by volume.
  • the aromatic compound concentration is lower than the fluid (C)! / Soot fluid (D) and the fluid (E) in which the hydrocarbon concentration of 4 or more carbon atoms is lower than the fluid (C)
  • At least a part of the fluid (D) is recycled to the reactor 10 via the pipe 102, and the fluid) is extracted from the process via the pipe 111.
  • the extracted fluid (E) may be mixed with a cracked gasoline fraction such as a steam cracking process.
  • the total concentration force of hydrocarbons having 4 carbon atoms contained in the fluid (E) is preferably less than 3% by weight.
  • fluid (X) A part of the fluid (D) (hereinafter, “fluid (X)”) may be extracted out of the process.
  • the extracted fluid (X) may be used as a cracker raw material for the steam cracking process.
  • the total concentration of aromatic compounds in the drawn fluid (X) is preferably less than 5.0 mol%.
  • the fluid (D) and the fluid (X) are not necessarily required, but it is preferable to extract at least one of the fluids from the process in order to prevent accumulation of norafines.
  • Carbon 4 or more olefin raw material, carbonization of 4 or more carbon from the second separation and purification system 30B At least one of hydrogen fluid (I), methanol, and dimethyl ether is supplied to the reactor 10 via pipes 101, 102, 103 and pipe 104, respectively. Thereafter, in the first separation purification system 20, from the outlet gas of the reactor 10, a fluid rich in hydrocarbons having 3 or less carbon atoms, a hydrocarbon fluid having 4 or more carbon atoms (A), and rich in water. The process until separation into a fluid is the same as in FIG.
  • the hydrocarbon fluid (A) having 4 or more carbon atoms is supplied from a pipe 108 to a general separation and purification system 30B such as distillation. Separation and purification system 30B separates the fluid (G) with a lower aromatic compound concentration than the fluid (A) and the hydrocarbon concentration with 4 or more carbon atoms lower than the fluid (A)! /, Fluid (F). . Fluid (F) is withdrawn from the process through line 112.
  • the extraction fluid (F) may be mixed with a cracked gasoline fraction such as a steam cracking process. In that case, it is preferable that the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (F) is less than 5% by weight.
  • the fluid (G) is taken out from the pipe 113, a part (H) is taken out from the process through the pipe 114, and the remaining fluid (I) is recycled to the reactor 10 through the pipe 102.
  • the extracted fluid (H) may be used as a cracker raw material for the steam cracking process.
  • the fluid (H) is preferably supplied to the steam cracking process as a fluid in which the concentration of paraffin is increased by contacting the hydrogenation catalyst. At this time, the total concentration of aromatic compounds in the fluid (H) is preferably less than 5.0% by volume.
  • FIG. 3 illustrates one embodiment of the process of the present invention.
  • 13 is a reactor
  • 23 is a compressor
  • 33 is a knockout drum
  • 43 is an oil-water separator
  • 53 is a first separation and purification system
  • 63 is a second separation and purification system.
  • To 315 indicate piping.
  • At least one of the olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (Q) having 4 or more carbon atoms from the first separation and purification system 53, methanol, and dimethyl ether is provided in the pipes 301, 302, 303, and It is supplied to the reactor 13 through the pipe 304.
  • the olefin raw material having 4 or more carbon atoms supplied to the reactor 13 may contain paraffins having 4 or more carbon atoms, such as calalebutane and isobutane.
  • the raw material fluid supplied to the reactor 13 via the pipe 304 may contain butadiene or an aromatic compound.
  • the butadiene concentration in the raw material fluid as described above is usually 2.0% by volume or less, and the total amount of aromatic compounds is mol relative to the total amount of olefins having 4 or more carbon atoms contained in the raw material fluid of the pipe 304.
  • the ratio is usually less than 0.05.
  • the raw material fluid means the sum of the fluids supplied via the pipes 301, 302, and 303!
  • the reactor outlet gas is cooled through, for example, a heat exchanger, and the cooled gas fluid (K) is pressurized by the compressor 23 through the pipe 305.
  • One compressor 23 may be used, but a plurality of compressors 23 are preferable.
  • a heat exchanger and a knockout drum 33 are installed after each compressor 23, and after the compressed gas is cooled, it is separated into a gas fluid (L) and a condensed component. Condensed components are sent to the oil / water separator 43 via the pipe 30 8 and separated into a hydrocarbon-rich liquid fluid (M) having 4 or more carbon atoms and a water-rich fluid.
  • the liquid fluid (M) rich in hydrocarbons with 4 or more carbon atoms extracted is sent to the second separation / purification system 63 through the pipe 309.
  • the gas fluid (L) separated by the knockout drum 33 is sent to a general first separation / purification system 53 such as distillation through a pipe 307, and a fluid rich in hydrocarbons having 3 or less carbon atoms. Then, it is separated into a hydrocarbon-rich fluid (N) having 4 or more carbon atoms and taken out via pipes 313 and 314, respectively.
  • a hydrocarbon-rich fluid having 3 or less carbon atoms represents one or more fluids.
  • a part (P) of the fluid (N) rich in hydrocarbons having 4 or more carbon atoms is extracted from the process through the pipe 315, and the remaining fluid (Q) is supplied to the reactor 13 through the pipe 302. Recycled.
  • the fluid (P) may be used as a cracker raw material for the steam cracking process.
  • the fluid (P) is preferably supplied to the steam cracking process as a fluid in which the paraffin concentration is increased by contacting the hydrogenation catalyst.
  • the total concentration of aromatic compounds in the fluid (P) is preferably less than 5.0% by volume! /.
  • the liquid fluid (M) separated by the oil / water separator 43 is a liquid component rich in hydrocarbons having 4 or more carbon atoms and containing an aromatic compound, which is directly extracted from the process.
  • the liquid fluid (M) may be used as a cracker raw material for the steam cracking process.
  • the fluid (M) is preferably supplied to the steam cracking process as a fluid in which the paraffin concentration is increased by contacting the hydrogenation catalyst.
  • the total concentration of aromatic compounds in the fluid (M) is preferably less than 5.0% by volume.
  • the hydrocarbon concentration of carbon number 4 in the liquid fluid (M) is low, it may be mixed with a cracked gasoline fraction such as a steam cracking process. In that case, it is preferable that the total concentration of the hydrocarbon having 4 carbon atoms contained in the fluid (M) is less than 5% by weight.
  • the second separation / purification system 60 which is a general separation step such as distillation, and the concentration of the aromatic compound is lower than that of the liquid fluid (M)! /, It is preferable to separate the fluid (R) and the C4 hydrocarbon concentration from the liquid fluid (M) and the fluid (S).
  • the separated fluid (R) is extracted from the pipe 111, but the fluid (R) is fluid (K), fluid (L), fluid (N), fluid (P), fluid (Q) flow. It is preferable to return to one or more of 305, 307, 314, 315, 302.
  • the fluid (S) is extracted from the pipe 312 and the fluid (S) may be mixed with a cracked gasoline fraction such as a steam cracking process.
  • the total concentration of C 4 hydrocarbons contained in the fluid (S) is preferably less than 5% by weight.
  • Extraction of the fluid (P) out of the process is not always necessary, but paraffins In order to prevent accumulation of at least one of the fluids is preferably withdrawn from the process.
  • Bromide tetra n- propyl ammonium Niu beam (TPABr) 26. 6 g of sodium hydroxide 4 ⁇ 8 g successively, in water 280g ⁇ Hayashi, then roller Ida Honoré silica (SiO 40 weight 0/0, [alpha] 1 ⁇ (0.1% i%) 75 g and a mixture of 35 g of water were slowly added and stirred sufficiently to obtain an aqueous gel. Next, this gel was charged into a 1000 ml autoclave and hydrothermal synthesis was performed for 72 hours at a force of S, etc .; The product was separated from solid components by pressure filtration, washed thoroughly with water, and dried at 100 ° C for 24 hours. The dried catalyst was calcined at 550 ° C for 6 hours under air flow to obtain Na type aluminosilicate.
  • This catalyst was confirmed by XRD (X-ray diffraction) to have a zeolite structure of MFI type.
  • XRD X-ray diffraction
  • Propylene was produced using the above catalyst.
  • a normal pressure fixed bed flow reactor was used for the reaction, and a quartz reaction tube having an inner diameter of 6 mm was filled with a mixture of the above catalyst (0.10 g) and quartz sand (1 Og).
  • Anti ⁇ inlet gas of the present invention in the reactor isobutene (40 vol 0/0) as a model gas, which corresponds to the composition (Fig. 1 or the pipe 104 in FIG. 2), methanol (20 vol 0/0), benzene (0 . 8 vol 0/0), were fed through butadiene (0.1 body volume%) and isobutane (evaporator 39. was prepared in 1% by volume) gas.
  • the reaction temperature (reactor inlet gas temperature) was 550 ° C. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography. The reaction conditions and reaction results at that time are shown in Table 1.
  • the selectivity for propylene was 54.8%, a very high level.
  • the reaction was continued, and the time until the methanol conversion fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 312 hours.
  • the reaction was carried out in the same manner as in Example 1 except that the concentration of benzene supplied to the reactor was 1.6% by volume and the isobutane concentration was 38.3% by volume. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography. Table of reaction conditions and reaction results at that time
  • the selectivity for propylene was 54.4%, a very high level.
  • the reaction was continued, and the time until the methanol conversion fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 305 hours.
  • the reaction was performed in the same manner as in Example 1 except that the concentration of benzene supplied to the reactor was 3.2% by volume and the isobutane concentration was 36.7% by volume. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography. Table of reaction conditions and reaction results at that time
  • the selectivity for propylene was 51.4%, which was a very low level compared to Examples 1 and 2.
  • the reaction was continued, and the time until the methanol conversion fell below 99% was evaluated as the catalyst life.
  • the catalyst life was 221 hours, which was very short compared to Examples 1 and 2. This is presumably because the alkylated benzene blocks the pores of the catalyst and promotes coking.
  • reducing the aromatic compound concentration at the inlet of the reactor by extracting at least a part of the aromatic compound without recycling can achieve a high propylene yield and suppress catalyst coking deterioration. It is very effective.
  • the present invention is a new and economical process for producing propylene by reacting olefins having 4 or more carbon atoms with at least one of methanol and dimethyl ether, and a new and economical process that integrates this process with steam cracking. To provide a realistic process.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé permettant de produire du propylène en faisant réagir une matière première oléfinique comportant 4 atomes de carbone ou plus avec au moins un élément choisi parmi le méthanol et l'éther diméthylique en présence d'un catalyseur, qui permet de produire du propylène à un rendement élevé en utilisant une matière première en petite quantité tout en empêchant l'apparition de la détérioration du catalyseur.
PCT/JP2007/068299 2006-09-21 2007-09-20 Procédé de production de propylène WO2008035743A1 (fr)

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JP2008074764A (ja) * 2006-09-21 2008-04-03 Mitsubishi Chemicals Corp プロピレンの製造方法
JP2008081417A (ja) * 2006-09-26 2008-04-10 Mitsubishi Chemicals Corp プロピレンの製造方法
WO2010100069A1 (fr) * 2009-03-03 2010-09-10 Total Petrochemicals Research Feluy Procédé de fabrication d'oléfines à partir de composés organiques et de paraffines
WO2011013780A1 (fr) * 2009-07-30 2011-02-03 三菱化学株式会社 Procédé de production du propylène et catalyseur de production du propylène
WO2012015060A1 (fr) * 2010-07-30 2012-02-02 日本ガス合成株式会社 Procédé de fabrication du propylène
CN108276238A (zh) * 2018-02-12 2018-07-13 浙江大学 费托合成轻油与甲醇共催化裂解制低碳烯烃的方法
CN110041157A (zh) * 2019-05-10 2019-07-23 国家能源投资集团有限责任公司 一种提高甲醇制丙烯收率和延长催化剂寿命的方法

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WO2005016856A1 (fr) * 2003-08-19 2005-02-24 Total Petrochemicals Research Feluy Production d'olefines
WO2007023706A1 (fr) * 2005-08-24 2007-03-01 Jgc Corporation Procédé de production d'un hydrocarbure inférieur et appareil de production

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EP1195424A1 (fr) * 2000-10-05 2002-04-10 ATOFINA Research Procédé pour le craquage de charges hydrocarbonées riches en oléfines
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US7060865B2 (en) * 2002-11-12 2006-06-13 Exxonmobil Chemical Patents Inc. Recovery of C4 olefins from a product stream comprising C4 olefins, dimethyl ether and C5+ hydrocarbons
CN1333052C (zh) * 2004-07-14 2007-08-22 中国石油化工股份有限公司 一种生产低碳烯烃和芳烃的方法和装置
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US7405337B2 (en) * 2004-09-21 2008-07-29 Uop Llc Conversion of oxygenate to propylene with selective hydrogen treatment of heavy olefin recycle stream

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JPS6124526A (ja) * 1984-07-14 1986-02-03 Agency Of Ind Science & Technol 低級オレフインの製造法
WO2005016856A1 (fr) * 2003-08-19 2005-02-24 Total Petrochemicals Research Feluy Production d'olefines
WO2007023706A1 (fr) * 2005-08-24 2007-03-01 Jgc Corporation Procédé de production d'un hydrocarbure inférieur et appareil de production

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074764A (ja) * 2006-09-21 2008-04-03 Mitsubishi Chemicals Corp プロピレンの製造方法
JP2008081417A (ja) * 2006-09-26 2008-04-10 Mitsubishi Chemicals Corp プロピレンの製造方法
WO2010100069A1 (fr) * 2009-03-03 2010-09-10 Total Petrochemicals Research Feluy Procédé de fabrication d'oléfines à partir de composés organiques et de paraffines
WO2011013780A1 (fr) * 2009-07-30 2011-02-03 三菱化学株式会社 Procédé de production du propylène et catalyseur de production du propylène
CN102471180A (zh) * 2009-07-30 2012-05-23 三菱化学株式会社 丙烯的制造方法及丙烯制造用催化剂
EA019862B1 (ru) * 2009-07-30 2014-06-30 Мицубиси Кемикал Корпорейшн Способ получения пропилена и катализатор получения пропилена
JP5700376B2 (ja) * 2009-07-30 2015-04-15 三菱化学株式会社 プロピレンの製造方法及びプロピレン製造用触媒
WO2012015060A1 (fr) * 2010-07-30 2012-02-02 日本ガス合成株式会社 Procédé de fabrication du propylène
JPWO2012015060A1 (ja) * 2010-07-30 2013-09-12 日本ガス合成株式会社 プロピレンの製造方法
CN108276238A (zh) * 2018-02-12 2018-07-13 浙江大学 费托合成轻油与甲醇共催化裂解制低碳烯烃的方法
CN108276238B (zh) * 2018-02-12 2021-02-02 浙江大学 费托合成轻油与甲醇共催化裂解制低碳烯烃的方法
CN110041157A (zh) * 2019-05-10 2019-07-23 国家能源投资集团有限责任公司 一种提高甲醇制丙烯收率和延长催化剂寿命的方法

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KR20090059123A (ko) 2009-06-10
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TWI405750B (zh) 2013-08-21
TW200831453A (en) 2008-08-01
CN102766010A (zh) 2012-11-07

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