WO2008041561A1 - Procédé de production de propylène - Google Patents

Procédé de production de propylène Download PDF

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Publication number
WO2008041561A1
WO2008041561A1 PCT/JP2007/068572 JP2007068572W WO2008041561A1 WO 2008041561 A1 WO2008041561 A1 WO 2008041561A1 JP 2007068572 W JP2007068572 W JP 2007068572W WO 2008041561 A1 WO2008041561 A1 WO 2008041561A1
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Prior art keywords
fluid
reactor
ethylene
propylene
carbon atoms
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PCT/JP2007/068572
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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 KR1020097005976A priority Critical patent/KR101512860B1/ko
Priority to CN2007800356086A priority patent/CN101516812B/zh
Publication of WO2008041561A1 publication Critical patent/WO2008041561A1/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
    • C07C4/06—Catalytic processes
    • 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
    • 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
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the present invention relates to a process for producing propylene using ethylene and at least one of methanol and dimethyl ether as raw materials.
  • Patent Document 2 WO2005 / 056504 — On the other hand, as a method for producing butene, a method for dimerizing ethylene is also disclosed! (Non-patent Documents 1 and 2).
  • Non-Patent Document 1 Catalysis Today, 14, (1992) 28
  • Non-Patent Document 2 Journal of Occupational Chemistry, Vol. 66, No. 7 (1963) 973
  • the propylene production method using ethylene as a raw material is effective.
  • One example is the reaction of at least one of the above-mentioned ethylene with methanol and dimethyl ether. To produce propylene A method is mentioned.
  • the present invention relates to a method for producing propylene using ethylene and at least one of methanol and dimethyl ether as raw materials! /, And the equipment cost and utility cost for reducing the amount of unreacted ethylene recycled are low.
  • the aim is to provide a low and novel process
  • ethylene is also produced as a by-product in addition to propylene, but the ethylene / propylene weight ratio at the outlet of the reactor is much lower than 12.0. Therefore, we have found that it is possible to reduce the amount of ethylene recycled to the reactor significantly, and to reduce equipment costs and service costs with the power S.
  • the present invention has been achieved based on such findings, and the gist thereof is as follows.
  • At least a part of the fluid (X) and at least one of methanol and dimethyl ether At least a part of the fluid (X) and at least one of methanol and dimethyl ether.
  • a method for producing propylene characterized in that a fluid containing propylene is obtained by reacting in a second reactor in the presence of a second catalyst.
  • a method for producing propylene using ethylene and at least one of methanol and dimethyl ether as raw materials ethylene, at least of methanol and dimethyl ether in the first reactor in the presence of the first catalyst.
  • ethylene at least of methanol and dimethyl ether in the first reactor in the presence of the first catalyst.
  • methanol and dimethyl ether Propylene is obtained by reacting at least one of them in a second reactor in the presence of a second catalyst.
  • a method for producing propylene according to [2], comprising a process comprising the following steps (IB), (2B), (3B), (4B) and (5B).
  • [11] A method for producing propylene according to [10], comprising a process comprising the following steps (1C), (2C), (3C), (4C) and (5C):
  • Fluid (S) from process (2C) is enriched in hydrocarbons rich in hydrocarbons with 2 or less carbons (T), fluids rich in propylene, and rich in hydrocarbons with 4 or more carbons Fluid (U) and water To separate into a rich fluid
  • the amount of ethylene contained in the fluid (S) is less than 2.0 by weight with respect to propylene contained in the fluid (S).
  • the equipment cost and the utility cost for reducing the amount of ethylene recycled are low. Process can be provided.
  • 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.
  • FIG. 4 is a system diagram showing an example of a method for producing propylene of a comparative example.
  • the method for producing propylene of the present invention is a method for producing propylene using ethylene as a raw material or at least one of ethylene, methanol and dimethyl ether as a raw material,
  • At least a part of the fluid (X) and at least one of methanol and dimethyl ether At least a part of the fluid (X) and at least one of methanol and dimethyl ether.
  • a fluid containing propylene is obtained by reacting in the second reactor in the presence of the second catalyst. Specifically, the following 1st-3rd aspects are mentioned.
  • the method for producing propylene of the present invention is a method for producing propylene using ethylene and at least one of methanol and dimethyl ether as raw materials.
  • ethylene and methanol are used in the first reactor in the presence of the first catalyst.
  • a fluid (A) containing a fluid containing propylene, olefin having 4 or more carbon atoms, ethylene, norafine, an aromatic compound and water is obtained.
  • a fluid (B) containing propylene, olefins having 4 or more carbon atoms, ethylene, paraffin, aromatic compounds and water is obtained.
  • the "rich" in the present invention the purity of the target product 50 mol% or more, preferably 7 0 mole 0/0 or more, more preferably 90 mol 0/0 or more, more preferably 95 mol It means and this is 0/0 or more.
  • “fluid rich in hydrocarbons having 4 or more carbon atoms (E)” means “hydrocarbons having 4 or more carbon atoms” in an amount of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol%. More preferably, the fluid contains 95 mol% or more.
  • extract from the process means that the first reactor and the second reactor in the process are not recycled even if they are misaligned!
  • the present invention preferably includes five steps (1A), (2A), (3A), (4A) and (5A) as described above, or steps (IB), (2B), ( 3B), (4B) and (5B) are included, but as long as the purpose of solving the problems of the present invention is followed, the existence of other processes is not excluded. There may be other processes between each process, even if a process exists!
  • a method for producing propylene using ethylene and at least one of methanol and dimethyl ether as raw materials! /, And at least one of methanol and dimethyl ether, and ethylene dimerization reaction A force that includes a step of reacting with the 4-carbon olefin obtained by the above, preferably from the following five steps (1C), (2 C), (3C), (4C) and (5C) become.
  • the "rich" in the present invention the purity of the target product 50 mol% or more, preferably 7 0 mole 0/0 or more, more preferably 90 mol 0/0 or more, more preferably 95 mol It means and this is 0/0 or more.
  • “fluid rich in hydrocarbons having 4 or more carbon atoms (F)” means “hydrocarbons having 4 or more carbon atoms” in an amount of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol%. More preferably, the fluid contains 95 mol% or more.
  • extract from the process means that the first reactor and the second reactor in the process are not recycled even if they are misaligned!
  • the present invention is preferably a force including five steps (1C), (2C), (3C), (4C) and (5C) as described above, as long as the object of the present invention is to solve the problems of the present invention, It is not something that excludes the existence of other processes. There may be other processes before and after the five processes! /, And there may be other processes between each process! / Yo! /
  • step (1A) ethylene as a raw material, at least one of methanol and dimethyl ether as a raw material, and fluid (F) recycled from step (4A) are supplied to the first reactor, and By contacting with 1 catalyst, a fluid (A) containing a fluid containing propylene, an olefin having 4 or more carbon atoms, ethylene, paraffin, an aromatic compound and water is obtained.
  • the “first catalyst” refers to the catalyst used in the first reactor, and reacts ethylene with methanol and / or dimethyl ether to produce propylene and an olefin having 4 or more carbon atoms.
  • a catalyst that can be manufactured! [0036]
  • the catalyst used in this reaction is not particularly limited as long as it is a solid having a Bronsted acid point, and a conventionally known catalyst is used, for example, clay minerals such as kaolin; clay minerals, etc.
  • Solid acid catalysts such as acid-type ion exchange resins; zeolites; aluminum phosphates; mesoporous silica alumina such as A1-MCM41;
  • solid acid catalysts those having a molecular sieving effect are preferred, and those having a very high acid strength are preferred.
  • the structures of zeolites and aluminum phosphates having a molecular sieving effect can be represented by codes stipulated by the International Zeolite Association (IZA).
  • IZA International Zeolite Association
  • OT / nm 3 or less is preferable, preferably MFI, MEL, MOR, MWW, FAU, BEA, CHA, more preferably MFI, MEL, MOR, MWW, CHA, particularly preferably MFI, MEL, MW W, 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 pore size has a 0. 3 to 0 9 nm micropores, BET specific surface area of 200-700 2 / g, a pore volume of 0.5; 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 molar ratio of iO / Al 2 O is usually 10000 or less.
  • 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.
  • These catalysts may be used alone or in combination of two or more.
  • a substance or binder that is inert to the reaction may be used for granulation and molding, or! / ⁇ may be mixed for use in the reaction.
  • the substance and 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, or 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 size of the catalytically active component used in the present invention varies depending on the conditions during synthesis. Usually, the average particle size is 0.01 m to 500 m. 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 it 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 ethylene used as a reaction raw material is not particularly limited.
  • Produced by catalytic cracking or steam cracking from petroleum feedstock, obtained by FT (Fischer-Tropsch) synthesis using hydrogen / CO mixed gas obtained from coal gasification Various known methods such as those obtained by dehydrogenation or oxidative dehydrogenation, those obtained by propylene metathesis reaction and homozygous reaction, those obtained by MTO reaction, those obtained by ethanol dehydration reaction, etc.
  • What is obtained by a method can be used arbitrarily, At this time, the thing in the state which compounds other than ethylene resulting from each manufacturing method mixed arbitrarily may be used as it is, and refined ethylene may be used.
  • the origin of production of at least one of methanol and dimethyl ether used as a raw material for the reaction is not particularly limited.
  • obtained by hydrogenation reaction of coal and natural gas, and by-product hydrogen / CO mixed gas in the steel industry obtained by reforming reaction of plant-derived alcohol, obtained by fermentation method And those obtained from organic materials such as recycled plastics and municipal waste.
  • the “fluid (F) recycled from step (4A)” refers to the recycled fluid (F) obtained by step (4A) and is a fluid containing ethylene.
  • This fluid (F) is a part of the fluid (D) rich in hydrocarbons having 2 or less carbon atoms in the step (3A).
  • the “part” is usually in the range of 10 to 99% by weight, preferably 50 to 95% by weight, of the flow rate of the fluid (D). Below this range, there is a disadvantage that the flow rate of ethylene supplied to the first reactor as a new raw material increases. It is not preferable because it causes inconvenience of accumulation.
  • the fluid (F) recycled to the first reactor contains V and compounds that are not involved in the reaction such as methane ethane!
  • 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 first reactor inlet, and the upper limit of the reaction temperature is usually 600 ° C or lower, preferably 500 ° C. C or less. 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 remarkably lowered and the conversion of ethylene tends to be lowered.
  • the first reactor preferably has a temperature at the outlet of the first reactor that is lower than the temperature at the outlet of the second reactor in step (2A) and / or step (2B) described later. More preferably, the outlet temperature is 50 ° C. or more, for example, about 50 to 200 ° C. lower than the temperature of the second reactor outlet.
  • the upper limit of the reaction pressure is usually 2 MPa or less (absolute pressure, the same applies hereinafter), 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, preferable amounts of paraffins and aromatic compounds and by-products are increased, and the yield of propylene tends to decrease. If the reaction pressure is too low, the reaction rate tends to be slow.
  • the amount of ethylene supplied to the first reactor is 0.2 or more in a molar ratio with respect to the total of the number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether, preferably 0.5 or more, 5 or less, preferably 2 or less.
  • the molar amount of ethylene supplied is Met
  • the molar amount of methanol supplied is Mm
  • Met is 0.2 to 5 times, preferably 0.5 to 2 times (Mm + 2Mdm).
  • this feed concentration ratio is too low or too high, the reaction will be slow and unfavorable. In particular, if this feed concentration ratio is too high, the amount of ethylene at the outlet of the reactor will increase and the recycle flow rate will increase.
  • the supply concentration ratio can be 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.
  • ethylene and at least one of methanol and dimethyl ether are supplied to the reactor, they may be supplied separately or after a part or all of them are mixed in advance.
  • the total concentration (substrate concentration) of ethylene, methanol, and dimethyl ether in all the feed components fed to the first reactor is 20% by volume or more and 80% by volume or less, preferably 30% of the total. % To 70% by volume.
  • the substrate concentration is determined by the force S known by quantifying the composition of each fluid supplied to the first reactor or the fluid after mixing by 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 later so as to obtain such a substrate concentration.
  • the method for controlling the substrate concentration include a method for controlling the flow rate of the fluid extracted from the process. By changing the flow rate of the fluid withdrawn from the process, it is possible to change the flow rate of the diluent gas recycled to the first reactor and change the substrate concentration.
  • paraffins and aromatics are defined as dilution gases because the reaction amount is small, 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 diluent gas may be mixed with the reaction raw material before entering the first reactor, or may be supplied to the first reactor separately from the reaction raw material.
  • 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 ethylene, methanol and dimethyl ether will be low. Also, if the space velocity is too low, the amount of catalyst necessary to obtain a constant production amount increases, and the first reactor becomes too large. Since a by-product is formed, it is not preferable.
  • the space velocity mentioned here is the flow rate of ethylene, which is the reaction raw material per weight of the catalyst (catalytic active component), and the weight of the catalyst here refers to the inert component used for the granulation / molding of the catalyst. It is the weight of the catalytically active component not containing a binder.
  • the flow rate is the flow rate (weight / time) of ethylene.
  • the sum of the molar flow rate of methanol fed to the first reactor and twice the molar flow rate of dimethyl ether is the sum of the molar flow rate of methanol at the outlet of the first reactor and twice the molar flow rate of dimethyl ether. Less than 1% is preferred. More preferably, it is less than 0.1%. If the amount of methanol or dimethyl ether at the outlet of the first reactor, which consumes less, is increased too much, it becomes difficult to purify the product olefin. One way to increase consumption is to increase the reaction temperature or decrease the space velocity.
  • the flow rates of methanol, dimethyl ether, and ethylene supplied to the first reactor are the same as the composition of each fluid supplied to the first reactor or the fluid after mixing. Quantitative analysis techniques can be used to determine the flow rate of each fluid, and methanol and dimethyl ether at the outlet of the first reactor.
  • the flow rate of ethylene is determined by quantifying the composition of the first reactor outlet fluid using a general method such as gas chromatography, and measuring or calculating the flow rate of the first reactor outlet fluid. I'll do it.
  • the ethylene conversion rate in the first reactor is usually 30% or more, preferably 40% or more and less than 80%. If the ethylene conversion is below this range, unreacted olefins increase, and the flow rate of the fluid recycled to the first reactor becomes too large. On the other hand, exceeding this range is not preferable because undesirable compounds such as paraffin and aromatic compounds are by-produced.
  • the “ethylene conversion rate” in the present invention refers to the rate at which ethylene is converted to a compound other than ethylene, and is represented by the following formula.
  • the ethylene conversion rate can be quantified by a general analytical method such as gas chromatography and a flow meter.
  • Fluid (A) containing fluid containing propylene, olefin having 4 or more carbon atoms, ethylene, paraffin, aromatic compound and water means the fluid at the outlet of the first reactor.
  • a mixed gas containing propylene as a reaction product, 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 ethylene.
  • Products include propylene, olefins with 4 or more carbon atoms, norafines, aromatic compounds and water.
  • step (2A) At least one of methanol and dimethyl ether as raw materials and the fluid (G) recycled from step (5A) are supplied to the second reactor and brought into contact with the second catalyst. And a fluid (B) containing propylene, olefin having 4 or more carbon atoms, ethylene, paraffin, an aromatic compound and water.
  • “Second catalyst” refers to the catalyst used in the second reactor, and reacts methanol and / or dimethyl ether with olefins having 4 or more carbon atoms to produce propylene and olefins having 4 or more carbon atoms.
  • the catalyst used as the second catalyst those described in the “first catalyst” in [Description of step (1A)] can be used.
  • the second catalyst a catalyst having the same structure and composition as that used as the first catalyst may be used, or a catalyst having a different structure and / or different composition may be used.
  • the SiO 2 / Al 2 O molar ratio of the second catalyst is higher than the SiO 2 / Al 2 O molar ratio of the first catalyst.
  • 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 mixed gas in the steel industry those obtained by reforming plant-derived alcohols, and obtained by fermentation And those obtained from organic materials such as plastic and municipal waste.
  • it can be used as it is in a state in which compounds other than methanol and dimethyl ether resulting from each production method are arbitrarily mixed, and it can also be used as a purified product.
  • fluid (G) recycled from step (5A) refers to the recycled fluid (G) obtained from step (5A).
  • Fluid (G) contains hydrocarbons with 4 or more carbon atoms.
  • This fluid (G) is a part of the fluid (E) rich in hydrocarbons having 4 or more carbon atoms in the step (3A).
  • the “part” usually refers to the range of 10 to 99% by weight, preferably 50 to 95% by weight, of the flow rate of the fluid (E).
  • the hydrocarbon-rich fluid (G) having 4 or more carbon atoms recycled to the second reactor is not particularly limited as long as it contains olefin, and includes paraffin and aromatic compounds. May be.
  • the form of the gas phase reactor is not particularly limited, but is usually selected from a continuous fixed bed reactor and a fluidized bed reactor.
  • a fixed bed reactor is preferred.
  • granular materials inert to the reaction such as quartz sand, alumina, silica, silica-alumina, etc. You may mix and fill with a catalyst.
  • there is no particular limitation on the amount of granular material inert to the reaction such as quartz sand.
  • this granular material is a particle size comparable as a catalyst from the surface of uniform mixing property with a catalyst.
  • 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 inlet of the second reactor, and the upper limit of the reaction temperature is usually 700 ° C or lower, preferably 600 ° C. C or less. 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 shall apply hereinafter) or less, preferably IMPa or less, and 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 amount of olefins having 4 or more carbon atoms supplied to the second reactor is supplied to the second reactor.
  • the molar ratio is 0.2 or more, preferably 0.5 or more, and 10 or less, preferably 5 or less, based on the total number of moles of methanol and twice the number of moles of dimethyl ether.
  • 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.
  • the supply concentration ratio refers to the force S that is lost by quantifying the composition of each fluid supplied to the second reactor or the fluid after mixing by a general analytical method such as gas chromatography.
  • the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol, and dimethyl ether in all feed components fed to the second reactor is 20% by volume or more and 80% by volume or less of the total.
  • It is preferably 30% by volume or more and 70% by volume or less of the whole.
  • the substrate concentration is known by quantifying the composition of each fluid supplied to the second reactor or the fluid after mixing by a general analytical method such as gas chromatography. Monkey.
  • 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 to be described later so as to obtain such a substrate concentration.
  • the hydrocarbon fluid recycled to the second reactor and / or the olefin raw material having 4 or more carbon atoms contains a butadiene compound! /.
  • the concentration of butadiene in all feed components fed to the second reactor is preferably 2.0% by volume or less.
  • the butadiene concentration can be determined by quantifying the composition of each fluid supplied to the second reactor or the fluid after mixing with a general analytical method such as gas chromatography.
  • Examples of the method for reducing the butadiene concentration include a partial hydrogenation method in which the fluid is converted into olefins using a hydrogenation catalyst.
  • the hydrocarbon fluid recycled to the second reactor may contain an aromatic compound.
  • the total amount of aromatic compounds contained in all the gases supplied to the second reactor is based on the total amount of olefins having 4 or more carbon atoms contained in all the gases supplied to the second reactor.
  • the molar ratio is preferably less than 0.05.
  • the ratio of the total amount of the aromatic compound and the total amount of olefins having 4 or more carbon atoms depends on the composition of each fluid supplied to the second reactor or the fluid after mixing, such as gas chromatography. This can be determined by quantitative analysis using a typical analysis method.
  • the aromatic compound reacts with at least one of methanol and dimethyl ether in the second reactor, and consumes at least one of methanol and dimethyl ether more than necessary. Therefore, it is not preferable.
  • a separation method by distillation may be mentioned.
  • the second reactor in addition to olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether, norafines, aromatics, water vapor, carbon dioxide, carbon monoxide, Gases that are inert to the reaction can be present such as nitrogen, argon, helium, and mixtures thereof. Of these dilution gases, paraffins and aromatics are defined as dilution gases because the reaction amount is small, which 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 second reactor, or the reaction raw material may be mixed. It may be supplied to the second reactor separately from the charge.
  • 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 necessary to obtain a certain production amount increases, the second reactor becomes too large, and undesirable by-products such as aromatic compounds and paraffin are generated. This is not preferable because the propylene selectivity is lowered.
  • the space velocity referred to here is the flow rate of olefins having 4 or more carbon atoms as the reaction raw material per weight of the catalyst (catalytic active component).
  • the weight of the catalyst refers to the granulation / molding of the catalyst. It is the weight of the inert component used and the catalytically active component that does not contain a binder.
  • the flow rate is the flow rate (weight / time) of olefin having 4 or more carbon atoms.
  • the sum of the molar flow rate of methanol fed to the second reactor and twice the molar flow rate of dimethyl ether is the sum of the molar flow rate of methanol at the outlet of the second reactor and twice the molar flow rate of dimethyl ether. Less than 1% is preferred. More preferably, it is less than 0.1%. If the amount of methanol or dimethyl ether at the outlet of the second reactor, which consumes less, is increased too much, it will be difficult to purify the product olefin. One way to increase consumption is to increase the reaction temperature or decrease the space velocity.
  • the total molar flow rate of olefins having 4 or more carbon atoms at the outlet of the second reactor is 20% or more of the total molar flow rates of olefins having 4 or more carbon atoms supplied to the second reactor. Less than 70% is preferable. Preferably it is 25% or more and less than 60%.
  • the flow rates of methanol and dimethyl ether and olefin having 4 or more carbon atoms to be supplied to the second reactor are the respective fluids to be supplied to the second reactor or after mixing.
  • the composition of each fluid can be quantified using a general analytical method such as gas chromatography, and the flow rate of each fluid can be measured to determine the methanol and dimethyl ether at the outlet of the second reactor, as well as those with 4 or more carbon atoms.
  • the olefin flow rate can be determined by quantifying the composition of the second reactor outlet fluid using a general technique such as gas chromatography and measuring or calculating the flow rate of the second reactor outlet fluid.
  • Fluid (B) containing propylene, olefin having 4 or more carbon atoms, ethylene, paraffin, aromatic compound and water means a fluid at the outlet of the second reactor.
  • a mixed gas containing propylene as a reaction product, 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, aromatic compounds and water.
  • the fluid (C) obtained by mixing the fluid (B) obtained in the step (2A) is mixed with a hydrocarbon-rich fluid (D) having 2 or less carbon atoms, a propylene-rich fluid, carbon Separated into a hydrocarbon-rich fluid (E) and water-rich fluid of number 4 or higher.
  • the amount of ethylene contained in the mixed fluid (C) is preferably less than 2.0 by weight with respect to propylene contained in the fluid. More preferably, it is less than 1.5, and more preferably less than 1.0. This makes it possible to significantly reduce equipment costs and utility costs for the entire process.
  • the weight ratio of ethylene and propylene contained in fluid (C) can be determined by quantifying the composition of the fluid using a general analytical method such as gas chromatography.
  • the weight ratio of ethylene and propylene in fluid (C) can be changed by adjusting the reaction conditions such as the reaction temperature and space velocity of the first reactor and / or the second reactor.
  • the fluid (C) is subjected to a general separation process such as cooling, compression and distillation, so that the fluid (D) rich in hydrocarbons having 2 or less carbon atoms, the fluid rich in propylene, or the hydrocarbons having 4 or more carbon atoms.
  • a fluid rich in water (E) and a fluid rich in water are separated into a fluid rich in water (E) and a fluid rich in water.
  • each fluid is not limited to one fluid, and may be a plurality of fluids.
  • a hydrocarbon-rich fluid (E) with 2 or less carbon atoms may be one fluid containing methane, ethylene, or ethane, but two fluids, a fluid rich in methane and a fluid rich in ethylene and ethane. good.
  • the fluid (C) contains an oxygen-containing compound
  • at least a part of the oxygen-containing compound is removed by the Quenche process.
  • acidic gas such as carbon dioxide is contained in the reactor outlet gas
  • at least a part of the acidic gas is removed by alkali cleaning. Separation of water is possible mainly by condensation through compression and cooling.
  • the remaining water is preferably removed 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 can also be used for process water. If this process is close to the steam cracking process, it should be used as a cracker steam source. Further, it may be recycled to the first reactor in the step (1A) and / or the second reactor in the step (2A) and used as a dilution gas.
  • the obtained propylene-rich fluid is further purified by a purification process such as distillation.
  • the purity of propylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.
  • Propylene produced can be used as a raw material for all of the generally produced propylene derivatives.
  • acrylonitrile is produced by ammoxidation, and acrolein, acrylic acid and acrylate esters are produced by selective oxidation.
  • oxo alcohols such as normal butanol alcohol and 2-ethylhexanol by the oxo reaction
  • polypropylene by the polymerization of propylene
  • propylene oxalate by the selective oxidation of propylene. It can be applied to the production of id and propylene glycol.
  • acetone can be produced by the Hacker reaction, and methylisobutyl ketone can be produced from acetone.
  • Acetone can also produce acetone cyanohydrin, which is ultimately converted to methyl methacrylate.
  • Isopropyl alcohol can also be produced by propylene hydration.
  • phenol, bisphenol A, and polycarbonate resin can be produced from cumene produced by alkylating benzene.
  • step (4A) a part of fluid (F) of fluid (D) in step (3A) is recycled to the first reactor, and the remaining fluid is the process of the present invention (hereinafter referred to as “the present process”). (March be removed)
  • the fluid (D) may be divided into a recycled fluid (F) and a fluid to be extracted without introducing the fluid (D) into the separation process, but the fluid (D) is introduced into the separation process and the fluid (D) Alternatively, the fluid with increased ethylene concentration may be recycled to the first reactor.
  • the extracted fluid may be purified to recover an active ingredient such as ethylene, or may be used as a fuel. It may also be used as a raw material for steam cracking.
  • step (5A) a part of fluid (G) of fluid (E) in step (3A) is recycled to the second reactor, and the remaining fluid is extracted from the process.
  • the fluid (E) may be divided into the recycled fluid (G) and the fluid to be extracted without being introduced into the separation process, but the fluid (E) is introduced into the separation process and the fluid (E) Alternatively, a fluid with a higher butene concentration may be recycled to the second reactor.
  • the extracted fluid may be purified to recover effective components such as butene and aromatic compounds, or may be used as fuel. It can also be used as a raw material for steam cracking.
  • step (IB) ethylene as a raw material, at least one of methanol and dimethyl ether as a raw material, and fluid (L) recycled from step (4B) are supplied to the first reactor, and By contacting with 1 catalyst, a fluid (A) containing a fluid containing propylene, an olefin having 4 or more carbon atoms, ethylene, paraffin, an aromatic compound and water is obtained.
  • step (1B) ⁇ first catalyst>, ⁇ reaction raw material>, ⁇ first reactor>, ⁇ reaction conditions>, ⁇ consumption of raw material by reaction>, ⁇ propylene, carbon number 4
  • the fluid (A)> containing olefin, ethylene, norafine, aromatic compound and water is substantially the same as that described in [Description of Step (1A)] in ⁇ First Aspect ⁇ . is there.
  • Recycled fluid (L) from step (4B) refers to the recycled fluid obtained from step (4B) (refers to U and is a fluid containing ethylene.
  • This fluid (U is the same as step (3B)). It is a part of the fluid (J) rich in hydrocarbons with 2 or less carbon atoms, where! /, “Part” is usually 10 to 99% by weight of the fluid (J) flow rate. In the range of 50 to 95% by weight, below this range, there is an inconvenience that the flow rate of ethylene supplied to the first reactor as a new raw material increases, and conversely, this range is exceeded. This is not preferable because of the inconvenience that methane ethane accumulates in the first reactor and recycle fluid.
  • the fluid (L) recycled to the first reactor may contain methane methatan.
  • the fluid (A) obtained in the step (1B), at least one of methanol and dimethyl ether as a raw material, and the fluid (M) whose step (5B) force is also recycled are used in the second step.
  • the fluid (I) containing propylene, olefin having 4 or more carbon atoms, ethylene, norafine, aromatic compound and water is obtained by supplying to the second reactor and contacting with the second catalyst.
  • Recycled fluid (M) from step (5B) refers to the recycled fluid (M) obtained in step (5B), which is a fluid containing hydrocarbons having 4 or more carbon atoms.
  • This fluid (M) is a part of the fluid (K) rich in hydrocarbons having 4 or more carbon atoms in the step (3B).
  • the “part” here is usually in the range of 10 to 99% by weight, preferably in the range of 50 to 95% by weight of the flow rate of the fluid (K). Below this range, the amount of olefins recycled to the reactor is reduced, causing the disadvantage of reduced propylene yield. Conversely, above this range, paraffin contained in fluid (K) accumulates. However, the flow rates of the fluids (I) and (M) are increased, resulting in inconveniences such as increased equipment costs and utility costs.
  • the fluid (M) recycled to the second reactor is not particularly limited as long as it contains olefin, and may contain paraffin or aromatic compounds.
  • Fluid containing propylene, olefin having 4 or more carbon atoms, ethylene, paraffin, aromatic compound and water (I) means the fluid at the outlet of the second reactor in step (2B).
  • the second reactor outlet fluid (I) As the second reactor outlet fluid (I), a mixed gas containing propylene as a reaction product, 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, aromatic compounds and water.
  • the amount of ethylene contained in the fluid (I) is preferably less than 2.0 by weight with respect to propylene contained in the fluid. More preferably less than 1.5, still more preferably 1.0 Is less than. This can significantly reduce equipment costs and utility costs for the entire process.
  • the weight ratio of ethylene and propylene contained in fluid (I) can be determined by quantifying the composition of the fluid using a general analytical method such as gas chromatography.
  • the weight ratio of ethylene and propylene in fluid (I) can be changed by adjusting the reaction conditions such as the reaction temperature and space velocity of the first reactor and / or the second reactor.
  • step (3B) the fluid (I) obtained in step (2B) is replaced with a fluid rich in hydrocarbons having 2 or less carbon atoms (J), a fluid rich in propylene, and rich in hydrocarbons having 4 or more carbon atoms. It separates into a fluid ( ⁇ ) and a water-rich fluid.
  • the fluid (I) obtained in the step (2 ⁇ ) is rich in hydrocarbons (J) and propylene rich in hydrocarbons having 2 or less carbon atoms by general separation steps such as cooling, compression and distillation. It is separated into a fluid rich in hydrocarbons with 4 or more carbon atoms ( ⁇ ) and a fluid rich in water.
  • each fluid is not limited to one fluid, and may be a plurality of fluids.
  • a hydrocarbon-rich fluid (J) with 2 or less carbon atoms may be one fluid containing methane, ethylene, or ethane, but two fluids, a fluid rich in methane and a fluid rich in ethylene and ethane. But it ’s okay.
  • the fluid (I) contains an oxygen-containing compound
  • at least a part of the oxygen-containing compound is removed by the Quenche process.
  • acidic gas such as carbon dioxide
  • alkali cleaning at least a part of the acidic gas is removed by alkali cleaning. Separation of water is possible mainly by condensation through compression and cooling. The remaining water is preferably removed 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 can also be used for process water. If this process is close to the steam cracking process, it should be used as a steamer steam source. Also, it can be recycled to the first reactor in step (1B) and / or the second reactor in step (2) and used as a dilution gas.
  • the obtained propylene-rich fluid is further purified by a purification process such as distillation.
  • a purification process such as distillation.
  • propylene is obtained.
  • the purity of propylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.
  • Propylene produced can be used as a raw material for all of the generally produced propylene derivatives.
  • acrylonitrile is produced by ammoxidation, and acrolein, acrylic acid and acrylate esters are produced by selective oxidation. It can be applied to the production of oxo alcohols such as normal butanol alcohol and 2-ethylhexanol by an oxo reaction, to the production of polypropylene by the polymerization of propylene, and to the production of propylene oxide and propylene glycol by the selective oxidation of propylene. it can.
  • acetone can be produced by the Ralpher reaction, and methylisobutyl ketone can be produced from acetone.
  • Acetone can also produce acetone cyanohydrin, which is ultimately converted to methyl methacrylate.
  • Isopropyl alcohol can also be produced by propylene hydration.
  • phenol, bisphenol A, and polycarbonate resin can be produced from cumene produced by alkylating benzene.
  • step (4B) a part of fluid (L) of fluid (J) in step (3B) is recycled to the first reactor, and the remaining fluid is extracted from the process of the present invention.
  • the fluid (J) into the recycle fluid (U and the fluid to be extracted) without introducing it into the separation process.
  • the fluid ⁇ is introduced into the separation process and the ethylene concentration is higher than that of the fluid ⁇ .
  • the elevated fluid may be recycled to the first reactor, and the extracted fluid may be purified to recover active components such as ethylene or used as fuel. It may also be used as a raw material for steam cracking.
  • step (5 ⁇ ) a part of fluid ( ⁇ ) in step (3 ⁇ ) is recycled to the second reactor, and the remaining fluid is extracted from this process.
  • the fluid ( ⁇ ) may be divided into the recycled fluid ( ⁇ ) and the extracted fluid without introducing the fluid ( ⁇ ) into the separation process, but the fluid ( ⁇ ) is introduced into the separation process and the fluid ( ⁇ ) Than butene
  • the concentrated fluid may be recycled to the second reactor.
  • the extracted fluid may be purified to recover active ingredients such as butene and aromatic compounds, or may be used as fuel. It may also be used as a raw material for steam cracking.
  • a fluid containing olefin having 4 or more carbon atoms is newly added to the second reactor in the aforementioned step (2A) or (2B) as a part of the raw material for the production of propylene. You may supply.
  • the olefin having 4 or more carbon atoms used as a raw material for the reaction is not particularly limited.
  • oil feedstock power catalytic cracking method or steam cracking, etc. (BB fraction, C4 rough rice toe 1, C4 rough rice toe 2, etc.), hydrogen / CO mixed gas obtained by coal gasification Materials obtained by FT (Fischer-Tropsch) synthesis as raw materials, those obtained by dehydrogenation or oxidative dehydrogenation of paraffins with 4 or more carbon atoms, those obtained by MTO reaction, alcohol dehydration reaction Olefins having 4 or more carbon atoms, especially 4 to 10 carbon atoms, which are obtained by various known methods, such as those obtained by hydrogenation reaction of gen compounds having 4 or more carbon atoms, are optionally used.
  • a compound in which a compound other than olefin having 4 or more carbon atoms resulting from each production method is arbitrarily mixed may be used as it is.
  • the reaction temperature can be easily controlled because paraffin plays the role of a dilution gas, and raw materials containing paraffin can be obtained at low cost. It is preferable because there are many cases. More preferred is an olefin raw material containing normal butane and / or isobutane. These preferred and raw materials include the above-mentioned BB fraction, C4 rough rice toe 1 and C4 rough rice toe 2. Since the BB fraction contains a large amount of butadiene, it is preferable to use a fluid that has been brought into contact with the hydrogenation catalyst to lower the butadiene concentration.
  • the supply amount of fluid containing olefins having 4 or more carbon atoms from outside this process is not particularly limited.
  • Steps (1A) to (5A) and Process Features of Steps (1B) to (5B) are characterized in that hydrocarbons having 3 or less carbon atoms such as ethylene and propylene produced in the first reactor are supplied to the second reactor. This is a point that cannot be avoided. For this reason, it is possible to efficiently take out propylene produced in each of the first reactor and the second reactor as a product.
  • the second aspect of the process (1B) to (5B) is characterized by the fact that ethylene and propylene produced in the first reactor are supplied to the second reactor. A part of the propylene thus reacted is converted into another compound.
  • the flow rate of the fluid (I) supplied to the separation and purification system in step (3B) is higher than the flow rate of the fluid (C) supplied to the separation and purification system in step (3A) of the first embodiment. Since it is very small, there is a feature that the cost of using the separation and purification system and the equipment cost are small.
  • step (1C) ethylene as a raw material and the fluid (P) recycled from the step (4C) are supplied to the first reactor and brought into contact with the ethylene dimerization catalyst. A fluid (Q) containing refin is obtained.
  • the “ethylene dimerization catalyst” used in the reaction according to the present invention (hereinafter sometimes referred to simply as “catalyst” in step (1C)) is a 4-carbon polyolefin (butene). ) A catalyst having the ability to produce!
  • Such a catalyst is not particularly limited as long as it has a catalyst function for the reaction of producing butene by dimerization of ethylene, and a conventionally known catalyst is used.
  • This catalyst may be a complex catalyst or a solid catalyst.
  • a catalyst containing titanium such as a tetroboxytitanium triethyl aluminum composite catalyst, a catalyst containing nickel, a catalyst containing noradium, or the like is used.
  • a catalyst containing nickel such as a nickel oxide supported catalyst is used as the solid catalyst.
  • the reaction is performed in the liquid phase, it is preferable to use a complex catalyst.
  • the solid catalyst is used.
  • a medium is preferred.
  • These catalysts may be used alone or as a mixture of two or more.
  • the ethylene used as a reaction raw material is not particularly limited.
  • those produced by catalytic cracking or steam cracking from petroleum feedstock those obtained by FT (Fischer-Tropsch) synthesis using hydrogen / CO mixed gas obtained by gasification of coal
  • FT Fischer-Tropsch
  • Known to be obtained by ethane dehydrogenation or oxidative dehydrogenation, obtained by propylene metathesis and homozygous reaction obtained by MTO reaction, obtained by ethanol dehydration, etc.
  • Those obtained by these various methods can be used arbitrarily, and at this time, a compound in which a compound other than ethylene resulting from each production method is arbitrarily mixed may be used as it is, or purified ethylene may be used. good.
  • “Recycled fluid from step (4C) (P)” means that the fluid (T) rich in hydrocarbons having 2 or less carbon atoms obtained in step (3C) is recycled to the first reactor.
  • This fluid (P) contains ethylene.
  • the “part” here is usually in the range of 10 to 99% by weight, preferably in the range of 50 to 95% by weight, of the flow rate of the fluid (T). If the ratio of fluid (P) is below this range, there will be an inconvenience that the flow rate of ethylene supplied to the reactor as a new raw material will increase.On the other hand, if it exceeds this range, methane will be added to the reactor and the reactor. This is not preferable because it causes inconvenience of accumulation in the recycle fluid.
  • the fluid (P) recycled to the first reactor is not involved in the reaction such as methane ethane! / Contains compounds!
  • the type of the reactor is not particularly limited, and may be a liquid phase reactor or a gas phase reactor.
  • a process for removing the catalyst from the reactor outlet fluid (Q) is incorporated.
  • a solid catalyst is used in the gas phase, it is selected from a continuous fixed bed reactor or a fluidized bed reactor. A fixed bed reactor is preferred.
  • reaction conditions vary greatly depending on the reaction type and the catalyst. Normally, when a complex catalyst is used in the liquid phase, the reaction temperature is 300 ° C or less, for example 20 to 200 ° C, the reaction pressure is 0.5 MPa or more, for example 1.0 to 5. OMPa is a preferred gas phase. In the case of using a solid catalyst at 200 ° C. or higher, for example, 300 to 700 ° C., IMPa or lower, for example, 0.;! To 0.5 MPa is preferable. In the case of a liquid phase reaction, the force that can use a solvent for the reaction, and the produced butene may be used as a solvent.
  • the solvent is not particularly limited as long as it is inert to the reaction, but noraffins are preferable.
  • the concentration of the solvent is preferably less than 90% by weight, for example, 0 to 50% by weight. If the concentration of the solvent is too high, the reaction rate becomes slow, which is not preferable.
  • a diluent gas can be used for the reaction.
  • the diluent gas is not particularly limited as long as it is inert to the reaction, and examples thereof include norafines, aromatics, water vapor, carbon dioxide, carbon monoxide, nitrogen, argon, helium, and mixtures thereof. .
  • the concentration of the dilution gas is preferably less than 90% by volume, for example, 0 to 80% by volume. If the concentration of the dilution gas is too high, the reaction rate becomes slow, which is not preferable.
  • the concentration of the solvent or the concentration of the dilution gas can be known by a general analytical method such as gas chromatography.
  • the ethylene consumption is preferably 50% or more of the amount of ethylene supplied to the first reactor. If the amount of ethylene consumed is too low, the unreacted ethylene recycling flow increases, which is not preferable.
  • means for increasing the consumption include a method for increasing the reaction temperature and pressure, and a method for increasing the amount of catalyst.
  • the “fluid containing Q 4 olefin (Q)” means the first reactor outlet fluid.
  • the outlet fluid (Q) of the first reactor usually contains unreacted ethylene and the by-product hexene in addition to the target butene.
  • a step for separating the catalyst is required, but without any other separation, a fluid containing ethylene, butene, and hexene is introduced into the second reactor in step (2C).
  • unreacted ethylene is separated by a general separation method such as distillation, the separated ethylene is recycled to the first reactor, and the remaining fluid is recycled to the second reactor in step (2C). May be introduced.
  • a part of the fluid (Q), for example, 0 to 80%, is not supplied to the second reactor in the step (2C), but outside the process of the present invention (hereinafter sometimes referred to as “the present process”). It can be extracted. In this case, it is preferable that butene is purified and separated from the extracted fluid and used for other purposes. Specific examples of other purposes include raw materials for butadiene production by oxidative dehydrogenation reaction or dehydrogenation reaction.
  • step (2C) fluid (Q) from step (1C), fluid (R) recycled from step (5C), and at least one of methanol and dimethyl ether are supplied to the second reactor.
  • a propylene production catalyst By contacting with a propylene production catalyst, a fluid (S) containing propylene, ethylene, other olefins, paraffin, an aromatic compound and water is obtained.
  • the “propylene production catalyst” in the present invention (hereinafter sometimes simply referred to as “catalyst” in step (2C)) is a process for producing propylene from olefins having 4 or more carbon atoms, methanol and dimethyl ether. Refers to a possible catalyst.
  • the catalyst used in this reaction is not particularly limited as long as it is a solid having a Bronsted acid point, and a conventionally known catalyst is used.
  • clay minerals such as kaolin
  • examples include impregnated and supported acids such as sulfuric acid and phosphoric acid; acidic ion exchange resins; zeolites; aluminum phosphates; and solid acid catalysts such as mesoporous silica alumina such as A1-MCM41.
  • solid acid catalysts those having a molecular sieving effect are preferred, and those having a very high acid strength are preferred.
  • the structure of zeolites and aluminum phosphates having a molecular sieving effect can be represented by codes stipulated by the International Zeolite Association (IZA).
  • IZA International Zeolite Association
  • AEI AEI, AET, AEL, AFI, AFO , AFS, AST, ATN, BEA, CAN, CHA, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MT T, MTW, MWW, OFF, PAU, RHO, STT, TON, etc.
  • OT / nm 3 or less is preferable, preferably MFI, MEL, MOR, MWW, FAU, BEA, CHA, more preferably MFI, MEL, MOR, MWW, CHA, particularly preferably MFI, MEL, MW W, 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 pore size has a 0. 3 to 0 9 nm micropores, BET specific surface area of 200-700 2 / g, a pore volume of 0.5; 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.
  • These catalysts may be used alone or in combination of two or more.
  • a substance inert to the reaction or a binder may be used for granulation and molding, or may be mixed for use in the reaction.
  • Substances and binders that are inert to the reaction include alumina or alumina sol, silica, silica gel, quartz, and mixtures thereof. Compound etc. are mentioned.
  • 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 catalyst is preferably a combination using a complex catalyst containing titanium or nickel as the aforementioned "ethylene dimerization catalyst” and a catalyst having an MFI structure or MWW structure as the "propylene production catalyst". Can be mentioned.
  • 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 mixed gas in the steel industry those obtained by reforming plant-derived alcohols, and obtained by fermentation And those obtained from organic materials such as plastic and municipal waste.
  • it can be used as it is in a state in which compounds other than methanol and dimethyl ether resulting from each production method are arbitrarily mixed, and it can also be used as a purified product.
  • Fluid (R) is a fluid rich in hydrocarbons with 4 or more carbon atoms. This fluid (R) is a part of the fluid (U) rich in hydrocarbons having 4 or more carbon atoms in the step (3C) and recycled to the second reactor.
  • the “part” here is usually in the range of 10 to 99% by weight, preferably in the range of 50 to 95% by weight of the flow rate of the fluid (U). If the ratio of the fluid (R) is below this range, the olefin flow rate of 4 or more carbon atoms fed to the second reactor will decrease, causing the disadvantage that the propylene yield will decrease, and conversely above this range. This is not preferable because paraffin is accumulated in the reactor and the recycle fluid.
  • the fluid (R) recycled to the second reactor is not particularly limited as long as it contains olefins! /, And includes paraffins and aromatic compounds! / .
  • the form of the gas phase reactor is not particularly limited, but is usually selected from a continuous fixed bed reactor and a fluidized bed reactor.
  • a fixed bed reactor is preferred.
  • granular materials inert to the reaction such as quartz sand, alumina, silica, silica-alumina, etc. You may mix and fill with a catalyst.
  • there is no particular limitation on the amount of granular material inert to the reaction such as quartz sand.
  • this granular material is a particle size comparable as a catalyst from the surface of uniform mixing property with a catalyst.
  • 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 shall apply 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 paraffins and aromatic compounds that are preferred and by-products will increase, and the yield of propylene will increase. There is a tendency to decrease. If the reaction pressure is too low, the reaction rate tends to be slow.
  • the amount of olefin having 4 or more carbon atoms fed to the second reactor is 0 in terms of a molar ratio with respect to the sum of the number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether. 2 or more, preferably 0.5 or more, and 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. If this supply concentration ratio is too low or too high, the reaction will be slow and unfavorable. In particular, if this supply concentration ratio is too low, the consumption of raw olefin will be reduced.
  • the supply concentration ratio can be 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.
  • olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether may be supplied separately or after partial or total mixing. May be.
  • the total concentration (substrate concentration) of olefin, methanol and dimethyl ether having 4 or more carbon atoms in all the feed components supplied to the second reactor is 20 vol% or more and 80 vol% or less of the whole. It is preferably 30% by volume or more and 70% by volume or less of the whole.
  • the substrate concentration can be determined 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 the method for controlling the substrate concentration include a method for controlling the flow rate of the fluid extracted from the process. By changing the flow rate of the fluid extracted from the process, It is possible to change the substrate concentration by changing the flow rate of the diluent gas recycled to the reactor.
  • a butadiene compound may be contained in the fluid (R) recycled to the second reactor and / or the olefin raw material fluid having 4 or more carbon atoms supplied from outside the process described later.
  • the concentration of butadiene in all the feed components fed to the second reactor is preferably 2.0% by volume or less.
  • the butadiene concentration is determined by the losing force S by quantifying the composition of each fluid supplied to the second reactor or the fluid after mixing by a general analytical method such as gas chromatography.
  • Examples of the method for reducing the butadiene concentration include a partial hydrogenation method in which the fluid is converted into olefins using a hydrogenation catalyst.
  • the fluid (R) recycled to the second reactor may contain an aromatic compound, but the aromatics contained in all the gases supplied to the second reactor. It is preferably less than 0.05 in terms of molar ratio to the total amount of the compound and the total amount of olefins having 4 or more carbon atoms contained in all the gases supplied to the second reactor.
  • the ratio of the total amount of the aromatic compounds and the total amount of olefins having 4 or more carbon atoms is determined by gas chromatography based on the composition of each fluid supplied to the second reactor or the fluid after mixing. It is possible to know by quantifying with a general analysis method such as.
  • the aromatic compound reacts with at least one of methanol and dimethyl ether in the reactor and consumes at least one of methanol and dimethyl ether more than necessary. It is not preferable.
  • a separation method by distillation may be mentioned.
  • the second reactor in addition to ethylene, olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether, norafines, aromatics, water vapor, carbon dioxide, carbon monoxide, There may be gases that are inert to the reaction, such as nitrogen, argon, helium, and mixtures thereof. Of these dilution gases, barraffins and aromatics may react slightly depending on the reaction conditions, but the reaction amount is small. Therefore, it is defined as a dilution gas.
  • 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 second reactor, or may be supplied to the second reactor separately from the reaction raw material.
  • 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 space velocity referred to here is the flow rate of the 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 the granulation / molding of the catalyst. It is the weight of the catalytically active component containing no inactive components or binder.
  • the flow rate is the flow rate (weight / hour) of olefin with 4 or more carbon atoms.
  • the sum of the molar flow rate of methanol fed to the second reactor and twice the molar flow rate of dimethyl ether is the sum of the molar flow rate of methanol at the outlet of the second reactor and twice the molar flow rate of dimethyl ether. Less than 1% is preferred. More preferably, it is less than 0.1%. If the amount of methanol or dimethyl ether at the outlet of the second reactor, which consumes less, is increased too much, it becomes difficult to purify the product olefin. Methods for increasing the consumption include increasing the reaction temperature and decreasing the space velocity.
  • the total molar flow rate of olefins having 4 or more carbon atoms at the outlet of the second reactor is 20% or more with respect to the total molar flow rate of olefins having 4 or more carbon atoms supplied to the second reactor. Less than 70% is preferable. Preferably it is 25% or more and less than 60%. If the consumption is too small, the amount of unreacted olefins increases, and the flow rate of the fluid recycled to the second reactor becomes too large. If the amount of consumption is too large, undesirable compounds such as paraffin and aromatic compounds are by-produced and the propylene yield decreases, which is not preferable. Adjust consumption Examples of the method include appropriately setting the reaction temperature and space velocity.
  • the flow rates of methanol and dimethyl ether and olefin having 4 or more carbon atoms to be supplied to the second reactor are the same as those of the gas supplied to the second reactor or the composition of the fluid after mixing, such as gas chromatography.
  • the flow rate of methanol and dimethyl ether at the outlet of the second reactor and olefins with 4 or more carbon atoms can be determined by measuring the flow rate of each fluid using a conventional analytical method.
  • the composition of the fluid can be determined by quantifying it with a general technique such as gas chromatography and measuring or calculating the flow rate of the second reactor outlet fluid.
  • Fluid (S) containing propylene, ethylene, other olefins, paraffin, aromatic compounds and water means the fluid at the outlet of the second reactor.
  • a mixed gas containing propylene as a reaction product, 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 having 4 or more carbon atoms, paraffins, aromatic compounds, and water.
  • the amount of ethylene contained in the reactor outlet fluid (S) is preferably less than 2.0 by weight with respect to propylene contained in the fluid. More preferably, it is less than 1.5, More preferably, it is less than 1.0. Beyond this range, there is a disadvantage that the facilities and utility facilities of the entire process become huge and the construction cost increases. Further, such equipment is not preferable because the utility cost is remarkably increased. Conversely, if it can fall within this range, it will be possible to significantly reduce equipment costs and utility costs for the entire process.
  • step (3C) fluid (S) from step (2C) is replaced with a fluid rich in hydrocarbons (T) having 2 or less carbon atoms, a fluid rich in propylene, or a fluid rich in hydrocarbons having 4 or more carbon atoms. Separate into (U) and water-rich fluid.
  • the fluid (S) obtained in the step (2C) is rich in hydrocarbons (T) and propylene rich in hydrocarbons having 2 or less carbon atoms by general separation steps such as cooling, compression and distillation. Separated into a fluid, a hydrocarbon rich fluid (U) and a water rich fluid with 4 or more carbon atoms.
  • each fluid is not limited to one fluid, and may be a plurality of fluids.
  • a hydrocarbon-rich fluid (T) having 2 or less carbon atoms may be one fluid containing methane, ethylene, or ethane, but two fluids, a fluid rich in methane and a fluid rich in ethylene and ethane. But it ’s okay
  • the oxygen-containing compound is contained in the reactor outlet fluid (S)
  • at least a part of the oxygen-containing compound is removed by the quenching process.
  • acidic gas such as carbon dioxide
  • alkali cleaning is possible mainly by condensation through compression and cooling.
  • the remaining water is preferably removed by 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 can also be used for process water. If this process is close to the steam cracking process, it should be used as a cracker steam source. It can also be recycled to the second reactor in step (2C) and used as a diluent gas.
  • the obtained propylene-rich fluid further obtains high-purity propylene by a purification process such as distillation.
  • the purity of propylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.
  • Propylene produced can be used as a raw material for all of the generally produced propylene derivatives.
  • acrylonitrile is produced by ammoxidation, and acrolein, acrylic acid and acrylate esters are produced by selective oxidation.
  • oxo alcohols such as normal butanol alcohol and 2-ethylhexanol by the oxo reaction
  • polypropylene by the polymerization of propylene
  • propylene oxalate by the selective oxidation of propylene. It can be applied to the production of id and propylene glycol.
  • acetone can be produced by the Hacker reaction, and methylisobutyl ketone can be produced from acetone.
  • Acetone can also produce acetone cyanohydrin, which is ultimately converted to methyl methacrylate.
  • Isopropyl alcohol can also be produced by propylene hydration.
  • phenol, bisphenol A, and polycarbonate resin can be produced from cumene produced by alkylating benzene.
  • step (4C) a part of fluid (P) of fluid (T) from step (3C) is recycled to the first reactor, and the remaining fluid is withdrawn from the process.
  • the fluid (T) may be divided into a recycled fluid (P) and a fluid to be extracted without being introduced into the separation process, but the fluid (T) is introduced into the separation process and the fluid (T A fluid having a higher ethylene concentration than T) may be recycled to the first reactor.
  • the fluid extracted outside the process may be purified to recover an active ingredient such as ethylene, or may be used as a fuel. It may also be used as a raw material for steam cracking.
  • the "part” here is usually in the range of 10 to 99% by weight, preferably in the range of 50 to 95% by weight of the flow rate of the fluid (T) as described above. Below this range, there is a disadvantage that the flow rate of ethylene supplied to the first reactor as a new raw material increases, and conversely, when this range is exceeded, methane ethane is contained in the first reactor and the recycle fluid. This is not preferable because it causes inconvenience of accumulation.
  • step (5C) a portion of the fluid (U) from step (3C) (R) is recycled to the second reactor and the remaining fluid is withdrawn from the process.
  • the fluid (U) may be divided into a recycled fluid (R) and a fluid to be extracted without introducing the fluid (U) into the separation process.
  • a fluid having a higher butene concentration than (U) may be recycled to the second reactor.
  • the extracted fluid may be purified to recover active ingredients such as butene and aromatic compounds, or may be used as fuel. It may also be used as a raw material for steam cracking.
  • the "part” here is usually in the range of 10 to 99% by weight, preferably in the range of 50 to 95% by weight of the flow rate of the fluid (U) as described above. Below this range, the flow rate of olefins having 4 or more carbon atoms supplied to the second reactor is reduced, resulting in a decrease in propylene yield. This is not preferable because it accumulates in the reactor and the recycling fluid.
  • a fluid containing olefin having 4 or more carbon atoms may be newly supplied to the second reactor in the above-described step (2C) as a part of the raw material for producing propylene.
  • the olefin having 4 or more carbon atoms used as a raw material for the reaction is not particularly limited.
  • oil feedstock power catalytic cracking method or steam cracking, etc. (BB fraction, C4 rough rice toe 1, C4 rough rice toe 2, etc.), hydrogen / CO mixed gas obtained by coal gasification Materials obtained by FT (Fischer-Tropsch) synthesis as raw materials, those obtained by dehydrogenation or oxidative dehydrogenation of paraffins with 4 or more carbon atoms, those obtained by MTO reaction, alcohol dehydration reaction Olefins having 4 or more carbon atoms, especially 4 to 10 carbon atoms, which are obtained by various known methods, such as those obtained by hydrogenation reaction of gen compounds having 4 or more carbon atoms, are optionally used.
  • a compound in which a compound other than olefin having 4 or more carbon atoms resulting from each production method is arbitrarily mixed may be used as it is.
  • the reaction temperature can be easily controlled because paraffin serves as a dilution gas, and raw materials containing paraffin are available at low cost. It is preferable because there are many cases. More preferred is an olefin raw material containing normal butane and / or isobutane. These preferred and raw materials include the above-mentioned BB fraction, C4 rough rice toe 1 and C4 rough rice toe 2. Since the BB fraction contains a large amount of butadiene, it is preferable to use a fluid that has been brought into contact with the hydrogenation catalyst to lower the butane concentration.
  • FIG. 1 shows a first embodiment of the process of the present invention
  • FIG. 2 shows a second embodiment of the process of the present invention.
  • 10 is a first reactor
  • 20 is a second reactor
  • 30 is a separation and purification system. 1 0;! To 117 indicate piping.
  • 12 is the first reactor
  • 22 is the second reactor
  • 32 is the separation and purification system. 20;! To 217 each indicate piping.
  • At least one of the ethylene raw material, methanol and dimethyl ether, and the hydrocarbon fluid (F) having 2 or less carbon atoms from the separation and purification system 30 passes through the piping 101, piping 102, piping 103, and piping 104, respectively, to the first reactor. Supplied to 10.
  • the fluid supplied to the reactor via the pipe 101 and / or the pipe 103 may contain paraffins having 2 or less carbon atoms, such as methanol.
  • the raw material fluid introduced through the pipe 104 means the sum of the fluids supplied through the pipe 101, the pipe 102, and the pipe 103, but these necessarily join before entering the first reactor 10.
  • the first reactor 10 may be supplied separately as necessary.
  • the raw material supplied to the first reactor 10 reacts in contact with the catalyst in the first reactor 10, and reacts with the catalyst, and exits the reactor containing propylene, carbon 4 olefin, ethylene, paraffin, aromatic compound and water. Fluid (A) is obtained.
  • At least one of methanol and dimethyl ether and hydrocarbon fluid (G) having 4 or more carbon atoms from separation and purification system 30 is supplied to second reactor 20 via piping 106, piping 107, and piping 109, respectively. Is done.
  • An olefin raw material having 4 or more carbon atoms may be supplied to the second reactor 20 through the pipe 108 and the pipe 109.
  • the fluid supplied to the second reactor 20 via the pipe 108 and / or the pipe 107 may contain paraffins having 4 or more carbon atoms, such as Kalemalbutane and isobutane.
  • the raw material fluid supplied to the second reactor 20 via the pipe 109 may contain butadiene, an aromatic compound, and water.
  • the raw material fluid introduced through the pipe 109 means the sum of the fluids supplied through the pipe 106, the pipe 107, and the pipe 108 as necessary. They do not necessarily have to be joined before entering the second reactor 20 and may be supplied separately to the second reactor 20.
  • the raw material supplied to the second reactor 20 reacted in contact with the catalyst in the second reactor 20 and contained propylene, olefins having 4 or more carbon atoms, ethylene, paraffin, aromatic compounds and water.
  • Reactor outlet gas fluid (B) is obtained.
  • the fluid (C) is supplied to a general separation and purification system 30 such as cooling, compression and distillation through a pipe 111, and is rich in hydrocarbons (D) having 2 or less carbon atoms, fluids rich in propylene, It is separated into a hydrocarbon-rich fluid (E) and a water-rich fluid having 4 or more carbon atoms, and taken out through piping 112, piping 113, piping 114, and piping 115, respectively.
  • each fluid represents one or more fluids.
  • one fluid containing methane, ethylene, and ethane may be used, but two fluids, a fluid rich in methane and a fluid rich in ethylene and ethane. Fluid may be used.
  • a part (F) of the fluid (D) rich in hydrocarbons having 2 or less carbon atoms is recycled to the first reactor 10 through the pipe 103, and the remaining fluid is recycled from the process through the pipe 116. Extracted.
  • the fluid having a higher ethylene concentration than the fluid (D) may be recycled to the first reactor 10 by separating and refining the fluid (D).
  • the fluid extracted through the pipe 116 may be purified to recover an active component such as ethylene or may be used as a fuel. It may also be used as a raw material for steam cracking.
  • the propylene-rich fluid obtained through the pipe 113 is highly pure! /, Preferably obtained by separation and purification such as distillation! /.
  • the water obtained through the pipe 115 may be used for a wastewater treatment process such as activated sludge, but can also be used for process water or the like. If this process is close to the steam cracking process, it should be used as a cracker steam source. Further, it may be recycled to the first reactor 10 and / or the second reactor 20 and used as a dilution gas.
  • a wastewater treatment process such as activated sludge
  • process water or the like If this process is close to the steam cracking process, it should be used as a cracker steam source. Further, it may be recycled to the first reactor 10 and / or the second reactor 20 and used as a dilution gas.
  • the fluid having a higher butene concentration than the fluid (E) may be recycled to the second reactor 20 by separating and purifying the fluid (E).
  • the fluid extracted through the piping 117 may be purified to recover active components such as butene and aromatic compounds, or may be used as fuel. It can also be used as a raw material for steam cracking! /.
  • At least one of the ethylene raw material, methanol and dimethyl ether, and the hydrocarbon-rich fluid (L) from the separation and purification system 32 passes through the pipe 201, the pipe 202, the pipe 203 and the pipe 204, respectively.
  • the fluid supplied to the reactor via at least one of the pipe 201 and the pipe 203 may contain paraffins having 2 or less carbon atoms, such as methane ethane.
  • the raw material fluid introduced via the pipe 204 is a force that means the sum of the fluids supplied via the pipe 201, the pipe 202, and the pipe 203, and these always join before entering the first reactor 12. It may be fed separately to the reactor 12 as necessary.
  • the raw material supplied to the first reactor 12 reacts in contact with the catalyst in the first reactor 12 and includes propylene, olefins having 4 carbon atoms, ethylene, paraffin, aromatic compounds and water.
  • a container outlet fluid (A) is obtained.
  • the outlet fluid (A) of the first reactor 12, at least one of methanol and dimethyl ether, and the hydrocarbon fluid (M) having 4 or more carbon atoms from the separation and purification system 32 are pipes 20 5, respectively. It is supplied to the second reactor 22 via the pipe 206, the pipe 207 and the pipe 209. An olefin raw material having 4 or more carbon atoms may be supplied to the second reactor 22 through the pipe 208 and the pipe 209. The fluid supplied to the second reactor 22 via the pipe 208 and / or the pipe 207 may contain paraffins having 4 or more carbon atoms, such as normal butane and isobutane.
  • the raw material fluid supplied to the second reactor 22 via the pipe 209 may contain butadiene, an aromatic compound, and water.
  • the raw material fluid introduced through the pipe 209 is a force S that means the sum of the fluid supplied through the pipe 205, the pipe 206, the pipe 207, and the pipe 208 as needed, and these are not necessarily the second reaction.
  • the reactors 22 may be fed separately without having to join before entering the reactor 22.
  • the raw material supplied to the second reactor 22 reacts in contact with the catalyst in the reactor 22 and contains propylene, olefins having 4 or more carbon atoms, ethylene, norafine, aromatic compounds and water. Outlet fluid (gas) (I) is obtained.
  • the outlet gas fluid (I) of the second reactor 22 is sent to a general separation and purification system 32 such as cooling, compression and distillation through a pipe 210, and is rich in hydrocarbons having 2 or less carbon atoms.
  • Fluid (J), propylene-rich fluid, hydrocarbon-rich fluid (K) with 4 or more carbon atoms and water-rich fluid are separated through pipe 212, pipe 213, pipe 214 and pipe 215, respectively. It is taken out.
  • each fluid represents one or more fluids.
  • one fluid containing methane, ethylene, and ethane may be used, but two fluids, a fluid rich in methane and a fluid rich in ethylene and ethane. Fluid may be used.
  • a part of the hydrocarbon-rich fluid (J) having 2 or less carbon atoms (U is recycled to the first reactor 12 through the pipe 203, and the remaining fluid is removed from the process through the pipe 216. Be issued
  • the fluid (J) may be recycled to the first reactor 12 by separating and purifying the fluid (J), etc., with a higher ethylene concentration than the fluid (J)!
  • the fluid extracted via the pipe 216 may be purified to recover an active component such as ethylene or may be used as a fuel. It can also be used as a raw material for steam cracking! /.
  • the propylene-rich fluid obtained through the pipe 213 is highly pure! /, Preferably obtained by separation and purification such as distillation! /.
  • the water obtained through the pipe 215 may be used for a wastewater treatment process such as activated sludge, but can also be used for process water or the like. If this process is close to the steam cracking process, it should be used as a cracker steam source. Further, it may be recycled to the first reactor 12 and / or the second reactor 22 and used as a dilution gas.
  • a wastewater treatment process such as activated sludge
  • process water or the like If this process is close to the steam cracking process, it should be used as a cracker steam source. Further, it may be recycled to the first reactor 12 and / or the second reactor 22 and used as a dilution gas.
  • a part ( ⁇ ) of the fluid rich in hydrocarbons having 4 or more carbon atoms ( ⁇ ) is recycled to the second reactor 22 via the pipe 207, and the remaining fluid passes through the pipe 217 to the process. Extracted from.
  • a fluid having a higher butene concentration than the fluid (22) may be recycled to the second reactor 22 by separating and refining the fluid ( ⁇ ).
  • the fluid extracted through the pipe 217 may be purified to recover active components such as butene and aromatic compounds, or may be used as fuel. It may also be used as a raw material for steam cracking.
  • FIG. 3 illustrates one embodiment of the process of the present invention.
  • FIG. 3 13 is a first reactor, 23 is a second reactor, and 33 is a separation and purification system. 3 0;! To 315 indicate piping.
  • a hydrocarbon-rich hydrocarbon fluid (P) from ethylene raw material, separation and purification system 33 is supplied to first reactor 13 via piping 301, piping 302, and piping 303, respectively.
  • the fluid supplied to the reactor 13 via at least one of the pipe 301 and the pipe 302 may contain paraffins having 2 or less carbon atoms, such as methane ethane.
  • the raw material fluid introduced through the pipe 303 is a force that means the sum of the fluids supplied through the pipe 301 and the pipe 302, and these do not necessarily have to join before entering the first reactor 13. They may be supplied separately to the reactor 13.
  • the raw material supplied to the first reactor 13 reacts in contact with the ethylene dimerization catalyst in the reactor 13 to obtain a reactor outlet fluid (Q) containing olefins having 4 carbon atoms.
  • the first reactor 13 may be a force-phase reactor shown as a liquid-phase reactor! In the case of a liquid phase reactor, the catalyst separation operation is performed after the reactor. Further, in FIG. 3, the force that all of the fluid (Q) is supplied to the second reactor 23 through the pipe 304 and the pipe 308, and part of it is extracted as necessary and used for other purposes. May be used.
  • An olefin raw material having 4 or more carbon atoms may be supplied to the second reactor 23 through the pipe 305 and the pipe 308.
  • the fluid supplied to the second reactor 23 via at least one of the pipe 306 and the pipe 305 may contain paraffins having 4 or more carbon atoms, such as normal butane and isobutane.
  • the raw material fluid supplied to the second reactor 23 via the pipe 308 may contain butadiene, an aromatic compound, and water.
  • the raw material fluid introduced via the pipe 308 means the total of the fluid supplied via the pipe 304, the pipe 306, the pipe 307, and the pipe 305 if necessary! They may be fed separately to the second reactor 23 without having to join before entering the second reactor 23.
  • the raw material supplied to the second reactor 23 reacts in contact with the propylene production catalyst in the second reactor 23 and contains propylene, ethylene, other olefins, paraffin, aromatic compounds and water.
  • Outlet fluid (gas) (S) is obtained.
  • the outlet gas fluid (S) of the second reactor 23 is sent to a general separation and purification system 33 such as cooling, compression and distillation, and is a fluid rich in hydrocarbons having 2 or less carbon atoms (T) They are separated into a fluid rich in propylene, a fluid (U) rich in hydrocarbons having 4 or more carbon atoms, and a fluid rich in water, and are taken out through pipe 310, pipe 311, pipe 312 and pipe 313, respectively.
  • each fluid represents one or more fluids.
  • one fluid containing methane, ethylene, and ethane may be used, but two fluids, a fluid rich in methane and a fluid rich in ethylene and ethane. But it ’s okay.
  • a part (P) of the hydrocarbon-rich fluid (T) having 2 or less carbon atoms is recycled to the first reactor 13 via the piping 302, and the remaining fluid is recycled from the process via the piping 314. Extracted.
  • the fluid having a higher ethylene concentration than the fluid (T) may be recycled to the first reactor 13 by separating and purifying the fluid (T).
  • the fluid extracted through the pipe 314 may be purified to recover an active component such as ethylene, or may be used as a fuel. It can also be used as a raw material for steam cracking! /.
  • the propylene-rich fluid obtained through the pipe 311 preferably obtains high purity propylene by separation and purification such as distillation. Further, the water obtained through the pipe 313 may be used for a wastewater treatment process such as activated sludge, but can also be used for process water or the like. If this process is close to the steam cracking process, it is preferable to use IJ as a steam source for crackers. Further, it may be recycled to the second reactor 23 and used as a dilution gas.
  • a part (R) of the hydrocarbon-rich fluid (U) having 4 or more carbon atoms is recycled to the second reactor via the pipe 306, and the remaining fluid is returned from the process via the pipe 315. Extracted.
  • the fluid having a higher butene concentration than the fluid (U) may be recycled to the second reactor 23 by separating and refining the fluid (U).
  • the fluid withdrawn via pipe 315 may be purified to recover active ingredients such as butene and aromatic compounds, or burned. It may be used as a fee. It may also be used as a raw material for steam cracking.
  • 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.
  • the flow rate (weight / time) of ethylene raw material (pipe 201 in the figure) in Fig. 2 is 100, and the flow rate (weight / time) of methanol raw material supplied from the pipe 202 and pipe 206 is 225 each (total 25).
  • the simulated gas (including ethylene and methanol) at the inlet (pipe 204) of the first reactor (12) is prepared, and the fluid newly entered the second reactor (22) (pipe 206).
  • a pipe 20 7 fluid) were prepared (including ethylene, methanol and butene), and two reactors were placed in series as shown in Figure 2 to produce propylene.
  • the power of the two reactors filled with the above catalyst and under normal pressure conditions The reactor outlet temperature of the first reactor was 450 ° C, and the reactor outlet temperature of the second reactor was 550 ° C. went.
  • an aspen plus simulator was used to determine the flow rate of each fluid containing recycled gas. Based on the flow rate of the obtained recycle gas (pipes 203 and 207), the fluid (fluid combining pipe 206 and pipe 207) newly entering the first reactor inlet and the second reactor (22) is added. The gas composition was calculated and the reaction was carried out again using the re-prepared simulated gas. By repeating these operations about 10 times, the flow rate of each fluid in the process of Fig. 2 was finally obtained by experiments and simulations.
  • the ethylene flow rate (weight / time) at the first reactor inlet (pipe 204) is 244
  • the ethylene flow rate (weight / time) at the first reactor outlet (pipe 205) is 144
  • the second reactor The olefin flow rate (weight / time) of 4 or more carbons in the fluid (pipe 207) recycled was 381.
  • the ethylene conversion in the first reactor was 41%.
  • the propylene flow rate (weight / hour) at the second reactor outlet (pipe 210: fluid I) was 185, the ethylene flow rate (weight / hour) was 156, and olefins with 4 or more carbon atoms were 385.
  • the amount of ethylene contained in fluid I was 0.84 by weight with respect to the amount of propylene.
  • a simulated gas (including ethylene, methanol and butene) at the inlet (pipe 308) was prepared, and propylene was produced using the catalyst at a reactor outlet temperature of 550 ° C and normal pressure.
  • an aspen plus simulator was used to determine the flow rate of each fluid containing the recycled gas.
  • the ethylene conversion rate in the first reactor for ethylene dimerization was assumed to be 90%.
  • the propylene flow rate (weight / hour) was 189, the ethylene flow rate (weight / hour) was 83, and olefins with 4 or more carbon atoms were 404.
  • the amount of ethylene contained in fluid S was 0.44 by weight with respect to the amount of propylene.
  • a simulated gas (containing ethylene, methanol, and butene) was prepared in tube 404), and propylene was produced using the catalyst under the conditions of a reactor outlet temperature of 550 ° C and atmospheric pressure.
  • an aspen plus simulator was used to determine the flow rate of each fluid including recycle gas.
  • the ethylene flow rate (weight / hour) at the reactor inlet was 589
  • the polyolefin flow rate (weight / hour) with 4 or more carbon atoms was 321
  • the propylene flow rate (weight / hour) at the reactor outlet pipe 405).
  • the amount of ethylene contained in the reactor outlet fluid was 2.95 by weight with respect to the amount of propylene, which was a large value as compared with Examples 1 and 2.
  • the present invention relates to a method for producing propylene using ethylene and at least one of methanol and dimethyl ether as raw materials! / And a novel equipment cost and a low utility cost for reducing the amount of unreacted ethylene recycled. Process can be provided.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un nouveau procédé destiné à produire du propylène qui utilise de l'éthylène et au moins un élément choisi parmi le méthanol et l'éther diméthylique en tant que matières premières. Ledit procédé peut permettre de réduire la quantité d'éthylène n'ayant pas réagi qui doit être recyclé et présente de faibles coûts d'équipement et de fonctionnement. L'invention concerne de manière spécifique un procédé destiné à produire du propylène qui utilise de l'éthylène et au moins un élément choisi parmi le méthanol et l'éther diméthylique en tant que matières premières. Le procédé consiste à faire réagir l'éthylène et au moins un élément choisi parmi le méthanol et l'éther diméthylique dans des conditions spécifiques, afin de produire un fluide contenant une oléfine possédant au moins 4 atomes de carbone, puis à faire réagir au moins une partie de l'oléfine, possédant au moins 4 atomes de carbone, contenue dans le fluide avec au moins un élément choisi parmi le méthanol et l'éther diméthylique dans des conditions spécifiques, produisant ainsi du propylène.
PCT/JP2007/068572 2006-09-26 2007-09-25 Procédé de production de propylène WO2008041561A1 (fr)

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KR1020097005976A KR101512860B1 (ko) 2006-09-26 2007-09-25 프로필렌의 제조 방법
CN2007800356086A CN101516812B (zh) 2006-09-26 2007-09-25 丙烯的制备方法

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JP2006260810 2006-09-26
JP2006-260810 2006-09-26
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KR (1) KR101512860B1 (fr)
CN (1) CN101516812B (fr)
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WO (1) WO2008041561A1 (fr)

Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2012015060A1 (fr) * 2010-07-30 2012-02-02 日本ガス合成株式会社 Procédé de fabrication du propylène

Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
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
CN103153921A (zh) * 2010-08-03 2013-06-12 道达尔研究技术弗吕公司 由甲醇和异丁醇制造烯烃的方法
CN102285858B (zh) * 2010-11-29 2014-07-23 中国科学院大连化学物理研究所 一种制取丙烯的方法
JP2015189720A (ja) * 2014-03-28 2015-11-02 三菱化学株式会社 プロピレンの製造方法
JP6172024B2 (ja) * 2014-03-28 2017-08-02 三菱ケミカル株式会社 プロピレンの製造方法
WO2017179108A1 (fr) * 2016-04-11 2017-10-19 旭化成株式会社 Procédé de production d'oléfine inférieure
FR3090393B1 (fr) * 2018-12-20 2021-04-23 Ifp Energies Now Procédé de traitement d’une charge alcool pour la production d’oléfines

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US20030181777A1 (en) * 2002-03-18 2003-09-25 Powers Donald H. Enhanced production of light olefins
WO2005016856A1 (fr) * 2003-08-19 2005-02-24 Total Petrochemicals Research Feluy Production d'olefines
WO2005056504A1 (fr) * 2003-12-12 2005-06-23 Mitsubishi Chemical Corporation Procede de production de propylene
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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DE19813720A1 (de) * 1998-03-27 1999-09-30 Basf Ag Verfahren zur Herstellung von Olefinen

Patent Citations (4)

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US20030181777A1 (en) * 2002-03-18 2003-09-25 Powers Donald H. Enhanced production of light olefins
WO2005016856A1 (fr) * 2003-08-19 2005-02-24 Total Petrochemicals Research Feluy Production d'olefines
WO2005056504A1 (fr) * 2003-12-12 2005-06-23 Mitsubishi Chemical Corporation Procede de production de propylene
WO2007023706A1 (fr) * 2005-08-24 2007-03-01 Jgc Corporation Procédé de production d'un hydrocarbure inférieur et appareil de production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012015060A1 (fr) * 2010-07-30 2012-02-02 日本ガス合成株式会社 Procédé de fabrication du propylène

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JP2008106056A (ja) 2008-05-08
KR20090059127A (ko) 2009-06-10
JP5391537B2 (ja) 2014-01-15
CN101516812B (zh) 2012-12-19
CN101516812A (zh) 2009-08-26
KR101512860B1 (ko) 2015-04-16
TW200831454A (en) 2008-08-01
TWI409249B (zh) 2013-09-21

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