WO2008035743A1

WO2008035743A1 - Process for production of propylene

Info

Publication number: WO2008035743A1
Application number: PCT/JP2007/068299
Authority: WO
Inventors: Masashi Yamaguchi; Tohru Setoyama; Kagoto Nakagawa; Fumitaka Utsumi; Shinji Iwade
Original assignee: Mitsubishi Chemical Corporation
Priority date: 2006-09-21
Filing date: 2007-09-20
Publication date: 2008-03-27
Also published as: CN102766010B; KR101435230B1; TWI405750B; TW200831453A; KR20090059123A; CN102766010A

Abstract

Disclosed is a process for producing propylene by reacting an olefin raw material having a 4 or more carbon atoms with at least one member selected from methanol and dimethyl ether in the presence of a catalyst, which enables to produce propylene at a high yield by using a raw material in a small quantity while preventing the occurrence of the deterioration of the catalyst.

Description

Specification

Propylene production method

Technical field

The present invention relates to a method for producing propylene from a raw material mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether. Background art

[0002] As a method for producing propylene, conventionally, steam cracking of naphthaethane and fluid catalytic cracking of vacuum gas oil have been generally performed. In recent years, metathesis reaction using ethylene and 2-butene as raw materials has been carried out. In addition, catalytic cracking of olefins with 4 or more carbon atoms, and MTO processes using at least one of methanol and dimethyl ether as a raw material are also attracting attention. On the other hand, a method for producing lower olefins using olefins having 4 or more carbon atoms and oxygen-containing compounds such as methanol as raw materials is also known (Patent Document 1).

Patent Document 1: U.S. Pat.No. 6888038

Disclosure of the invention

Problems to be solved by the invention

[0003] Conventionally, a number of proposals have been made as methods for producing propylene, and most of them have been disclosed for each reaction and purification! The above-mentioned methods using olefins and oxygen-containing compounds such as methanol as raw materials! / Although the reaction itself has been proposed, the process including the purification system on the downstream side of the reactor has been proposed. It was not proposed.

Accordingly, a first object of the present invention is to provide a novel and economical process for producing propylene by reacting olefin having 4 or more carbon atoms with at least one of methanol and dimethyl ether.

[0004] On the other hand, in the steam cracking process, which is the mainstream method for producing ethylene and propylene, the ratio of ethylene and propylene to be produced cannot be changed greatly. The ratio of ethylene and propylene can be changed significantly. In addition, these two processes will be integrated As a result, it becomes possible to effectively use fluids that are not required in each other's processes.

Therefore, the second object of the present invention is to provide a new and economical process that integrates this process and steam cracking.

Means for solving the problem

[0005] The inventors of the present invention examined the reaction of obtaining propylene by reacting olefins having 4 or more carbon atoms with at least one of methanol and dimethyl ether, and obtained the following findings.

[0006] When too much olefin is consumed by the reaction, undesirable by-products such as aromatic compounds and paraffin are prominently produced. On the other hand, when too little olefin is consumed, the yield of propylene is too low. It will be a thing. Propylene can be obtained with high selectivity and high yield by appropriately setting reaction conditions such as temperature, pressure, partial pressure, space velocity, and controlling the amount of olefins consumed within a specific range. When the reaction is carried out under such conditions, the reactor outlet fluid contains many olefins having 4 or more carbon atoms that can serve as reaction raw materials, and it is preferable to recycle these compounds into the reactor. ,.

[0007] On the other hand, in the reaction of olefins having 4 or more carbon atoms with at least one of methanol and dimethyl ether, aromatic compounds and paraffins are also produced in trace amounts, and are contained in the reactor outlet fluid. In particular, when a raw material containing paraffin is used as an olefin raw material having 4 or more carbon atoms, the concentration of paraffin in the reactor outlet fluid increases. Since noraffins hardly react in the reactor, paraffin concentrates and accumulates in the system when recycled to the reactor together with olefins having 4 or more carbon atoms. For this reason, it is preferable to extract a part of the fluid containing paraffins from the system. In this case, the fluid to be extracted is preferably a fluid having a composition that can be effectively used.

[0008] In addition, when an aromatic compound is present in a recycled olefin fluid having 4 or more carbon atoms in a specific concentration or more, the reaction between the aromatic compound and olefin having 4 or more carbon atoms, or the aromatic compound and methanol. In addition, the reaction with at least one of dimethyl ether becomes remarkable, and at least one of the supplied olefins having 4 or more carbon atoms, methanol and dimethyl ether is consumed more than necessary. Furthermore, when an aromatic compound is supplied to the reactor, the compound produced by the reaction with the olefin having 4 or more carbon atoms clogs the pores of the catalyst, thereby promoting the deterioration of the catalyst. It is preferable to remove the aromatic compounds present in the reactor outlet fluid from the system as much as possible and reduce the concentration of the aromatic compounds in the fluid recycled to the reactor. Also in this case, the fluid to be extracted is preferably a fluid having a composition that can be used effectively.

[0009] As described above, the present inventors have found various problems in a method for producing propylene using olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether as raw materials, and solved these problems. By constructing a process capable of producing propylene, it was found that propylene could be produced in a high yield while suppressing deterioration of the catalyst using a small amount of raw materials.

Furthermore, by supplying the fluid extracted from this process to the steam cracking process and supplying the fluid in the steam cracking process to this process, it is possible to effectively use low-value fluids and realize a highly efficient process. I found it.

The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] In a method for producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst,

At least a part of the aromatic compound contained in the reactor outlet effluent gas (reactor outlet gas) is withdrawn and contained in the reactor outlet effluent gas (reactor outlet gas)! A method for producing propylene, wherein at least a part of olefin having 4 or more carbon atoms is brought into contact with a catalyst again in the reactor.

[2] A method for producing propylene according to [1], wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

[3] The method for producing propylene according to [2], wherein the paraffins contain at least one of normal butane and isobutane.

[4] In any one of [1] to [3], butadiene is contained in the raw material supplied to the reactor. A process for producing propylene, characterized by comprising an ethylene.

[5] In any one of [1] to [4], the total amount of aromatic compounds contained in all raw materials fed to the reactor is the total of olefins having 4 or more carbon atoms contained in all the raw materials. A method for producing propylene, wherein the molar ratio is less than 0.05 with respect to the amount.

[6] In any one of [1] to [5], the quantity of polyolefin having 4 or more carbon atoms fed to the reactor, the number of moles of methanol fed to the reactor, and twice the number of moles of dimethyl ether A method for producing propylene, wherein the molar ratio is 0.2 or more and 10 or less with respect to the total of the above.

[7] In any one of [1] to [6], the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in all raw materials fed to the reactor is 20 vol% or more. Propylene production method characterized by controlling to volume% or less.

[8] In a method for producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following step (1) , (2) and a process comprising (3A), characterized in that it comprises a process for producing propylene.

Step (1): olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (D) recycled from step (3A), and at least one of methanol and dimethyl ether are supplied to the reactor, and carbon at the outlet of the reactor is supplied. The molar flow rate of olefins of 4 or more is contacted with the catalyst under reaction conditions such that the molar flow rate of the olefins at the inlet of the reactor is 20% or more and less than 90%. Of obtaining gas (reactor outlet gas) containing olefins, paraffins, aromatic compounds and water

Step (2): Reactor outlet gas from step (1) above is rich in hydrocarbons rich in hydrocarbons having 3 or less carbon atoms, fluids rich in hydrocarbons having 4 or more carbon atoms (A), and rich in water. Separating into fluid

Step (3A): At least a part of fluid (C) of fluid (A) in step (2) above has an aromatic compound concentration lower than that of fluid (C) !, fluid (D) and carbon number 4 is separated into a fluid (E) having a hydrocarbon concentration lower than that of the fluid (C), the fluid (D) is recycled to the reactor, and the fluid (E) is extracted from the process. [9] In a method for producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1 ), (2) and (3A).

Step (3A): A part (B) of the fluid (A) in the step (2) is extracted from the process, and the remaining fluid (C) has a lower aromatic compound concentration than the fluid (C)! /ヽ Fluid (D) and C4 hydrocarbon concentration are lower than fluid (C)! /, Fluid (E), and fluid (D) is recycled to the reactor and fluid (D) Step of extracting E) from the process

[10] In [8] or [9], the reactor is composed of two or more reaction forces connected in series, the olefin raw material having 4 or more carbon atoms supplied to the reactor; methanol and dimethyl ether At least one of them; and at least one of the recycled hydrocarbon-containing fluid (D) is divided and supplied to the first-stage reaction section and the second-stage and subsequent reaction sections. Propylene production method.

[11] The method for producing propylene according to any one of [8] to [10], wherein the fluid (B) is supplied to a steam cracking process and used as a cracker raw material.

[12] The method for producing propylene according to [11], wherein at least a part of the fluid (B) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process. [13] The method for producing propylene according to any one of [8] to [12], wherein the total concentration of aromatic compounds contained in the fluid (B) is less than 5.0% by volume.

[14] The method for producing propylene according to any one of [8] to [13], wherein the fluid (E) is mixed with a cracked gasoline fraction of a steam cracking process.

[15] The method for producing propylene according to any one of [8] to [14], wherein the total concentration of the hydrocarbon having 4 carbon atoms contained in the fluid (E) is less than 5% by weight.

[16] In any one of [8] to [15], by controlling the flow rates of the fluid (B) and the fluid (E), the number of carbon atoms contained in all raw materials supplied to the reactor is 4 A method for producing propylene, characterized in that the total concentration (substrate concentration) of the above olefin, methanol and dimethyl ether is controlled to 20 vol% or more and 80 vol% or less.

[17] In a method for producing propylene by contacting a mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps ( 1) A process for producing propylene characterized by comprising a process comprising (2) and (3B).

Step (1): olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (I) recycled from step (3B), and at least one of methanol and dimethyl ether are supplied to the reactor, and the number of carbons at the outlet of the reactor Contact with the catalyst under reaction conditions such that the molar flow rate of 4 or more olefins is 20% or more and less than 90% of the molar flow rate of the olefins at the inlet of the reactor. Step of obtaining gas (reactor outlet gas) containing olefin, paraffins, aromatic compounds and water

Step (2): The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, a fluid rich in hydrocarbons having 4 or more carbon atoms (A), and a fluid rich in water Step (3B): In the step (2), the fluid (A) has an aromatic concentration lower than that of the fluid (A) !, and the fluid (G) and the hydrocarbon concentration of 4 carbon atoms are fluid ( A) is separated into a fluid (F), at least a part (I) of the fluid (G) is recycled to the reactor, and the remaining fluid (H) is extracted from the process.

[18] Propylene is produced by contacting a mixture of olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst. A process for producing propylene characterized by comprising a process comprising the following steps (1), (2) and (3B):

Step (1): olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (I) recycled from step (3B), and at least one of methanol and dimethyl ether are supplied to the reactor, and the number of carbons at the outlet of the reactor Contact with the catalyst under reaction conditions such that the molar flow rate of 4 or more olefins is 20% or more and less than 90% with respect to the molar flow rate of the olefins at the inlet of the reactor, and propylene and other olefins from the reactor outlet. To obtain gas containing gas, paraffins, aromatic compounds and water (reactor outlet gas)

Step (2): The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, a fluid rich in hydrocarbons having 4 or more carbon atoms (A), and a fluid rich in water Step (3B): In the step (2), the fluid (A) has an aromatic concentration lower than that of the fluid (A) !, and the fluid (G) and the hydrocarbon concentration of 4 carbon atoms are fluid ( A) is separated into a fluid (F), and the fluid (F) is withdrawn from the process, and a part (I) of the fluid (G) is recycled to the reactor, and the remaining fluid Step of extracting (H) from the process

[19] In [17] or [18], the reactor comprises two or more reaction parts connected in series, and the olefin raw material having 4 or more carbon atoms to be supplied to the reactor; methanol and dimethyl ether At least one of them; and at least one of the recycled hydrocarbon-containing fluid (I) is divided into a first-stage reaction section and a second-stage reaction section to be supplied. A method for producing propylene, which is characterized.

[20] A method for producing propylene according to [17] to [19], wherein the fluid (H) is supplied to a steam cracking process and used as a cracker raw material.

[21] The method for producing propylene according to [20], wherein at least a part of the fluid (H) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.

Yes

[22] The method for producing propylene according to any one of [17] to [21], wherein the total concentration of aromatic compounds contained in the fluid (H) is less than 5.0% by volume.

[23] The method for producing propylene according to any one of [17] to [22], wherein the fluid (F) is mixed with a cracked gasoline fraction of a steam cracking process. [24] The method for producing propylene according to any one of [17] to [23], wherein the total concentration of the hydrocarbon having 4 carbon atoms contained in the fluid (F) is less than 5% by weight.

[25] In any one of [17] to [24], by controlling the flow rates of the fluid (F) and the fluid (H), the total raw material supplied to the reactor has 4 or more carbon atoms. A method for producing propylene, characterized in that the total concentration (substrate concentration) of olefin, methanol, and dimethyl ether is controlled to 20 volume% or more and 80 volume% or less.

[26] In any one of [8] to [25], after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, carbonization having 2 or less carbon atoms is performed by distillation. A fluid rich in hydrogen and a fluid rich in hydrocarbons having 3 or more carbon atoms are separated, and the fluid rich in hydrocarbons having 3 or more carbon atoms is separated from the fluid rich in hydrocarbons and carbon atoms containing 3 carbon atoms by distillation. A method for producing propylene, comprising a step of separating the fluid into a hydrocarbon-rich fluid having a number of 4 or more.

[27] In any one of [8] to [25], after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, carbonization of 3 or less carbon atoms is performed by distillation. A fluid rich in hydrogen and a fluid rich in hydrocarbons having 4 or more carbon atoms are separated into a fluid rich in hydrocarbons having 3 or less carbon atoms, and a fluid rich in hydrocarbons having 2 or less carbon atoms by distillation. A process for separating propylene into a hydrocarbon-rich fluid having 3 carbon atoms.

[28] In any one of the forces described in [8] to [25], in step 1, the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, and then the number of carbon atoms by distillation. A fluid containing a hydrocarbon having 2 or less hydrocarbons and a hydrocarbon having 3 carbon atoms is separated into a fluid rich in hydrocarbons having 3 or more carbon atoms, and the fluid rich in hydrocarbons having 3 or more carbon atoms is distilled by distillation. A method for producing propylene, comprising a step of separating a fluid rich in hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms.

[29] In any one of [8] to [25], after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, the distillation has a carbon number of 3 or less. A fluid rich in hydrocarbons and a fluid rich in hydrocarbons having 4 or more carbon atoms are separated, and the fluid rich in hydrocarbons having 3 or less carbon atoms is separated into hydrocarbons having 2 or less carbon atoms by distillation. A process for producing propylene, comprising a step of separating a fluid containing elemental hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms.

[30] The method for producing propylene according to any one of [8] to [29], wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

[31] The method for producing propylene according to [30], wherein the paraffins contain at least one of normal butane and isobutane.

[32] The method for producing propylene according to any one of [8] to [31], wherein the raw material supplied to the reactor contains butadiene.

[33] In any one of [8] to [32], the total amount of aromatic compounds contained in all the raw materials fed to the reactor is olefin having 4 or more carbon atoms contained in all the raw materials. Propylene production method, characterized in that the molar ratio is less than 0.05 with respect to the total amount of

[34] In any one of [8] to [33], in item 1, the quantity S of olefin having 4 or more carbon atoms to be supplied to the reactor, the number of moles of methanol to be fed to the reactor, and the number of moles of dimethyl ether The method for producing propylene, characterized in that the molar ratio is 0.2 or more and 10 or less with respect to the total of 2 times.

[35] In any one of [8] to [34], including the olefin raw material force S having 4 or more carbon atoms to be supplied to the reactor, and a hydrocarbon fluid having 4 carbon atoms obtained by the steam cracking process Propylene production method characterized by the above.

[36] In a method for producing propylene by contacting a mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps ( 1C), (2C), (3C), and a process comprising (4C).

Step (1C): olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (Q) recycled from step (4C), and at least one of methanol and dimethyl ether are supplied to the reactor, and the reactor outlet The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefins having 4 or more carbon atoms is 20% or more and less than 90% with respect to the molar flow rate of the olefins at the inlet of the reactor, and propylene and other components are discharged from the reactor outlet. Olefins, paraffins, aromatization Step of obtaining a gas (reactor outlet gas) containing a compound and water

Step (2C): Reactor outlet gas from step (1C) is cooled, gas fluid (L), liquid fluid (M) rich in hydrocarbons having 4 or more carbon atoms and containing aromatic compounds, and water To separate into a rich fluid

Step (3C): a step of separating the gas fluid (L) in the step (2C) into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid (N) rich in hydrocarbons having 4 or more carbon atoms.

Step (4C): Process of recycling at least a part of the fluid (N) (Q) to the reactor.

[37] In a method for producing propylene by contacting a mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps ( 1C), (2C), (3C), and a process comprising (4C).

Step (1C): olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (Q) recycled from step (4C), and at least one of methanol and dimethyl ether are supplied to the reactor, and the reactor outlet The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefins having 4 or more carbon atoms is 20% or more and less than 90% with respect to the molar flow rate of the olefins at the inlet of the reactor, and propylene and other components are discharged from the reactor outlet Of obtaining gas (reactor outlet gas) containing olefins, paraffins, aromatic compounds and water

Step (2C): The reactor outlet gas from the step (1C) is cooled, and the gas fluid (K) after cooling is compressed by gas fluid (L), rich in hydrocarbons having 4 or more carbon atoms, and aromatic compounds. Separation into liquid fluid (M) containing water and fluid rich in water

Step (4C): A step of extracting a part (P) of the fluid (N) from the process and recycling the remaining fluid (Q) to the reactor.

[38] In [36] or [37], the liquid fluid (M) has an aromatic concentration lower than that in the liquid fluid (M) by distillation! /, The fluid (R) and the carbon number of 4 A method for producing propylene, characterized in that the hydrocarbon concentration is separated into a fluid (S) lower than the liquid fluid (M). [39] In [38], the fluid (R) may be any force selected from the fluids (K), (L), (M), (P), and (Q), and one or more fluids A method for producing propylene, which is returned to the distribution location.

[40] In any one of [36] to [39], in the step (3C), the gas fluid (L) is obtained by distilling the fluid rich in hydrocarbons having 2 or less carbon atoms and 3 or more carbon atoms by distillation. It is separated into a fluid rich in hydrocarbons, and a fluid rich in hydrocarbons with 3 or more carbon atoms is distilled to enrich a fluid rich in hydrocarbons with 3 carbon atoms and rich in hydrocarbons with 4 or more carbon atoms. A process for producing propylene, which comprises a step of separating into a fluid (N).

[41] In any one of [36] to [39], in the step (3C), the gas fluid (L) is obtained by distilling the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms. The hydrocarbon-rich fluid (N) is separated into the above-mentioned hydrocarbon-rich fluid, and further, the hydrocarbon-rich fluid having 3 or less carbon atoms is distilled, and the hydrocarbon-rich fluid having 3 or less carbon atoms and carbon 3 or less are obtained by distillation. A process for producing propylene, comprising the step of separating into a hydrocarbon-rich fluid.

[42] In any one of the powers of [36] to [39], in step 1, the step (3C) includes distilling the gas fluid (L) into a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms. Is separated into a fluid rich in hydrocarbons containing 3 or more carbon atoms, and a fluid rich in hydrocarbons containing 3 or more carbon atoms is distilled into a fluid rich in hydrocarbons containing 3 carbon atoms. And a fluid rich in hydrocarbons (N) having 4 or more carbon atoms, and a process for producing propylene.

[43] In any one of the forces [36] to [39], in the step (3C), the gas fluid (L) is obtained by distilling the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms and the carbon number. It is separated into a hydrocarbon-rich fluid (N) having 4 or more hydrocarbons, and a fluid rich in hydrocarbons having 3 or less carbon atoms is distilled by distillation to produce hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms. A process for producing propylene, comprising a step of separating the fluid into a fluid rich in hydrocarbons containing 3 carbon atoms.

[44] In any one of the forces of [36] to [43], the olefin raw material having 4 or more carbon atoms, which is composed of two or more reaction parts connected in series with each other and fed to the reactor; At least one of methanol and dimethyl ether; and recycled charcoal A method for producing propylene, characterized in that at least one of the hydride-containing fluids is divided and supplied to a first-stage reaction section and a second-stage reaction section and thereafter.

[45] A method for producing propylene according to any one of [36] to [44], wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

[46] The method for producing propylene according to [45], wherein the paraffin contains at least one of normal butane and isobutane.

[47] The method for producing propylene according to any one of [36] to [46], wherein the raw material supplied to the reactor contains butadiene.

[48] In any one of the powers of [36] to [47], the total amount of aromatic compounds contained in all the raw materials fed to the reactor is olefin having 4 or more carbon atoms contained in all the raw materials. Propylene production method, characterized in that the molar ratio is less than 0.05 with respect to the total amount of

[49] In any one of the forces of [36] to [48], in item 1, at least one of the fluid (M) and the fluid (P) is supplied to a steam cracking process and used as a cracker raw material. A method for producing propylene, which is characterized.

[50] In [49], at least a part of at least one of the fluid (M) and the fluid (P) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process. Propylene production method.

[51] In any one of [36] to [50], the total concentration of aromatic compounds contained in at least one of the fluid (M) and the fluid (P) is less than 5.0% by volume. A process for producing propylene characterized by the above.

[52] The method for producing propylene according to any one of [36] to [51], wherein the fluid (M) is mixed with a cracked gasoline fraction of a steam cracking process.

[53] The production of propylene according to any one of [36] to [52], wherein the total concentration of C 4 hydrocarbons contained in the fluid (M) is less than 5% by weight Method.

[54] Any force of [36] to [53], wherein the fluid (M) and the fluid (P) The total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in all raw materials fed to the reactor is controlled to 20 vol% or more and 80 vol% or less. Propylene production method characterized by the above.

[55] A method for producing propylene according to any one of [38] to [54], wherein the fluid (R) is supplied to a steam cracking process and used as a cracker raw material.

[56] A method for producing propylene according to [55], wherein at least a part of the fluid (R) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.

[57] In any one of the forces of [38] to [56], the total concentration of aromatic compounds contained in the fluid (R) is less than 5.0% by volume of propylene. Production method.

[58] The method for producing propylene according to any one of the powers of [38] to [57], wherein the fluid (S) is mixed with a cracked gasoline fraction of a steam cracking process.

[59] The method for producing propylene according to any one of [38] to [58], wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (S) is less than 5% by weight. Law.

[60] In any one of the forces of [38] to [59], the total amount of fluid supplied to the reactor is controlled by controlling the flow rates of the fluid (P), fluid (R), and fluid (S). A method for producing propylene, characterized in that the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in the raw material is controlled to 20 volume% or more and 80 volume% or less.

[61] In any one of [38] to [60], the fluid (R) may be any force selected from the fluids (K), (L), (N), (P), and (Q), When returning to the location of 1 or 2 or more fluids, by controlling the return location and flow rate of the fluid (R), olefin and methanol having 4 or more carbon atoms contained in all the raw materials supplied to the reactor Propylene production method characterized in that the total concentration of dimethyl ether and substrate (substrate concentration) is controlled to 20 vol% or more and 80 vol% or less.

[62] In any one of [36] to [61], the quantity S of olefin having 4 or more carbon atoms to be fed to the reactor, the number of moles of methanol to be fed to the reactor, and the number of moles of dimethyl ether The molar ratio is 0.2 or more and 10 or less with respect to the total of 2 times. Propylene production method.

[63] In any one of the forces [36] to [62], including the olefin raw material power S having 4 or more carbon atoms to be supplied to the reactor, and the hydrocarbon fluid having 4 carbon atoms obtained by the steam cracking process Propylene production method characterized by the above.

The invention's effect

[0013] According to the present invention, in the method for producing propylene by reacting an olefin raw material having 4 or more carbon atoms with at least one of methanol and dimethyl ether in the presence of a catalyst, the raw material is highly advanced. Utilizing the power S to produce propylene in a high yield while suppressing catalyst deterioration.

It is also the power of integrating the method of the present invention with a steam cracking process to provide an economical process.

Brief Description of Drawings

FIG. 1 is a system diagram showing an example of an embodiment of a method for producing propylene of the present invention.

FIG. 2 is a system diagram showing another example of the embodiment of the method for producing propylene of the present invention.

FIG. 3 is a system diagram showing another example of the embodiment of the method for producing propylene of the present invention. Explanation of symbols

[0015] 10 reactors

20 First separation and purification system

30A, 30B Second separation and purification system

13 Reactor

23 Compressor

33 Knockout drum

43 Oil-water separator

53 First separation and purification system

63 Second separation and purification system

BEST MODE FOR CARRYING OUT THE INVENTION

[0016] Hereinafter, typical embodiments for carrying out the present invention will be described in detail. Beyond that gist! /, As long as it is not limited to the following aspects.

The method for producing propylene of the present invention is different from the method for producing propylene by contacting a olefin having 4 or more carbon atoms and a raw material containing at least one of methanol and dimethyl ether in the presence of a catalyst in a reactor. Thus, at least a part of the aromatic compound contained in the reactor outlet effluent gas is extracted and at least a part of the olefins having 4 or more carbon atoms contained in the reactor outlet effluent gas. The reactor is again brought into contact with the catalyst.

More specific first and second embodiments include those including the three steps (1), (2), (3A) or (1), (2), (3B) as described above, As long as it follows the purpose of solving the problem of the present invention, the force S including the four steps (1C), (2C), (3C) and (4C) as described above as the third embodiment There is no need to exclude the existence of other processes. Other processes may exist before and after the four processes, and other processes may exist between each process.

Note that the "rich" in the present invention, purity of 50 mol% or more of the desired product, preferably 7 0 mole ^_0/0 or more, more preferably 90 mol ^_0/0 or more, more preferably 95 mol ^_0/0 That means it is above. For example, “fluid rich in hydrocarbons having 4 or more carbon atoms (N)” means “hydrocarbons having 4 or more carbon atoms” of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol%. More preferably, the fluid contains 95 mol% or more.

[0017] [Catalyst]

First, the catalyst used in the present invention will be described.

The catalyst used in the reaction according to the present invention is not particularly limited as long as it is a solid having a Bronsted acid point, and a conventionally known catalyst is used. For example, clay minerals such as kaolin; clay minerals and the like Solid acid catalyst such as mesoporous silica alumina such as A1-MCM41; acidic type ion exchange resin; zeolites; aluminum phosphates;

Of these solid acid catalysts, those having a molecular sieving effect are preferred, and those having a very high acid strength are preferred.

[0019] Among the solid acid catalysts, zeolites and aluminum phosphates having a molecular sieve effect As a structure, for example, AEI, AET, AEL, AFI, AFO, AFS, AST, ATN, BEA, CAN, CHA, EMT, ERI, EUO, FAU, FER, LEV, LTL, MAZ, MEL, MFI, MOR, MTT, MTW, MWW, OFF, PAU, RHO, STT, TON, etc. Of these, catalysts with a catalyst framework density of 18. OT / nm ³ or less are preferred. MFI, MEL, MOR, MWW, FAU, BEA, and CHA are preferred. Preferably, MFI, MEL, MOR, MWW, CHA, particularly preferably MFI, MEL, MWW, CHA.

Here, 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.

[0020] Further, the solid acid catalyst more preferably has micropores having a pore diameter of 0.3 to 0.9 nm, a BET specific surface area of 200 to 700 m ² / g, and a pore volume of 0.3; Crystalline aluminosilicates, metamouth silicates, crystalline aluminum phosphates, etc. that are in the range of ~ 0.5 g / ml are preferred. Here, 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.

[0021] Of the aluminosilicates, those having a SiO 2 / Al 2 O molar ratio of 10 or more are preferred.

2 2 3

Yes. If the SiO 2 / Al 2 O molar ratio is too low, the durability of the catalyst is lowered, which is not preferable. S

2 2 3

The upper limit of the iO / AlO molar ratio is usually 10,000 or less. This is the molar ratio of Si〇 / Al〇.

If it is higher than 2 2 3 2 2 3, the catalytic activity will decrease, such being undesirable. 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.

[0022] These catalysts may be used alone or as a mixture of two or more. In the present invention, the catalytically active component as described above may be used as it is as a catalyst in the reaction, or granulated and molded using a substance or binder that is inert to the reaction, or may be used. These may be mixed for use in the reaction. Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica gel, quartz, and a mixture thereof.

[0024] 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. Thus, when 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.

[0025] 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.

[0026] 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. In addition, 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.

[0027] [Reaction raw materials]

Next, olefins having 4 or more carbon atoms, methanol, and dimethyl ether used as reaction raw materials in the present invention will be described.

[0028] <Olefin raw material>

The olefin having 4 or more carbon atoms used as a raw material for the reaction is not particularly limited. For example, oil produced by catalytic cracking or steam cracking, etc. (BB fraction, C4 rough rice toe 1, C4 rough rice toe 2, etc.), hydrogen / CO mixed gas obtained by gasification of coal It is obtained by synthesis of FT (Fischer-Tropsch) as a raw material and obtained by oligomerization reaction including ethylene dimerization reaction. Those obtained by dehydrogenation or oxidative dehydrogenation of paraffins having 4 or more carbon atoms, those obtained by MTO reaction, those obtained by dehydration reaction of alcohol, hydrogenation reaction of gen compounds having 4 or more carbon atoms Olefins having 4 or more carbon atoms, particularly 4 to 10 carbon atoms, which are obtained by various known methods such as those obtained by the above, can be used arbitrarily. At this time, 4 or more carbon atoms resulting from each production method can be used. A compound in which a compound other than olefin is arbitrarily mixed may be used as it is, or purified olefin may be used.

[0029] Among these, when using an olefin raw material containing paraffins having 4 or more carbon atoms, the reaction temperature can be easily controlled because norafine serves as a diluent gas, and the raw material containing paraffin is inexpensive. It is preferable because it is often available. More preferred

These preferable raw materials include the above-mentioned BB fraction, C4 rough rice toe 1 and C4 rough rice toe 2. These raw materials usually contain butadiene. Since butadiene is easily converted to an aromatic compound by reaction, it is very important to extract at least a part of the produced aromatic compound without recycling it to the reactor as in the present invention. Since the BB fraction contains a large amount of butadiene, it is preferable to use a fluid that has been brought into contact with a hydrogenation catalyst to lower the butadiene concentration as a raw material.

[0030] <Methanol, dimethyl ether>

The production origin of at least one of methanol and dimethyl ether used as a reaction raw material is not particularly limited. For example, those obtained by hydrogenation reaction of coal and natural gas, and by-product hydrogen / CO gas mixture in the steel industry, those obtained by reforming reaction of plant-derived alcohols, by fermentation method And those obtained from organic materials such as recycled plastic and municipal waste. At this time, it is possible to use a compound in which compounds other than methanol and dimethyl ether resulting from each production method are arbitrarily mixed, and it is also possible to use a purified product.

[0031] [Reaction Operation · Conditions: Step (1) (1C) in Embodiments 1 to 3]

In the following, the operation of the propylene production reaction of the present invention using the aforementioned catalyst and reaction raw materials • Explain the conditions.

[0032] <Reactor>

In the present invention, the reaction between olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether is a gas phase reaction. There are no particular restrictions on the form of the gas phase reactor, but it is usually selected from continuous fixed bed reactors and fluidized bed reactors. A fixed bed reactor is preferred.

[0033] When the above-mentioned catalyst is packed in a fixed bed reactor, in order to keep the temperature distribution of the catalyst layer small, particles inert to the reaction such as quartz sand, alumina, silica, silica-alumina, etc. The product may be mixed with the catalyst and filled. In this case, there is no particular limitation on the amount of particulates inert to the reaction such as quartz sand. In addition, it is preferable that this granular material is a particle size comparable as a catalyst from the surface of uniform mixing property with a catalyst.

[0034] The reactor may be composed of two or more reaction units connected in series.

In this case, one reactor may be divided into a plurality of reaction chambers, or two or more reactors may be connected in series.

When two or more reactors are connected in series as described above, a heat exchanger may be disposed between the reactors for the purpose of removing heat generated by the reaction.

In addition, the reaction substrate (reaction raw material) may be divided and supplied for the purpose of dispersing heat generation. Preferably, at least one of methanol and dimethyl ether is divided and supplied to the first-stage reaction section (reactor or reaction chamber) and the second-stage reaction section (reactor or reaction chamber).

[0035] Under the reaction conditions used in the present invention, the catalyst has little coking and the rate of catalyst deterioration is slow. However, when performing continuous operation for more than one year, it is necessary to regenerate the catalyst during operation. When selecting a fixed bed reactor, it is desirable to install at least two reactors in parallel and switch between reaction and regeneration. As the form of the fixed bed reactor, a multitubular reactor or an adiabatic reactor is selected.

On the other hand, when selecting a fluidized bed reactor, it is preferable to carry out the reaction while continuously feeding the catalyst to the regeneration tank and continuously returning the catalyst regenerated in the regeneration tank to the reactor. Here, examples of the catalyst regeneration operation include a method of regenerating the catalyst deteriorated by coking by treating it with nitrogen gas containing oxygen or water vapor. As the regeneration operation in the fixed bed reactor, preferably, after removing volatile organic compounds adhering to the catalyst with nitrogen gas, the coke content is burned and removed with nitrogen gas containing a low concentration of oxygen, and thereafter. An example is a method of removing molecular oxygen contained in the catalyst layer by treating with nitrogen gas.

[0037] <Concentration ratio of at least one of olefin and methanol and dimethyl ether supplied to the reactor>

In the present invention, the amount of olefin having 4 or more carbon atoms fed to the reactor is 0.2 in terms of a molar ratio to the sum of the number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether. Or more, preferably 0.5 or more, 10 or less, preferably 5 or less

Yes

That is, 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, which is preferable. In particular, if this supply concentration ratio is too low, the consumption of olefins as a raw material will be reduced.

[0038] Here, the supply concentration ratio is obtained by quantifying the composition of each fluid supplied to the reactor or the mixed fluid by a general analytical method such as gas chromatography. .

When supplying olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether to the reactor, they may be supplied separately or after mixing in part or in advance. Also good.

In the present invention, the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether in all the feeds fed to the reactor is preferably 20% by volume or more and 80% by volume or less, more preferably 30%. The volume is not less than 70% by volume.

Here, the substrate concentration is determined for each fluid supplied to the reactor or after mixing. It can be determined by quantifying the composition using a general analytical method such as gas chromatography.

[0040] If the substrate concentration is too high, aromatic compounds and paraffins are prominently produced, and the propylene selectivity tends to decrease. On the other hand, if 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.

In the present invention, the reaction substrate is diluted with a diluent gas described below so as to obtain such a substrate concentration. In this case, the method for controlling the substrate concentration includes a method for controlling the flow rate of the fluid extracted from the process. That is, by changing the flow rate of the fluid withdrawn from the process, it is possible to change the flow rate of the dilution gas recycled to the reactor and change the substrate concentration.

[0041] <Impurity concentration in gas supplied to reactor>

In the present invention, butadiene may be contained in the olefin raw material having 4 or more carbon atoms and / or in the hydrocarbon-containing fluid to be recycled, but butadiene in all the raw materials supplied to the reactor. The concentration of is preferably 2.0% by volume or less. If the concentration of butadiene in the raw material is high, the production of aromatic compounds increases and deterioration due to catalyst coking is accelerated.

[0042] Here, the butadiene concentration is determined by the force S known by quantifying the composition of each fluid supplied to the reactor or the fluid after mixing by a general analytical method such as gas chromatography.

Examples of a method for reducing the concentration of butadiene in the raw material include a partial hydrogenation method in which the fluid is brought into contact with a hydrogenation catalyst and converted into olefins.

[0043] The hydrocarbon-containing fluid to be recycled to the reactor may contain an aromatic compound! /, But the aromatic compound contained in all raw materials supplied to the reactor Is preferably less than 0.05 in terms of a molar ratio with respect to the total amount of olefins having 4 or more carbon atoms contained in all raw materials fed to the reactor. When the concentration of the aromatic compound in the raw material is high, the reaction between the aromatic compound and olefin having 4 or more carbon atoms, or the reaction between the aromatic compound and at least one of methanol and dimethyl ether in the reactor becomes remarkable. Therefore, it is not preferable because it consumes at least one of olefins having 4 or more carbon atoms, methanol and dimethyl ether more than necessary.

Furthermore, when an aromatic compound is supplied to the reactor, the compound produced by the reaction with the olefin having 4 or more carbon atoms clogs the pores of the catalyst, thereby promoting the deterioration of the catalyst. It is preferable to remove the aromatic compounds present in the reactor outlet fluid from the system as much as possible and reduce the concentration of the aromatic compounds in the fluid recycled to the reactor.

[0044] Here, the ratio of the total amount of the aromatic compounds and the total amount of olefins having 4 or more carbon atoms depends on the composition of each fluid supplied to the reactor or the fluid after mixing, such as gas chromatography. This can be determined by quantitative analysis using a typical analysis method.

An example of a method for reducing the concentration of aromatic compounds in the raw material is a separation method by distillation.

[0045] <Dilution gas>

In the reactor, in addition to olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether, paraffins, aromatics, steam, carbon dioxide, carbon monoxide, nitrogen, argon, helium, and There can be a gas inert to the reaction, such as a mixture of them. Of these diluting gases, paraffins and aromatics are defined as diluting gases because of the small amount of reaction that may react slightly depending on the reaction conditions.

As such 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.

Further, the dilution gas may be mixed with the reaction raw material before entering the reactor, or may be supplied to the reactor separately from the reaction raw material.

Preferred diluent gases are paraffins having 4 or more carbon atoms. More preferably, what is contained in the raw material for polyolefin can be used, and since the heat capacity is relatively high and the compound is used, the reaction temperature can be easily controlled.

[0046] <Space velocity> The space velocity mentioned here is the flow rate of olefin having 4 or more carbon atoms as the reaction raw material per weight of the catalyst (catalytic active component). Here, the weight of the catalyst is used for granulating and molding the catalyst. It is the weight of the catalytically active component which does not contain an inactive component or a binder. The flow rate is the flow rate (weight / hour) of olefins with 4 or more carbon atoms.

[0047] 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.

[0048] <Reaction temperature>

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.

[0049] <Reaction pressure>

The upper limit of the reaction pressure is usually 2 MPa (absolute pressure, the same applies hereinafter) or less, preferably IMPa or less, more preferably 0.7 MPa or less. The lower limit of the reaction pressure is not particularly limited, but is usually 1 kPa or more, preferably 50 kPa or more. If the reaction pressure is too high, the amount of preferable les and by-products such as paraffins and aromatic compounds increases, and the yield of propylene tends to decrease. If the reaction pressure is too low, the reaction rate tends to be slow.

[0050] <Raw material consumption by reaction>

The total of the molar flow rate of methanol fed to the reactor and twice the molar flow rate of dimethyl ether is preferably less than 1%. More preferably, it is less than 0.1%.

Reducing the consumption of methanol and dimethyl ether in the reactor If the amount of methanol or dimethyl ether at the reactor outlet increases too much, purification of the product olefin is difficult. Methods for increasing the consumption of methanol and dimethyl ether include increasing the reaction temperature and decreasing the space velocity.

[0051] In the present invention, the molar flow rate of olefins having 4 or more carbon atoms at the outlet of the reactor is set to 20% or more and less than 90% with respect to the molar flow rate of olefins having 4 or more carbon atoms supplied to the reactor. The molar flow rate is preferably 20% or more and less than 70%, more preferably 25% or more and less than 60%. If the consumption of olefins having 4 or more carbon atoms in the reactor is too small, the amount of unreacted olefins increases, and the flow rate of the fluid recycled to the reactor becomes too large. On the other hand, if the amount of consumption is too large, paraffin and aromatic compounds are not desirable! /, Which is preferable because the compounds are by-produced and the propylene yield is reduced! /.

Examples of the method for adjusting the consumption of olefins having 4 or more carbon atoms in the reactor include a method of appropriately setting the reaction temperature and space velocity.

[0052] Here, the flow rates of methanol and dimethyl ether and olefins having 4 or more carbon atoms to be supplied to the reactor are different from those of each fluid supplied to the reactor or the composition of the fluid after mixing such as gas chromatography. It is possible to know by measuring the flow rate of each fluid and measuring the flow rate of each fluid. The flow rate of methanol and dimethyl ether and olefins having 4 or more carbon atoms at the outlet of the reactor determines the composition of the outlet fluid of the reactor by gas chromatography. Quantify using a general technique such as graphing, and measure or calculate the flow rate of the reactor outlet fluid.

[0053] <Reaction product>

As the reactor outlet gas (reactor effluent), a mixed gas containing the reaction product, propylene, unreacted raw materials, by-products and a diluent is obtained. The propylene concentration in the mixed gas is usually 5 to 95% by weight.

The unreacted raw material is usually olefin having 4 or more carbon atoms. Depending on the reaction conditions, it is preferable to carry out the reaction under the reaction conditions such that at least one of methanol and dimethyl ether does not remain, and force S containing at least one of methanol and dimethyl ether.

. Thereby, separation of the reaction product and the unreacted raw material becomes easy.

By-products include ethylene, olefins with 4 or more carbon atoms, paraffins, and aromatics. Compounds and water are mentioned.

[0054] [Separation step]

Separation process in the first and second embodiments

The reactor outlet gas is separated into a hydrocarbon-rich fluid having 3 or less carbon atoms, a fluid rich in hydrocarbons having 4 or more carbon atoms (A), and water by a general separation process such as cooling, compression and distillation. Separated into rich fluid.

[0055] As a first aspect of the above general separation process, after condensing and removing moisture by a cooling and compression process, a fluid rich in hydrocarbons having 2 or less carbon atoms and carbonization having 3 or more carbon atoms by distillation. A fluid rich in hydrocarbons containing 3 or more carbon atoms is separated into a fluid rich in hydrocarbons, and a fluid rich in hydrocarbons containing 3 or more carbon atoms and a fluid rich in hydrocarbons containing 4 or more carbon atoms (A) A method including a step of separating into two is applied.

[0056] As a second aspect of a general separation step, after condensing and removing moisture by a cooling and compression step, a fluid rich in hydrocarbons having 3 or less carbon atoms and hydrocarbons having 4 or more carbon atoms by distillation. And a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms by distillation. A method including a step of separating is applied.

[0057] As a third aspect of a general separation process, after condensing and removing moisture by a cooling and compression process, a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms by distillation and carbon number Separation into a fluid rich in hydrocarbons with 3 or more hydrocarbons, and a fluid rich in hydrocarbons with 3 or more carbon atoms by distillation, fluids rich in hydrocarbons with 3 carbon atoms and fluids rich in hydrocarbons with 4 or more carbon atoms A method including the step of separating into (A) is applied.

[0058] As a fourth aspect of a general separation process, after condensing and removing moisture by a cooling and compression process, a fluid rich in hydrocarbons having 3 or less carbon atoms and hydrocarbons having 4 or more carbon atoms are obtained by distillation. And a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms and carbon having 3 carbon atoms by distillation. A method is applied that includes the step of separating into a hydrofluoric fluid.

[0059] In the first to fourth embodiments of the general separation step described above, if necessary, It is preferable to perform treatments such as alkali washing and dehydration. When the oxygen-containing compound is contained in the reactor outlet gas, at least a part of the oxygen-containing compound is removed by the quenching process. When 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. It is preferable to remove the remaining water with an adsorbent such as molecular sieve. The water removed by condensation and / or adsorption may be used for wastewater treatment processes such as activated sludge, but it can be used for process water.

When the process of the present invention (hereinafter sometimes referred to as “the process”) is in the vicinity of a steam cracking process, the water recovered from the reactor outlet gas is preferably utilized as a steamer steam source. . It may be recycled to the reactor of this process and used as a diluted gas.

[0060] In addition, hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms obtained from the reactor outlet gas can be further purified to ethylene and propylene with high purity by a purification process such as distillation. preferable. The purity of ethylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more. The purity of propylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.

[0061] The ethylene and propylene thus obtained can be used as raw materials for ethylene and propylene derivatives that are generally produced from the viewpoint of quality such as the amount of impurities. For the production of oxides, ethylene glycol, ethanolamine, glycol ethers, etc., for the production of chlorinated butyl monomers, 1, 1, 1 trichloroethane, chlorinated resin, vinylidene chloride by chlorination, and for the polymerization of ethylene, α-olefin, It can be used for the production of low density or high density polyethylene and for the production of ethylbenzene and the like by benzene ethylation.

[0062] Polyethylene terephthalate can be further produced from ethylene glycol produced from ethylene power, using _α- olefin as a raw material, and higher alcohol is converted into ethyl benzene by an oxo reaction and subsequent hydrogenation reaction. Can be used to produce styrene monomer, ABS resin, etc. Also, by reaction with acetic acid Acetaldehyde and its derivative ethyl acetate can also be produced by the reaction.

[0063] Propylene is produced, for example, by ammoxidation for the production of acrylonitrile, by selective oxidation for the production of acrolein, acrylic acid and acrylate esters, and by oxo reaction by oxo-reactions such as cal- butyl alcohol and 2-ethylhexanol. It can be applied to the production of alcohol, the production of polypropylene by polymerization of propylene, and the production of propylene oxide and propylene glycol by the selective oxidation of propylene. In addition, acetone can be produced by one reaction, and further, methylisoptyl ketone can be produced from acetone. Acetone can also produce acetone cyanohydrin, which is ultimately converted to methylmethalate. Isopropyl alcohol can also be produced by propylene hydration. In addition, phenol, bisphenol A, and polycarbonate resin can be produced from cumene produced by alkylating benzene.

[0064] In addition, the fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms obtained in the third and fourth aspects of the above general separation step! It is preferable to supply it to an ethylene and propylene production process other than this process for purification. Other than this process, ethylene and propylene production processes include steam cracking processes such as naphthaetane. This can significantly reduce the capital investment of this process.

On the other hand, if the fluid containing ethylene produced in this process cannot be supplied to other ethylene and propylene production processes, it is necessary to purify ethylene in this process. It is preferable to adopt the first embodiment or the second embodiment.

[0065] Separation step in the third embodiment

[Separation process]

In the present invention, the reactor outlet gas is cooled, and the gas fluid (K) after cooling is compressed by gas fluid (L), rich in hydrocarbons having 4 or more carbon atoms, and liquid fluid (M) containing aromatic compounds. And a fluid rich in water (process (2C)), and then a gas fluid (U is separated by a general separation process such as distillation and a fluid rich in hydrocarbons having 3 or less carbon atoms and 4 or more carbon atoms). hydrocarbon Into a rich fluid (N) (step (3C)).

[0066] In the step (2C), the reactor outlet gas is usually at a temperature of about 300 to 600 ° C. The reactor outlet gas is cooled to about 20 to 200 ° C. This cooling may be performed directly by mixing with a fluid usually performed in a heat exchanger or a fluid having a temperature lower than that of the gas. The cooled fluid (K) is compressed into a hydrocarbon-rich gas fluid (L) and hydrocarbons with 4 or more carbon atoms by compression using a compressor, knockout drum or oil-water separator. It is separated into a rich fluid (M) containing aromatics and a fluid rich in water. In the above heat exchanger, the partner fluid that exchanges heat with the reactor outlet gas is not particularly limited! /, But is preferably one or more fluids supplied to the reactor! / ,.

[0067] The gas fluid (L) rich in hydrocarbons having 6 or less carbon atoms separated in this step (2C) contains hydrocarbons. In step (3C), general separation such as distillation is performed. The process separates the fluid rich in hydrocarbons with 3 or less carbon atoms and the fluid (N) rich in hydrocarbons with 4 or more carbon atoms.

[0068] As a first aspect of the above general separation process, the separation is performed by distillation into a hydrocarbon-rich fluid having 2 or less carbon atoms and a hydrocarbon-rich fluid having 3 or more carbon atoms. A method including a step of separating a fluid rich in hydrocarbons having 3 or more hydrocarbons into a fluid rich in hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms (N) by distillation is applied.

[0069] As a second aspect of the separation step, by distillation, a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid (N) rich in hydrocarbons having 4 or more carbon atoms are separated into 3 or less carbon atoms. A method including a step of separating a fluid rich in hydrocarbons into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms by distillation is applied.

[0070] As a third aspect of the separation step, separation is performed by distillation into a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms, A method including a step of separating a fluid rich in hydrocarbons having 3 or more carbon atoms into a fluid rich in hydrocarbons having 3 or more carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms (N) by distillation is applied.

[0071] As a fourth aspect of the separation step, a hydrocarbon-rich fluid having a carbon number of 3 or less and a fluid (N) rich in a hydrocarbon having a carbon number of 4 or more are separated by distillation to obtain a hydrocarbon having a carbon number of 3 or less. To hydrocarbon A method including a step of separating a rich fluid into a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms and a fluid rich in a hydrocarbon having 3 carbon atoms by distillation is applied.

[0072] In the above-described process, it is preferable to perform treatment such as taenchi, alkali washing, dehydration and the like as necessary. When the oxygen-containing compound is contained in the reactor outlet gas, at least a part of the oxygen-containing compound is removed by the taenti process. When 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.

[0073] In addition, hydrocarbons having 2 or less carbon atoms or hydrocarbons having 3 carbon atoms obtained from the reactor outlet gas can be further purified to ethylene and propylene with high purity by a purification process such as distillation. preferable. The purity of ethylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more. The purity of propylene is 95% or more, preferably 99% or more. More preferably, it is 99.9% or more.

[0074] The ethylene and propylene thus obtained can be used for all of the generally produced ethylene and propylene derivatives. For example, ethylene is produced by the oxidation reaction to produce ethylene oxide, ethylene glycol, ethanolamine, glycol ether, etc. Benzyl chloride, 1, 1, 1 trichloroethane, chlorinated resin, vinylidene chloride by chlorination, and _α- olefin, low density or high density polyethylene by polymerization of ethylene. These can be used for the production of ethylbenzene and the like by ethenylation.

[0075] Polyethylene from ethylene glycol produced from ethylene power Terephthalate can be produced, and styrene monomer, ABS resin, etc. can be produced from higher alcohol ethylbenzene as a raw material by the oxo reaction using a-olefin and the subsequent hydrogenation reaction. In addition, butyl acetate can be produced by reaction with acetic acid, and cetyl acetate and its derivatives, such as acetoaldehyde, can be produced by the reaction of Zucker.

[0076] In addition, propylene is produced by, for example, ammoxidation for the production of acrylonitrile, by selective oxidation for the production of acrolein, acrylic acid and acrylate esters, and by oxo reaction by oxo-reactions such as cal- butyl alcohol and 2-ethylhexanol. It can be applied to the production of alcohol, the production of polypropylene by polymerization of propylene, and the production of propylene oxide and propylene glycol by the selective oxidation of propylene. In addition, acetone can be produced by one reaction, and further, methylisoptyl ketone can be produced from acetone. Acetone can also produce acetone cyanohydrin, which is ultimately converted to methylmethalate. Isopropyl alcohol can also be produced by propylene hydration. In addition, phenol, bisphenol A, and polycarbonate resin can be produced from cumene produced by alkylating benzene.

[0077] Further, the fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms obtained in the third and fourth aspects of the separation step described above is a mixture of ethylene and propylene other than this process. It is preferably supplied to the production process for purification. Other processes for producing ethylene and propylene include steam cracking processes such as naphthaetane. This can significantly reduce the capital investment of this process.

[0078] First and second embodiments

At least a portion of the hydrocarbon-rich fluid (A) separated from the reactor outlet gas (A) (hereinafter referred to as hydrocarbon fluid (A) having 4 or more carbon atoms) is recycled to the reactor. The remaining fluid is withdrawn from the process.

Here, “extracted from this process” means that it is not recycled to the reactor of this process, and it may be supplied directly to other processes through piping or through piping. Once stored in the tank, it may be supplied to another process. It may also be used as fuel without being supplied to other processes.

[0079] As a first aspect of the method for recycling the hydrocarbon fluid (A) having 4 or more carbon atoms to the reactor, a part (B) of the hydrocarbon fluid (A) having 4 or more carbon atoms is removed from the process. Extract the remaining fluid (C) using a general separation method such as distillation. The concentration of aromatic compounds (% by weight) is lower than that of fluid (C)! /, And the concentration of fluid (D) and hydrocarbons with 4 carbon atoms is fluid. Lower than (C)! /, Fluid (E) is separated, fluid (D) is recycled to the reactor, and a method including the step of withdrawing fluid (E) from the process is applied.

[0080] As a second embodiment, the concentration of aromatic compounds is lower than that of fluid (A) by using a general separation method such as distillation of hydrocarbon fluid (A) having 4 or more carbon atoms! /, Fluid (G) And the hydrocarbon concentration of carbon number 4 is lower than that of the fluid (A)! /, And the fluid (F) is separated, and at least a part of the fluid (F) is extracted from the process, and at least the fluid (G) A method including a step of recycling a part of the fluid (I) to the reactor and extracting the remaining fluid (H) from the process is applied.

[0081] When a raw material containing paraffin having 4 or more carbon atoms is used as the olefin raw material having 4 or more carbon atoms, the fluid (B) in the first embodiment or the fluid (H) in the second embodiment. Is a composition fluid containing a lot of paraffin, so it is difficult to separate and purify active ingredients such as butene. Therefore, when the process is in the vicinity of the steam cracking process, it is preferably supplied to the steam cracking process and effectively used as a cracker raw material.

[0082] Thereby, these fluids (B) and (H) can be used as raw materials for producing ethylene and propylene in steam cracking. At this time, at least a part of the fluid (B) or fluid (H) is brought into contact with the hydrogenation catalyst, and a fluid having a paraffin concentration increased from that of the fluid (B) or fluid (H) is supplied to the steam cracking process. preferable. If a fluid having a high olefin concentration is supplied to the cracker in the steam cracking process, carbon deposition is likely to occur in the cracker, which is preferable. [0083] In this case, the total concentration of aromatic compounds contained in fluid (B) or fluid (H) is preferably less than 5.0% by volume, more preferably less than 3.0% by volume. is there. When the aromatic compound concentration is high, there is a large amount of carbon precipitation when fed to the cracker, and the ethylene yield tends to decrease, which is not preferable.

[0084] The fluid (E) in the first aspect or the fluid (F) in the second aspect is preferably mixed with a cracked gasoline fraction such as a steam cracking process. This makes it possible to effectively use fluid (E) or fluid (F).

[0085] The cracked gasoline here is a fluid mainly containing paraffin, olefin, gen, and aromatic compounds having 5 to 10 carbon atoms, and the ability to collect active ingredients from the cracked gasoline as required. S can. Examples of active ingredients include hydrocarbons having 5 carbon atoms and aromatic compounds such as benzene, toluene and xylene.

[0086] If the cracked gasoline contains hydrocarbons having 4 carbon atoms, it is not preferable because hydrocarbons having 4 carbon atoms are mixed in the hydrocarbon fluid having 5 carbon atoms recovered from the cracked gasoline. Therefore, it is preferable that the C4 hydrocarbon in the fluid (E) or fluid (F) mixed with the cracked gasoline fraction is less than 5% by weight. More preferably, it is less than 2% by weight.

[0087] The feature of the first aspect is that the load of the separation process such as distillation can be reduced by extracting the fluid (B). More advantageous. However, fluid (B) is a fluid having the same composition as fluid (A), and the concentration of the aromatic compound is higher than that of fluid (H) obtained in the second mode. Therefore, the process is selected according to the intended use of the fluid to be extracted.

[0088] Third aspect

Part (P) of the fluid rich in hydrocarbons with 4 or more carbon atoms (N) separated in step (3C) (hereinafter referred to as “hydrocarbon fluids with 4 or more carbon atoms (N)”) The remaining fluid (Q) is withdrawn and recycled to the reactor, and at least one of the liquid fluid (M) rich in hydrocarbons having 4 or more carbons condensed in the compression process and containing aromatic compounds. Departments are extracted from this process.

Here, “extracted from the process” is not recycled to the reactor of the process. This means that it may be supplied directly to other processes through piping, or once stored in a tank through piping, it may be supplied to other processes. It may also be used as fuel without being supplied to other processes.

[0089] Liquid fluid (M) has a lower concentration of aromatic compounds (wt%) than liquid fluid (M) due to distillation! The concentration of fluid (R) and hydrocarbons with 4 carbon atoms is higher than liquid fluid (M). It may be separated into lower fluid and fluid (S). In this case, the fluid (R) is preferably returned to one or a plurality of fluid circulation locations selected from the fluids (K), (L), (N), (P), and (Q). This distillation operation is particularly preferred when the liquid fluid (M) contains a large amount of hydrocarbons having 4 or less carbon atoms.

[0090] When a raw material containing paraffin having 4 or more carbon atoms is used as the olefin raw material having 4 or more carbon atoms, the fluids (M), (P), and (R) have a composition containing a large amount of paraffin. Since it is a fluid, it is difficult to separate and purify active ingredients such as butene. Therefore, when the process is in the vicinity of the steam cracking process, one of these fluids (M), (P), (R), one or more fluids are supplied to the steam cracking process, and the cracker raw material is supplied. It is preferable to use as effective.

[0091] This can be a raw material for producing ethylene or propylene in steam cracking. At this time, at least a part of the fluids (M), (P), and (R) is brought into contact with the hydrogenation catalyst, and the fluid whose paraffin concentration is increased from the fluids (M), (P), and (R) is steamed. It is preferable to supply it to the cracking process. It is not preferable to feed a fluid with a high olefin concentration to the cracker in the steam cracking process because carbon is likely to precipitate in the cracker.

Yes

[0092] In this case, the total concentration of aromatic compounds contained in the fluids (M), (P), and (R) is preferably less than 5.0% by volume. More preferably, it is less than 3.0 volume%. A high concentration of the aromatic compound is not preferable because when it is supplied to the cracker, there is a large amount of carbon precipitation and the ethylene yield tends to decrease.

[0093] The fluid (S) is preferably mixed with a cracked gasoline fraction such as a steam cracking process. As a result, the fluid (S) can be used effectively. If the concentration of hydrocarbons with 4 or less carbon atoms in the fluid (M) is low, the fluid (M) You may mix with a catalytic cracking gasoline fraction.

[0094] The cracked gasoline here is a fluid mainly containing paraffin, olefin, gen, and aromatic compounds having 5 to 10 carbon atoms, and has the ability to collect active ingredients from the cracked gasoline as necessary. S can. Examples of active ingredients include hydrocarbons having 5 carbon atoms and aromatic compounds such as benzene, toluene and xylene.

[0095] When cracked gasoline contains hydrocarbons having 4 carbon atoms, it is not preferable because hydrocarbons having 4 carbon atoms are mixed in the hydrocarbon fluid having 5 carbon atoms recovered from the cracked gasoline.

. Therefore, it is preferable that the C4 hydrocarbon in the fluid (M) or fluid (S) mixed with the cracked gasoline fraction is less than 5% by weight. More preferably, it is less than 2% by weight.

[0096] <Control of substrate concentration at reactor inlet>

In the first aspect described above, by controlling the flow rates of fluid (B) and fluid (E), it is possible to control the flow rate of dilution gas such as paraffin contained in fluid (D) recycled to the reactor. It is.

In the second mode, the flow rate of the dilution gas such as paraffin contained in the fluid (I) recycled to the reactor is controlled by controlling the flow rates of the fluid (F) and the fluid (H). Is possible.

[0097] In the third embodiment, the fluid (M) and the fluid (P), the flow rate of the fluid (P), the fluid (R) and the fluid (S), and the fluid (K ), (L), (N), (P), and (Q), and by controlling the flow rate of fluid (R) to be returned to one or more fluid locations and the return location, It is possible to control the flow rate of dilution gas such as paraffin contained in the fluid (Q) recycled to the reactor.

Thereby, it is preferable to control the total concentration (substrate concentration) of olefins, methanol and dimethyl ether having 4 or more carbon atoms in all the feeds supplied to the reactor to 20 vol% or more and 80 vol% or less.

[0098] [Integration with steam cracking process]

In the steam cracking process, the required value is removed from the obtained hydrocarbon fluid (BB fraction) with 4 carbon atoms! /, And the fluid (mainly C4 rough rice toe 2) is hydrogenated and returned to the cracker. Te! In this process, this low-value fluid can be used as a raw material, and fluids that are unnecessary in this process can be used in the steam cracking process. It is an extremely efficient process that can.

[0099] [Process Embodiment]

Hereinafter, embodiments of the process of the present invention will be described with reference to the drawings. FIG. 1 shows a first embodiment of the process of the present invention, and FIG. 2 shows a second embodiment.

In FIGS. 1 and 2, 10 is a reactor, 20 is a first separation and purification system, and 30A and 30B are second separation and purification systems. 10;! To 114 each indicate piping.

[0101] <Description of first mode (Fig. 1)>

At least one of the olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (D) having 4 or more carbon atoms from the second separation and purification system 30A, methanol and dimethyl ether is connected to pipes 101, 102, 103 and 104, respectively. Then, it is supplied to the reactor 10. The olefin raw material having 4 or more carbon atoms supplied to the reactor 10 may contain paraffins having 4 or more carbon atoms, such as calalebutane and isobutane. The raw material fluid supplied to the reactor 10 via the pipe 104 may contain butadiene or an aromatic compound. The butadiene concentration in the raw material fluid as described above is usually 2.0% by volume or less, and the total amount of aromatic compounds is moles relative to the total amount of olefins having 4 or more carbon atoms contained in the raw material fluid in the pipe 104. The ratio is usually less than 0.05. Note that the feed fluid is a force S, which means the sum of the fluids supplied via pipes 101, 102 and 103, which do not necessarily have to be joined before entering reactor 10, 10 may be supplied. The raw material gas supplied to the reactor 10 reacts in contact with the catalyst in the reactor 10 to obtain a reactor outlet gas containing propylene, other olefins, paraffins, aromatic compounds and water.

[0102] The reactor outlet gas is sent to a general separation and purification system 20 such as cooling, compression, and distillation through a pipe 105, and in this separation and purification system 20, a fluid rich in hydrocarbons having 3 or less carbon atoms, They are separated into a hydrocarbon-rich fluid (A) and water-rich fluid with 4 or more carbon atoms, and taken out through pipes 106, 108, and 107, respectively. Here, a hydrocarbon-rich fluid having 3 or less carbon atoms indicates one or more fluids. For example, including all hydrocarbons with 3 or less carbon atoms One fluid may be used, a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms, or a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms. Two fluids, such as a fluid rich in 3 carbon atoms, may be used. Furthermore, three or more fluids may be used.

[0103] A part of the hydrocarbon-rich fluid (A) with 4 or more carbon atoms is withdrawn out of the process through the pipe 109, and the remaining fluid (C) is separated through the pipe 110 through general separation such as distillation. Supplied to purification system 30A. A part of the fluid (A) (B) may be extracted out of the process. At this time, the extracted fluid (B) may be used as a cracker raw material for the steam cracking process. In that case, it is preferable to supply the extracted fluid (B) to the steam cracking process as a fluid in which the concentration of paraffin is increased by contacting the hydrogenation catalyst. At this time, the total concentration of aromatic compounds in the extracted fluid (B) is preferably less than 5.0% by volume.

[0104] In the separation and purification system 30A, the aromatic compound concentration is lower than the fluid (C)! / Soot fluid (D) and the fluid (E) in which the hydrocarbon concentration of 4 or more carbon atoms is lower than the fluid (C) At least a part of the fluid (D) is recycled to the reactor 10 via the pipe 102, and the fluid) is extracted from the process via the pipe 111. The extracted fluid (E) may be mixed with a cracked gasoline fraction such as a steam cracking process. In that case, the total concentration force of hydrocarbons having 4 carbon atoms contained in the fluid (E) is preferably less than 3% by weight.

A part of the fluid (D) (hereinafter, “fluid (X)”) may be extracted out of the process. At this time, the extracted fluid (X) may be used as a cracker raw material for the steam cracking process. In that case, it is preferable to supply the extracted fluid (X) to the steam cracking process as a fluid in which the concentration of paraffin is increased by contacting the hydrogenation catalyst. At this time, the total concentration of aromatic compounds in the drawn fluid (X) is preferably less than 5.0 mol%.

[0105] The fluid (D) and the fluid (X) are not necessarily required, but it is preferable to extract at least one of the fluids from the process in order to prevent accumulation of norafines.

Carbon 4 or more olefin raw material, carbonization of 4 or more carbon from the second separation and purification system 30B At least one of hydrogen fluid (I), methanol, and dimethyl ether is supplied to the reactor 10 via pipes 101, 102, 103 and pipe 104, respectively. Thereafter, in the first separation purification system 20, from the outlet gas of the reactor 10, a fluid rich in hydrocarbons having 3 or less carbon atoms, a hydrocarbon fluid having 4 or more carbon atoms (A), and rich in water. The process until separation into a fluid is the same as in FIG.

[0107] The hydrocarbon fluid (A) having 4 or more carbon atoms is supplied from a pipe 108 to a general separation and purification system 30B such as distillation. Separation and purification system 30B separates the fluid (G) with a lower aromatic compound concentration than the fluid (A) and the hydrocarbon concentration with 4 or more carbon atoms lower than the fluid (A)! /, Fluid (F). . Fluid (F) is withdrawn from the process through line 112. The extraction fluid (F) may be mixed with a cracked gasoline fraction such as a steam cracking process. In that case, it is preferable that the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (F) is less than 5% by weight.

[0108] The fluid (G) is taken out from the pipe 113, a part (H) is taken out from the process through the pipe 114, and the remaining fluid (I) is recycled to the reactor 10 through the pipe 102. The The extracted fluid (H) may be used as a cracker raw material for the steam cracking process. In that case, the fluid (H) is preferably supplied to the steam cracking process as a fluid in which the concentration of paraffin is increased by contacting the hydrogenation catalyst. At this time, the total concentration of aromatic compounds in the fluid (H) is preferably less than 5.0% by volume.

[0109] It is not always necessary to extract the fluid (H) out of the process, but it is preferable to extract at least a part of the fluid from the process in order to prevent accumulation of paraffins.

[Process embodiment]

Hereinafter, embodiments of the process of the present invention will be described with reference to the drawings.

FIG. 3 illustrates one embodiment of the process of the present invention.

In FIG. 3, 13 is a reactor, 23 is a compressor, 33 is a knockout drum, 43 is an oil-water separator, 53 is a first separation and purification system, and 63 is a second separation and purification system. 30;! To 315 indicate piping. [0111] At least one of the olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (Q) having 4 or more carbon atoms from the first separation and purification system 53, methanol, and dimethyl ether is provided in the pipes 301, 302, 303, and It is supplied to the reactor 13 through the pipe 304. The olefin raw material having 4 or more carbon atoms supplied to the reactor 13 may contain paraffins having 4 or more carbon atoms, such as calalebutane and isobutane. The raw material fluid supplied to the reactor 13 via the pipe 304 may contain butadiene or an aromatic compound. The butadiene concentration in the raw material fluid as described above is usually 2.0% by volume or less, and the total amount of aromatic compounds is mol relative to the total amount of olefins having 4 or more carbon atoms contained in the raw material fluid of the pipe 304. The ratio is usually less than 0.05. Note that the raw material fluid means the sum of the fluids supplied via the pipes 301, 302, and 303! /, And these forces are not necessarily merged before entering the reactor 13 separately. It may be supplied to the reactor 13. The raw material gas supplied to the reactor 13 is reacted with the catalyst in the reactor 13 to obtain a reactor outlet gas containing propylene, other olefins, paraffins, aromatic compounds and water.

[0112] The reactor outlet gas is cooled through, for example, a heat exchanger, and the cooled gas fluid (K) is pressurized by the compressor 23 through the pipe 305. One compressor 23 may be used, but a plurality of compressors 23 are preferable. A heat exchanger and a knockout drum 33 are installed after each compressor 23, and after the compressed gas is cooled, it is separated into a gas fluid (L) and a condensed component. Condensed components are sent to the oil / water separator 43 via the pipe 30 8 and separated into a hydrocarbon-rich liquid fluid (M) having 4 or more carbon atoms and a water-rich fluid. The liquid fluid (M) rich in hydrocarbons with 4 or more carbon atoms extracted is sent to the second separation / purification system 63 through the pipe 309.

[0113] The gas fluid (L) separated by the knockout drum 33 is sent to a general first separation / purification system 53 such as distillation through a pipe 307, and a fluid rich in hydrocarbons having 3 or less carbon atoms. Then, it is separated into a hydrocarbon-rich fluid (N) having 4 or more carbon atoms and taken out via pipes 313 and 314, respectively. Here, a hydrocarbon-rich fluid having 3 or less carbon atoms represents one or more fluids. For example, a single fluid containing all hydrocarbons with 3 or less carbon atoms, a fluid rich in hydrocarbons with 2 or less carbon atoms, a fluid rich in hydrocarbons with 3 carbon atoms, Two fluids may be used, such as a fluid containing a hydrocarbon having a carbon number of 2 or less and a hydrocarbon having 3 carbon atoms and a fluid rich in a hydrocarbon having 3 carbon atoms. Furthermore, three or more fluids may be used.

[0114] A part (P) of the fluid (N) rich in hydrocarbons having 4 or more carbon atoms is extracted from the process through the pipe 315, and the remaining fluid (Q) is supplied to the reactor 13 through the pipe 302. Recycled. The fluid (P) may be used as a cracker raw material for the steam cracking process. In that case, the fluid (P) is preferably supplied to the steam cracking process as a fluid in which the paraffin concentration is increased by contacting the hydrogenation catalyst. At this time, the total concentration of aromatic compounds in the fluid (P) is preferably less than 5.0% by volume! /.

[0115] On the other hand, the liquid fluid (M) separated by the oil / water separator 43 is a liquid component rich in hydrocarbons having 4 or more carbon atoms and containing an aromatic compound, which is directly extracted from the process. In this case, the liquid fluid (M) may be used as a cracker raw material for the steam cracking process. In that case, the fluid (M) is preferably supplied to the steam cracking process as a fluid in which the paraffin concentration is increased by contacting the hydrogenation catalyst. At this time, the total concentration of aromatic compounds in the fluid (M) is preferably less than 5.0% by volume.

[0116] When the hydrocarbon concentration of carbon number 4 in the liquid fluid (M) is low, it may be mixed with a cracked gasoline fraction such as a steam cracking process. In that case, it is preferable that the total concentration of the hydrocarbon having 4 carbon atoms contained in the fluid (M) is less than 5% by weight.

[0117] Further, at least a part of the liquid fluid (M) is the second separation / purification system 60, which is a general separation step such as distillation, and the concentration of the aromatic compound is lower than that of the liquid fluid (M)! /, It is preferable to separate the fluid (R) and the C4 hydrocarbon concentration from the liquid fluid (M) and the fluid (S). The separated fluid (R) is extracted from the pipe 111, but the fluid (R) is fluid (K), fluid (L), fluid (N), fluid (P), fluid (Q) flow. It is preferable to return to one or more of 305, 307, 314, 315, 302.

[0118] On the other hand, the fluid (S) is extracted from the pipe 312 and the fluid (S) may be mixed with a cracked gasoline fraction such as a steam cracking process. In that case, the total concentration of C 4 hydrocarbons contained in the fluid (S) is preferably less than 5% by weight.

Extraction of the fluid (P) out of the process is not always necessary, but paraffins In order to prevent accumulation of at least one of the fluids is preferably withdrawn from the process.

Example

[0119] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

[0120] [Catalyst preparation]

The catalysts used in the following examples and comparative examples were prepared as follows.

Bromide tetra n- propyl ammonium Niu beam (TPABr) 26. 6 g of sodium hydroxide 4 · 8 g successively, in water 280g溶角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.

[0121] This Na-type aluminosilicate 2. Og was suspended in 40 ml of 1M ammonium nitrate aqueous solution and stirred at 80 ° C for 2 hours. After the treatment, the solid component was separated by suction filtration, washed thoroughly with water, then suspended in 40 ml of 1M aqueous ammonium nitrate solution and stirred at 80 ° C for 2 hours. After the treatment, the solid component was separated by suction filtration, washed thoroughly with water, and dried at 100 ° C for 24 hours. The dried catalyst was calcined at 500 ° C for 4 hours under air flow to obtain H-type aluminosilicate.

[0122] This catalyst was confirmed by XRD (X-ray diffraction) to have a zeolite structure of MFI type. When the composition of the catalyst was quantified by chemical analysis, it was SiO 2 / Al 2 O = 1100 (molar ratio).

2 2 3

I got it.

[0123] [Production of propylene]

The production examples and comparative examples of propylene using the above catalyst are shown below.

[0124] <Example 1>

Propylene was produced using the above catalyst. A normal pressure fixed bed flow reactor was used for the reaction, and a quartz reaction tube having an inner diameter of 6 mm was filled with a mixture of the above catalyst (0.10 g) and quartz sand (1 Og). Anti応器inlet gas of the present invention in the reactor isobutene (40 vol ^_0/0) as a model gas, which corresponds to the composition (Fig. 1 or the pipe 104 in FIG. 2), methanol (20 vol ^_0/0), benzene (0 . 8 vol ^_0/0), were fed through butadiene (0.1 body volume%) and isobutane (evaporator 39. was prepared in 1% by volume) gas. The reaction temperature (reactor inlet gas temperature) was 550 ° C. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography. The reaction conditions and reaction results at that time are shown in Table 1.

The selectivity for propylene was 54.8%, a very high level.

Further, the reaction was continued, and the time until the methanol conversion fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 312 hours.

[0125] <Example 2>

The reaction was carried out in the same manner as in Example 1 except that the concentration of benzene supplied to the reactor was 1.6% by volume and the isobutane concentration was 38.3% by volume. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography. Table of reaction conditions and reaction results at that time

Shown in 1.

The selectivity for propylene was 54.4%, a very high level.

Further, the reaction was continued, and the time until the methanol conversion fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 305 hours.

[0126] <Comparative Example 1>

The reaction was performed in the same manner as in Example 1 except that the concentration of benzene supplied to the reactor was 3.2% by volume and the isobutane concentration was 36.7% by volume. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography. Table of reaction conditions and reaction results at that time

Shown in 1.

The selectivity for propylene was 51.4%, which was a very low level compared to Examples 1 and 2.

This is because butene and / or methanol and benzene react with each other to produce alkylated benzene. Or it is due to wasteful consumption of methanol.

Further, the reaction was continued, and the time until the methanol conversion fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 221 hours, which was very short compared to Examples 1 and 2. This is presumably because the alkylated benzene blocks the pores of the catalyst and promotes coking.

Thus, in accordance with the method of the present invention, reducing the aromatic compound concentration at the inlet of the reactor by extracting at least a part of the aromatic compound without recycling can achieve a high propylene yield and suppress catalyst coking deterioration. It is very effective.

[table 1]

«1: Selectivity of olefins with 5 or more carbon atoms

«2: Total selectivity of aromatic compounds and paraffin

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on a Japanese patent application filed on September 21, 2006 (Japanese Patent Application 2006-255503) and a Japanese patent application filed on September 21, 2006 (Japanese Patent Application 2006-255504). The contents are incorporated here by reference.

Industrial applicability The present invention is a new and economical process for producing propylene by reacting olefins having 4 or more carbon atoms with at least one of methanol and dimethyl ether, and a new and economical process that integrates this process with steam cracking. To provide a realistic process.

Claims

The scope of the claims

[1] In a method of producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst,

At least a part of the aromatic compound contained in the reactor outlet effluent gas (reactor outlet gas) is withdrawn, and

In the reactor outlet effluent gas (reactor outlet gas), at least part of the olefin having 4 or more carbon atoms contained in the reactor is again brought into contact with the catalyst in the reactor. Len production method

[2] The method for producing propylene according to claim 1, wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

[3] The method for producing propylene according to claim 2, wherein the paraffins contain at least one of normal butane and isobutane.

[4] The propylene production method according to any one of claims 1 to 3, wherein the raw material supplied to the reactor contains butadiene.

[5] Claims: In any one of! To 4, the total amount of aromatic compounds contained in all raw materials supplied to the reactor is the sum of olefins having 4 or more carbon atoms contained in all the raw materials. A method for producing propylene, wherein the molar ratio is less than 0.05 with respect to the amount.

[6] In any one of claims 1 to 5, the amount of olefin having 4 or more carbon atoms to be supplied to the reactor is twice the number of moles of methanol to be fed to the reactor and the number of moles of dimethyl ether. The method for producing propylene, wherein the molar ratio is 0.2 or more and 10 or less with respect to the total.

[7] Claim: In any one of! To 6, the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in all raw materials fed to the reactor is 20% by volume or more. Propylene production method characterized by controlling to 80% by volume or less.

[8] In the method for producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following step (1) , (2) and (3A) Propylene production method.

Step (3A): At least a part of fluid (C) of fluid (A) in step (2) above has an aromatic compound concentration lower than that of fluid (C) !, fluid (D) and carbon number 4 is separated into a fluid (E) having a hydrocarbon concentration lower than that of the fluid (C), the fluid (D) is recycled to the reactor, and the fluid (E) is extracted from the process.

In a method for producing propylene by contacting a raw material containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), (2 ) And (3A), and a process for producing propylene.

Step (3A): A part (B) of the fluid (A) in the step (2) is extracted from the process, and the residue The fluid (C) has a lower aromatic compound concentration than the fluid (C)! / ヽ fluid (D) and the hydrocarbon concentration of 4 carbon atoms is lower than the fluid (C)! /, Fluid (E And the fluid (D) is recycled to the reactor, and the fluid (E) is withdrawn from the process.

[10] The olefin raw material having 4 or more carbon atoms, which is composed of two or more reaction parts connected in series, and is supplied to the reactor according to claim 8 or 9, of methanol and dimethyl ether At least one; and at least one of the recycled hydrocarbon-containing fluid (D) is divided and supplied to the first-stage reaction section and the second-stage and subsequent reaction sections. Propylene production method.

[11] A method for producing propylene according to any one of claims 8 to 10, wherein the fluid (B) is supplied to a steam cracking process and used as a cracker raw material.

[12] The method for producing propylene according to claim 11, wherein at least a part of the fluid (B) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.

[13] The process for producing propylene according to any one of claims 8 to 12, wherein the total concentration of the aromatic compounds contained in the fluid (B) is less than 5.0% by volume.

14. The propylene production method according to any one of claims 8 to 13, wherein the fluid (E) is mixed with a cracked gasoline fraction of a steam cracking process.

[15] The method for producing propylene according to any one of claims 8 to 14, wherein the total concentration of the hydrocarbon having 4 carbon atoms contained in the fluid (E) is less than 5% by weight.

[16] The power of any one of claims 8 to 15, wherein the number of carbon atoms contained in all raw materials supplied to the reactor is 4 by controlling the flow rates of the fluid (B) and the fluid (E). A method for producing propylene, characterized in that the total concentration (substrate concentration) of olefin, methanol and dimethyl ether is controlled to 20 vol% or more and 80 vol% or less.

[17] In a method for producing propylene by contacting a mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), A method for producing propylene characterized by comprising a process comprising (2) and (3B). Step (1): olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (I) recycled from step (3B), and at least one of methanol and dimethyl ether are supplied to the reactor, and the number of carbons at the outlet of the reactor Contact with the catalyst under reaction conditions such that the molar flow rate of 4 or more olefins is 20% or more and less than 90% of the molar flow rate of the olefins at the inlet of the reactor. Step of obtaining gas (reactor outlet gas) containing olefin, paraffins, aromatic compounds and water

Step (2): The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, a fluid rich in hydrocarbons having 4 or more carbon atoms (A), and a fluid rich in water Step (3B): In the step (2), the fluid (A) has an aromatic concentration lower than that of the fluid (A) !, and the fluid (G) and the hydrocarbon concentration of 4 carbon atoms are fluid ( A) lower! /, Separated into the fluid (F), and at least a part (I) of the fluid (G) is recycled to the reactor.

[18] In a method for producing propylene by contacting a mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), A method for producing propylene characterized by comprising a process comprising (2) and (3B).

[19] The two or more reaction parts according to claim 17 or 18, wherein the reactors are connected in series. The olefin raw material having 4 or more carbon atoms to be fed to the reactor; at least one of methanol and dimethyl ether; and at least one of the recycled hydrocarbon-containing fluid (I), A method for producing propylene, characterized in that it is divided into a reaction part for the second eye and a reaction part for the second and subsequent stages.

[20] The propylene production method according to any one of claims 17 to 19, wherein the fluid (H) is supplied to a steam cracking process and used as a cracker raw material.

[21] The method for producing propylene according to claim 20, wherein at least a part of the fluid (H) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.

Yes

[22] The method for producing propylene according to any one of claims 17 to 21, wherein the total concentration of aromatic compounds contained in the fluid (H) is less than 5.0% by volume.

23. The method for producing propylene according to any one of claims 17 to 22, wherein the fluid (F) is mixed with a cracked gasoline fraction of a steam cracking process.

[24] The method for producing propylene according to any one of claims 17 to 23, wherein the total concentration of the hydrocarbon having 4 carbon atoms contained in the fluid (F) is less than 5% by weight.

[25] The force of any one of claims 17 to 24, wherein the number of carbon atoms contained in all the raw materials supplied to the reactor is 4 or more by controlling the flow rates of the fluid (F) and the fluid (H). A method for producing propylene, characterized in that the total concentration (substrate concentration) of olefin, methanol, and dimethyl ether is controlled to 20% by volume or more and 80% by volume or less.

[26] The force according to any one of claims 8 to 25, wherein the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step and then distills to remove 2 carbon atoms. The following fluids rich in hydrocarbons and fluids rich in hydrocarbons having 3 or more carbon atoms are separated, and the fluids rich in hydrocarbons having 3 or more carbon atoms are enriched in hydrocarbons having 3 or more carbon atoms by distillation. A method for producing propylene, comprising a step of separating a fluid and a fluid rich in hydrocarbons having 4 or more carbon atoms.

[27] The force according to any one of claims 8 to 25, wherein the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, and then the number of carbon atoms by distillation. A hydrocarbon-rich fluid having 3 or less carbon atoms and a hydrocarbon-rich fluid having 4 or more carbon atoms are separated, and the hydrocarbon-rich fluid having 3 or less carbon atoms is separated by distillation into a hydrocarbon having 2 or less carbon atoms. A process for producing propylene, comprising a step of separating a fluid rich in water and a fluid rich in hydrocarbons having 3 carbon atoms.

[28] The power according to any one of claims 8 to 25, wherein, in the step (2), water is condensed and removed from the reactor outlet gas by a cooling and compression step, and then the number of carbon atoms is reduced by distillation. The fluid containing the following hydrocarbons and hydrocarbons having 3 carbon atoms and the fluid rich in hydrocarbons having 3 or more carbon atoms are separated, and the fluid rich in hydrocarbons having 3 or more carbon atoms is distilled to obtain 3 carbon atoms. A process for producing propylene, comprising a step of separating a fluid rich in hydrocarbons and a fluid rich in hydrocarbons having 4 or more carbon atoms.

[29] The power according to any one of claims 8 to 25, wherein the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, and then distills to remove 3 carbon atoms. The following hydrocarbon-rich fluid and hydrocarbon-rich fluid having 4 or more carbon atoms are separated, and the hydrocarbon-rich fluid having 3 or less carbon atoms is separated by distillation into hydrocarbons having 2 or less carbon atoms and A method for producing propylene, comprising a step of separating a fluid containing a hydrocarbon having 3 carbon atoms and a fluid rich in a hydrocarbon having 3 carbon atoms.

[30] The process for producing propylene according to any one of claims 8 to 29, wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

31. The method for producing propylene according to claim 30, wherein the paraffins contain at least one of normal butane and isobutane.

32. The method for producing propylene according to any one of claims 8 to 31, wherein the raw material supplied to the reactor contains butagen.

[33] The power of any one of claims 8 to 32, wherein the total amount of aromatic compounds contained in all raw materials supplied to the reactor is olefins having 4 or more carbon atoms contained in all the raw materials. A method for producing propylene, wherein the molar ratio is less than 0.05 with respect to the total amount.

[34] The force of any one of claims 8 to 33, wherein the amount of olefin having 4 or more carbon atoms fed to the reactor is twice the number of moles of methanol and dimethyl ether fed to the reactor. The molar ratio is 0.2 or more and 10 or less with respect to the total. A method for producing lopyrene.

[35] The power of any one of claims 8 to 34, comprising the olefin raw material power S having 4 or more carbon atoms fed to the reactor, and a hydrocarbon fluid having 4 carbon atoms obtained by a steam cracking process. A method for producing propylene, which is characterized.

[36] In a method for producing propylene by contacting a mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1C), A process for producing propylene characterized by comprising a process comprising (2C), (3C) and (4C).

[37] In a method for producing propylene by contacting a mixture containing olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1C), A process for producing propylene characterized by comprising a process comprising (2C), (3C) and (4C).

Step (1C): olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (Q) recycled from step (4C), and at least one of methanol and dimethyl ether are supplied to the reactor, and the reactor outlet The molar flow rate of olefins with 4 or more carbon atoms Contact with the catalyst under reaction conditions such that the molar flow rate of olefin is 20% or more and less than 90%. From the reactor outlet, propylene and other olefins, paraffins, aromatic compounds and water are contained. To obtain gas to be discharged (reactor outlet gas)

38. The liquid fluid (M) according to claim 36 or 37, wherein the concentration of the aromatic compound is lower than that in the liquid fluid (M) by distillation! /, The concentration of the fluid (R) and the hydrocarbon having 4 carbon atoms. Is separated into a fluid (S) lower than the liquid fluid (M).

39. The fluid (R) according to claim 38, wherein the fluid (R) is any force selected from the fluids (K), (L), (M), (P), and (Q), and one or more fluids. A method for producing propylene, which is returned to the distribution location.

[40] The force according to any one of claims 36 to 39, wherein the step (3C) comprises distilling the gas fluid (L) into a hydrocarbon-rich fluid having 2 or less carbon atoms and 3 or more carbon atoms by distillation. The hydrocarbon-rich fluid is separated into a hydrocarbon-rich fluid with a carbon number of 3 or more, and the hydrocarbon-rich fluid with a carbon number of 3 or more is distilled into a hydrocarbon-rich fluid with a carbon number of 3 and a hydrocarbon with a carbon number of 4 or more. A process for producing propylene, comprising a step of separating into a rich fluid (N).

[41] The force of any one of claims 36 to 39, wherein the step (3C) comprises distilling the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms and 4 or more carbon atoms. The hydrocarbon-rich fluid (N) is separated into a hydrocarbon-rich fluid having a carbon number of 3 or less, and a hydrocarbon-rich fluid having a carbon number of 2 or less and a fluid having a carbon number of 3 or less by distillation. A method for producing propylene, comprising a step of separating into a hydrocarbon-rich fluid.

[42] The force according to any one of claims 36 to 39, wherein the step (3C) includes a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms by distillation of the gas fluid (L). Fluid and charcoal A fluid rich in hydrocarbons having 3 or more carbon atoms is separated into a fluid rich in hydrocarbons having 3 or more carbon atoms, and a fluid rich in hydrocarbons having 3 or more carbon atoms is distilled, and a fluid rich in hydrocarbons having 3 or more carbon atoms and carbonized with 4 or more carbon atoms. A method for producing propylene, comprising a step of separating into a fluid (N) rich in hydrogen.

[43] The force according to any one of claims 36 to 39, wherein the step (3C) comprises distilling the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms and 4 or more carbon atoms. The hydrocarbon-rich fluid (N) is separated into a hydrocarbon-rich fluid (N), and a hydrocarbon-rich fluid containing 3 or less carbon atoms contains a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms by distillation. A method for producing propylene, comprising a step of separating the fluid into a fluid rich in hydrocarbons having 3 carbon atoms.

[44] The olefin raw material of 4 or more carbon atoms according to any one of claims 36 to 43, wherein the reactor comprises two or more reaction parts connected in series and is supplied to the reactor; methanol and dimethyl ether And at least one of the recycled hydrocarbon-containing fluid is divided and supplied to the first-stage reaction section and the second-stage and subsequent reaction sections. Propylene production method.

[45] The propylene production method according to any one of claims 36 to 44, wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

[46] The method for producing propylene according to claim 45, wherein the paraffins contain at least one of normal butane and isobutane.

[47] The method for producing propylene according to any one of claims 36 to 46, wherein the raw material supplied to the reactor contains butadiene.

[48] The power of any one of claims 36 to 47, wherein the total amount of aromatic compounds contained in all the raw materials fed to the reactor is the sum of olefins having 4 or more carbon atoms contained in all the raw materials. Propylene production method, characterized in that the molar ratio with respect to the amount is less than 0.05

[49] The method according to any one of claims 36 to 48, wherein at least one of the fluid (M) and the fluid (P) is supplied to a steam cracking process and used as a cracker raw material. Propylene production method. [50] The propylene according to claim 49, wherein at least a part of at least one of the fluid (M) and the fluid (P) is contacted with a hydrogenation catalyst and then supplied to a steam cracking process. Manufacturing method.

[51] The force according to any one of claims 36 to 50, wherein the total concentration of aromatic compounds contained in at least one of the fluid (M) and the fluid (P) is less than 5.0% by volume. And a method for producing propylene.

[52] The propylene production method according to any one of claims 36 to 51, wherein the fluid (M) is mixed with a cracked gasoline fraction of a steam cracking process.

53. The method for producing propylene according to any one of claims 36 to 52, wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (M) is less than 5% by weight.

[54] In any one of claims 36 to 53, by controlling the flow rates of the fluid (M) and the fluid (P), the number of carbon atoms contained in all the raw materials supplied to the reactor is 4 or less. A method for producing propylene, characterized in that the total concentration (substrate concentration) of the above olefin, methanol and dimethyl ether is controlled to 20 vol% or more and 80 vol% or less.

[55] The method for producing propylene according to any one of claims 38 to 54, wherein the fluid (R) is supplied to a steam cracking process and used as a cracker raw material.

[56] The method for producing propylene according to claim 55, wherein at least a part of the fluid (R) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.

[57] The method for producing propylene according to any one of claims 38 to 56, wherein the total concentration of the aromatic compounds contained in the fluid (R) is less than 5.0% by volume.

58. The method for producing propylene according to any one of claims 38 to 57, wherein the fluid (S) is mixed with a cracked gasoline fraction of a steam cracking process.

[59] The method for producing propylene according to any one of claims 38 to 58, wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (S) is less than 5% by weight.

[60] The force of any one of claims 38 to 59, wherein the fluid (P), fluid (R) and fluid

By controlling the flow rate of (S), the number of carbons contained in all raw materials supplied to the reactor A method for producing propylene, comprising controlling the total concentration (substrate concentration) of 4 or more olefins, methanol and dimethyl ether to 20 vol% or more and 80 vol% or less.

[61] The fluid according to any one of claims 38 to 60, wherein the fluid (R) is any force selected from the fluids (K), (L), (N), (P), and (Q), 1 or When returning to the location of two or more fluids, by controlling the return location of the fluid (R) and its flow rate, olefin and methanol having 4 or more carbon atoms contained in all the raw materials supplied to the reactor A method for producing propylene, characterized in that the total concentration (substrate concentration) of dimethyl ether is controlled to 20 vol% or more and 80 vol% or less.

[62] The power of any one of claims 36 to 61, wherein the quantity S of olefins having 4 or more carbon atoms fed to the reactor is 2; the number of moles of methanol fed to the reactor and the number of moles of dimethyl ether The method for producing propylene, characterized in that the molar ratio is 0.2 or more and 10 or less with respect to the total.

[63] The force according to any one of claims 36 to 62, comprising the olefin raw material power S having 4 or more carbon atoms fed to the reactor, and a hydrocarbon fluid having 4 carbon atoms obtained by a steam cracking process. A method for producing propylene, which is characterized.