JP5521264B2 - Propylene production method - Google Patents

Description

  The present invention relates to a method for producing propylene from a raw material mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether.

As a method for producing propylene, steam cracking of naphtha and ethane 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, 4 or more carbon atoms. Attention has also been focused on the catalytic cracking of olefins and the MTO process using methanol and / or dimethyl ether as raw materials. On the other hand, a method of producing a lower olefin using an olefin having 4 or more carbon atoms and an oxygen-containing compound such as methanol as raw materials is also known (Patent Document 1).
US Pat. No. 6,888,038

Conventionally, many proposals have been made as methods for producing propylene, most of which have been disclosed for reaction and purification, respectively. However, olefins having 4 or more carbon atoms and oxygen-containing compounds such as methanol are used as raw materials. As for the method, the reaction itself has been proposed, but the process including the purification system on the downstream side of the reactor has not been proposed.
Accordingly, a first object of the present invention is to provide a new and economical process for producing propylene by reacting an olefin having 4 or more carbon atoms with methanol and / or dimethyl ether.

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. However, by integrating the process of the present invention with the steam cracking process, ethylene and propylene can be obtained. It is possible to significantly change the ratio of. Furthermore, by integrating these two processes, it becomes possible to effectively use fluids that are not required in each other process, and therefore, a highly efficient process construction is expected due to the synergistic effect.
Therefore, the second object of the present invention is to provide a new and economical process that integrates this process and steam cracking.

  When the present inventors examined the reaction of obtaining propylene by reacting an olefin having 4 or more carbon atoms with methanol and / or dimethyl ether, the following knowledge was obtained.

  If the amount of olefin consumed by the reaction is too large, by-products of undesirable compounds such as aromatic compounds and paraffin will become prominent, while if the amount of olefin consumed is too small, the yield of propylene will be too low. . By appropriately setting reaction conditions such as temperature, pressure, partial pressure, and space velocity, and controlling the amount of olefin consumed within a specific range, propylene can be obtained with high selectivity and high yield. When the reaction is carried out under such conditions, the reactor outlet fluid contains a large amount of olefins having 4 or more carbon atoms that can serve as a reaction raw material, and therefore it is preferable to recycle these compounds into the reactor.

  On the other hand, in the reaction of an olefin having 4 or more carbon atoms with methanol and / or dimethyl ether, an aromatic compound and paraffin are also produced in a small amount and are contained in the reactor outlet fluid. In particular, when a raw material containing paraffin is used as the olefin raw material having 4 or more carbon atoms, the concentration of paraffin in the reactor outlet fluid increases. Since paraffins 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.

Further, when an aromatic compound is present in a recycled olefin fluid having 4 or more carbon atoms in a specific concentration or more, a reaction between the aromatic compound and an olefin having 4 or more carbon atoms, an aromatic compound and methanol, and / or Reaction with dimethyl ether becomes remarkable, and the supplied olefin having 4 or more carbon atoms, methanol and / or dimethyl ether are consumed more than necessary, which is not preferable.
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 promotes deterioration of the catalyst due to clogging of the catalyst pores. It is preferable that the aromatic compound present in the reactor outlet fluid is extracted from the system as much as possible to reduce the concentration of the aromatic compound 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.

Thus, the present inventors have found various problems in the method of producing propylene using olefins having 4 or more carbon atoms and methanol and / or dimethyl ether as raw materials, and by constructing a process that can solve these problems, It has been found that propylene can 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 on the basis of such findings, and the gist thereof is as follows .

[1 ] In a method for producing propylene by contacting a raw material containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1) and (2) And a process comprising (3A).
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (D) recycled from the step (3A), and methanol and / or dimethyl ether are supplied to the reactor, and the number of carbon atoms at the reactor outlet is 4 or more. The olefin is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor. Step (2) for obtaining a gas (reactor outlet gas) containing a kind, an aromatic compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, Step (3A) of separation into fluid (A) rich in hydrocarbons having 4 or more carbon atoms and fluid rich in water: Fluid (C) of at least part of fluid (A) in step (2) ) Is separated into a fluid (D) having a lower aromatic compound concentration than the fluid (C) and a fluid (E) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (C), and the fluid (D) Step 2 for recycling to a reactor and extracting the fluid (E) from the process [ 2 ] A raw material containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether is contacted in the reactor in the presence of a catalyst. A method for producing propylene, comprising a process comprising the following steps (1), (2) and (3A):
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (D) recycled from the step (3A), and methanol and / or dimethyl ether are supplied to the reactor, and the number of carbon atoms at the reactor outlet is 4 or more. The olefin is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor. Step (2) for obtaining a gas (reactor outlet gas) containing a kind, an aromatic compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, Step (3A) of separation into a fluid (A) rich in hydrocarbons having 4 or more carbon atoms and a fluid rich in water: A part (B) of the fluid (A) in the step (2) The remaining fluid (C) is separated into a fluid (D) having a lower aromatic compound concentration than the fluid (C) and a fluid (E) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (C). The fluid (D) is recycled to the reactor and the fluid (E) is withdrawn from the process.

[ 3 ] In [ 1 ] or [ 2 ], 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, containing recycled hydrocarbons Propylene characterized in that at least one of the fluid (D) and methanol and / or dimethyl ether is divided and supplied to the first-stage reaction section and the second-stage reaction section and thereafter. Production method.

[ 4 ] A process for producing propylene according to any one of [ 1 ] to [ 3 ], wherein the fluid (B) is supplied to a steam cracking process and used as a cracker raw material.

[ 5 ] The method for producing propylene according to [ 4 ], 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.

[ 6 ] The method for producing propylene according to any one of [ 1 ] to [ 5 ], wherein the total concentration of aromatic compounds contained in the fluid (B) is less than 5.0% by volume.

[ 7 ] A process for producing propylene according to any one of [ 1 ] to [ 6 ], wherein the fluid (E) is mixed with a cracked gasoline fraction of a steam cracking process.

[ 8 ] The method for producing propylene according to any one of [ 1 ] to [ 7 ], wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (E) is less than 5% by weight.

[ 9 ] In any one of [ 1 ] to [ 8 ], by controlling the flow rates of the fluid (B) and the fluid (E), the total number of carbon atoms contained in all raw materials supplied to the reactor is 4 or more. The total concentration (substrate concentration) of olefin, methanol and dimethyl ether is controlled to be 20 vol% or more and 80 vol% or less.

[ 10 ] In a method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1) and (2) And a process comprising (3B).
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (I) recycled from the step (3B), and methanol and / or dimethyl ether are supplied to the reactor, and the reactor has 4 or more carbon atoms at the outlet of the reactor. The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor, and propylene, other olefins, paraffins, aromas from the reactor outlet. Step (2) for obtaining a gas (reactor outlet gas) containing a group compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, 4 or more carbon atoms The step (3B) of separating the hydrocarbon-rich fluid (A) and the water-rich fluid into the fluid (A) in the step (2), the aromatic compound concentration from the fluid (A) A step of separating a low fluid (G) into a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than that of the fluid (A), and recycling at least a part (I) of the fluid (G) to the reactor.

[ 11 ] In a method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1) and (2) And a process comprising (3B).
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (I) recycled from the step (3B), and methanol and / or dimethyl ether are supplied to the reactor, and the reactor has 4 or more carbon atoms at the outlet of the reactor. The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor, and propylene, other olefins, paraffins, aroma Step (2) for obtaining a gas (reactor outlet gas) containing a group compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, 4 or more carbon atoms The step (3B) of separating the hydrocarbon-rich fluid (A) and the water-rich fluid into the fluid (A) in the step (2), the aromatic compound concentration from the fluid (A) The fluid (G) is separated into a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than that of the fluid (A), the fluid (F) is withdrawn from the process, and a part of the fluid (G) ( I) is recycled to the reactor and the remaining fluid (H) is withdrawn from the process

[ 12 ] In [ 10 ] or [ 11 ], the reactor is composed of 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, containing recycled hydrocarbons Propylene, characterized in that at least one of fluid (I) and methanol and / or dimethyl ether is divided and supplied to a first-stage reaction section and a second-stage reaction section or later. Production method.

[ 13 ] A method for producing propylene according to any one of [ 10 ] to [ 12 ], wherein the fluid (H) is supplied to a steam cracking process and used as a cracker raw material.

[ 14 ] The method for producing propylene according to [ 13 ], 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.

[ 15 ] The method for producing propylene according to any one of [ 10 ] to [ 14 ], wherein the total concentration of the aromatic compounds contained in the fluid (H) is less than 5.0% by volume.

[ 16 ] A process for producing propylene according to any one of [ 10 ] to [ 15 ], wherein the fluid (F) is mixed with a cracked gasoline fraction of a steam cracking process.
[ 17 ] The method for producing propylene according to any one of [ 10 ] to [ 16 ], wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (F) is less than 5% by weight.

[ 18 ] In any one of [ 10 ] to [ 17 ], 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 of olefin, methanol and dimethyl ether (substrate concentration) is controlled to 20 vol% or more and 80 vol% or less.

[ 19 ] In any one of [ 1 ] to [ 18 ], after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, the hydrocarbon having 2 or less carbon atoms is distilled. And a fluid rich in hydrocarbons having 3 or more carbon atoms. The fluid rich in hydrocarbons having 3 or more carbon atoms is separated into a fluid rich in hydrocarbons and carbon numbers having 3 carbon atoms by distillation. A method for producing propylene, comprising a step of separating into a fluid rich in four or more hydrocarbons.

[ 20 ] In any one of [ 1 ] to [ 18 ], after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, the hydrocarbon having 3 or less carbon atoms is distilled. And a fluid rich in hydrocarbons having 4 or more carbon atoms, 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 carbon by distillation. A method for producing propylene, comprising a step of separating the fluid into a hydrocarbon-rich fluid of formula (3).

[ 21 ] In any one of [ 1 ] to [ 18 ], after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, the hydrocarbon having 2 or less carbon atoms is distilled. And a fluid containing a hydrocarbon having 3 or more carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms, and the fluid rich in hydrocarbons having 3 or more carbon atoms is converted into a hydrocarbon having 3 carbon atoms by distillation. A method for producing propylene, comprising a step of separating a rich fluid and a fluid rich in hydrocarbons having 4 or more carbon atoms.

[ 22 ] In any one of [ 1 ] to [ 18 ], after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, the hydrocarbon having 3 or less carbon atoms is distilled. Is separated into a fluid rich in hydrocarbons and a fluid rich in hydrocarbons having 4 or more carbon atoms, and the fluid rich in hydrocarbons having 3 or less carbon atoms is separated by distillation into hydrocarbons having 2 or less carbon atoms and carbonization with 3 carbon atoms. A method for producing propylene, comprising a step of separating a fluid containing hydrogen and a fluid rich in hydrocarbons having 3 carbon atoms.

[ 23 ] The method for producing propylene according to any one of [ 1 ] to [ 22 ], wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

[ 24 ] The method for producing propylene according to [ 23 ], wherein the paraffins contain normal butane and / or isobutane.

[ 25 ] The process for producing propylene according to any one of [ 1 ] to [ 24 ], wherein the raw material supplied to the reactor contains butadiene.

[ 26 ] In any one of [ 1 ] to [ 25 ], the total amount of aromatic compounds contained in all raw materials supplied to the reactor is the total amount of olefins having 4 or more carbon atoms contained in all the raw materials. The propylene production method, wherein the molar ratio is less than 0.05.

[ 27 ] In any one of [ 1 ] to [ 26 ], the amount of the olefin having 4 or more carbon atoms supplied to the reactor is twice the number of moles of methanol and dimethyl ether fed to the reactor. The 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.

[ 28 ] In any one of [ 1 ] to [ 27 ], the olefin raw material having 4 or more carbon atoms to be supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained by a steam cracking process. Propylene production method.

[ 29 ] In a method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1C), (2C) , (3C) and (4C).
Step (1C): Olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (Q) recycled from step (4C), and methanol and / or dimethyl ether are supplied to the reactor, and 4 or more carbon atoms at the outlet of the reactor The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor, and propylene, other olefins, paraffins from the reactor outlet Step of obtaining a gas (reactor outlet gas) containing an aromatic compound and water Step (2C): Cooling the reactor outlet gas from the step (1C), gas fluid (L), having 4 or more carbon atoms Separating into a liquid fluid (M) rich in hydrocarbons and containing an aromatic compound, and a fluid rich in water Step (3C): The gas fluid (L) in the step (2C) Separating into a hydrocarbon-rich fluid having a prime number of 3 or less and a hydrocarbon-rich fluid having a carbon number of 4 or more (N) Step (4C): At least part of the fluid (Q) of the fluid (N) Recycling process to reactor

[ 30 ] In the method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1C), (2C) , (3C) and (4C).
Step (1C): Olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (Q) recycled from step (4C), and methanol and / or dimethyl ether are supplied to the reactor, and 4 or more carbon atoms at the outlet of the reactor The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the reactor inlet, and propylene, other olefins and paraffins are fed from the reactor outlet. Step of obtaining a gas (reactor outlet gas) containing an aromatic compound and water Step (2C): The reactor outlet gas from the step (1C) is cooled, and the cooled gas fluid (K) is compressed. Separating into a gas fluid (L), a liquid fluid (M) rich in hydrocarbons having 4 or more carbon atoms and containing an aromatic compound, and a fluid rich in water Step (3C): Step of separating the gas fluid (L) in (2C) into a hydrocarbon-rich fluid having 3 or less carbon atoms and a fluid (N) rich in hydrocarbon having 4 or more carbon atoms Step (4C): the fluid (N A part of (P) is extracted from the process and the remaining fluid (Q) is recycled to the reactor.

In [ 31 ] [ 29 ] or [ 30 ], the liquid fluid (M) is subjected to distillation so that the concentration of the aromatic compound and the hydrocarbon having 4 carbon atoms is lower than that in the liquid fluid (M). A method for producing propylene, characterized in that separation is made into a fluid (S) lower than the liquid fluid (M).

[ 32 ] In [ 31 ], the fluid (R) is circulated through any one or more fluids selected from the fluids (K), (L), (M), (P), and (Q). A method for producing propylene, which is returned to the location.

[ 33 ] In any one of [ 29 ] to [ 32 ], in the step (3C), the gas fluid (L) is obtained by distilling the gas fluid (L) into a hydrocarbon-rich fluid having 2 or less carbon atoms and 3 or more carbon atoms. It is separated into a fluid rich in hydrocarbons, and a fluid rich in hydrocarbons having 3 or more carbon atoms is distilled to enrich a fluid rich in hydrocarbons having 3 or more carbon atoms and rich in hydrocarbons having 4 or more carbon atoms. A method for producing propylene, comprising a step of separating the fluid (N).

[ 34 ] In any one of [ 29 ] to [ 32 ], 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 4 or more carbon atoms. The hydrocarbon-rich fluid (N) is separated into a hydrocarbon-rich fluid and 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 hydrocarbon having a carbon number of 3 by distillation. A process for producing propylene, comprising the step of separating into a fluid rich in water.

[ 35 ] In any one of [ 29 ] to [ 32 ], the step (3C) includes a hydrocarbon having 3 or less carbon atoms in a hydrocarbon having 2 or less carbon atoms by distillation of the gas fluid (L). The fluid is separated into a fluid rich in hydrocarbons having 3 or more carbon atoms, and further, a fluid rich in hydrocarbons having 3 or more carbon atoms is distilled to obtain a fluid rich in hydrocarbons having 3 carbon atoms and 4 carbon atoms. A method for producing propylene, comprising a step of separating the hydrocarbon-rich fluid (N).

[ 36 ] In any one of [ 29 ] to [ 32 ], 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 4 or more carbon atoms. The fluid rich in hydrocarbon (N) is separated into 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 is obtained by distillation. A method for producing propylene, comprising a step of separating into a fluid rich in hydrocarbon having 3 carbon atoms.

[ 37 ] In any one of [ 29 ] to [ 36 ], 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 is recycled. Propylene characterized in that at least one of a hydrocarbon-containing fluid and methanol and / or dimethyl ether is divided and supplied to a first-stage reaction section and a second-stage reaction section or later. Production method.

[ 38 ] The method for producing propylene according to any one of [ 29 ] to [ 37 ], wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.

[ 39 ] The method for producing propylene according to [ 38 ], wherein the paraffins contain normal butane and / or isobutane.

[ 40 ] The process for producing propylene according to any one of [ 29 ] to [ 39 ], wherein the raw material supplied to the reactor contains butadiene.

[ 41 ] In any one of [ 29 ] to [ 40 ], the total amount of aromatic compounds contained in all raw materials supplied to the reactor is the total amount of olefins having 4 or more carbon atoms contained in all the raw materials. The propylene production method, wherein the molar ratio is less than 0.05.

[ 42 ] The method for producing propylene according to any one of [ 29 ] to [ 41 ], wherein the fluid (M) and / or the fluid (P) is supplied to a steam cracking process and used as a cracker raw material. .

[ 43 ] The production of propylene according to [ 42 ], wherein at least a part of the fluid (M) and / or the fluid (P) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process. Method.

[ 44 ] In any one of [ 29 ] to [ 43 ], the total concentration of aromatic compounds contained in the fluid (M) and / or the fluid (P) is less than 5.0% by volume. Propylene production method.

[ 45 ] A process for producing propylene according to any one of [ 29 ] to [ 44 ], wherein the fluid (M) is mixed with a cracked gasoline fraction of a steam cracking process.

[ 46 ] The method for producing propylene according to any one of [ 29 ] to [ 45 ], wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (M) is less than 5% by weight.

[ 47 ] In any one of [ 29 ] to [ 46 ], by controlling the flow rate 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 more. The total concentration (substrate concentration) of olefin, methanol and dimethyl ether is controlled to be 20 vol% or more and 80 vol% or less.

[ 48 ] The method for producing propylene according to any one of [ 29 ] to [ 47 ], wherein the fluid (R) is supplied to a steam cracking process and used as a cracker raw material.

[ 49 ] The method for producing propylene according to [ 48 ], 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.

[ 50 ] The method for producing propylene according to any one of [ 31 ] to [ 49 ], wherein the total concentration of aromatic compounds contained in the fluid (R) is less than 5.0% by volume.

[ 51 ] The method for producing propylene according to any one of [ 31 ] to [ 50 ], wherein the fluid (S) is mixed with a cracked gasoline fraction of a steam cracking process.

[ 52 ] The method for producing propylene according to any one of [ 31 ] to [ 51 ], wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (S) is less than 5% by weight.

[ 53 ] In any one of [ 31 ] to [ 52 ], the flow rate of the fluid (P), the fluid (R), and the fluid (S) is controlled so as to be included in all raw materials supplied to the reactor. A method for producing propylene, characterized in that the total concentration (substrate concentration) of an olefin having 4 or more carbon atoms, methanol and dimethyl ether is controlled to 20 vol% or more and 80 vol% or less.

[ 54 ] In any one of [ 31 ] to [ 53 ], the fluid (R) is any one selected from the fluids (K), (L), (N), (P), and (Q). Alternatively, when returning to the location of two or more fluids, by controlling the return location of the fluid (R) and its flow rate, the olefin having 4 or more carbon atoms and methanol and dimethyl ether contained in all the raw materials supplied to the reactor A method for producing propylene, characterized in that the total concentration (substrate concentration) is controlled to 20 vol% or more and 80 vol% or less.

[ 55 ] In any one of [ 29 ] to [ 54 ], the amount of the olefin having 4 or more carbon atoms supplied to the reactor is twice the number of moles of methanol and dimethyl ether supplied to the reactor. The 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.

[ 56 ] In any one of [ 29 ] to [ 55 ], the olefin raw material having 4 or more carbon atoms supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained by a steam cracking process. Propylene production method.

According to the present invention, in a method for producing propylene by reacting an olefin raw material having 4 or more carbon atoms with methanol and / or dimethyl ether in the presence of a catalyst, the raw material is highly utilized to suppress catalyst deterioration. However, it is possible to produce propylene with a high yield.
Also, the method of the present invention can be integrated with a steam cracking process to provide an economical process.

Below, the typical aspect for implementing this invention is demonstrated concretely, However, This invention is not limited to the following aspects, unless the summary is exceeded.
The method for producing propylene of the present invention is a method for producing propylene by bringing a raw material containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether into contact with each other in the presence of a catalyst in the reactor outlet gas. At least a part of the aromatic compound contained in the reactor, and at least a part of the olefin having 4 or more carbon atoms contained in the reactor outlet gas is again brought into contact with the catalyst in the reactor. It is.

  More specifically, embodiments include the following steps, but as long as the purpose of solving the problems of the present invention is followed, the present invention does not exclude the presence of steps other than the following steps. Instead, other steps may exist before and after the following three steps or four steps, and other steps may exist between the steps.

First embodiment: Step (1), step (2) and step (3A) described above
Second embodiment: Step (1), step (2) and step (3B) described above
Third Embodiment: Step (1C), Step (2C), Step (3C) and Step (3D) described above

  In the present invention, “rich” means that the purity of the target product is 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, and further preferably 95 mol% or more. . For example, the “fluid rich in hydrocarbon having 4 or more carbon atoms (N)” means “hydrocarbon having 4 or more carbon atoms” in an amount of 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more. More preferably, the fluid contains 95 mol% or more.

[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 catalysts such as those obtained by impregnating and supporting an acid such as sulfuric acid and phosphoric acid on a support; acidic ion exchange resins; zeolites; aluminum phosphates; and mesoporous silica alumina such as Al-MCM41.

  Among these solid acid catalysts, those having a molecular sieving effect are preferable, and those having a low acid strength are preferable.

Among the solid acid catalysts, the structures of zeolites and aluminum phosphates having a molecular sieving effect are represented by codes defined by the International Zeolite Association (IZA), 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. It is done. Among them, a catalyst having a catalyst framework density of 18.0 T / nm ³ or less is preferable, and as such, preferably, MFI, MEL, MOR, MWW, FAU, BEA, CHA, more 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 (atoms other than oxygen among the atoms constituting the skeleton of the zeolite) present per unit volume (1 nm ³ ) of the zeolite. This value is determined by the structure of the zeolite.

More preferably, the solid acid catalyst 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 0.1 to 0.00. Crystalline aluminosilicates, metallosilicates, crystalline aluminum phosphates and the like that are 5 g / ml are preferred. In addition, the pore diameter mentioned here indicates a crystallographic channel diameter (Crystallographic free diameter of the channels) defined by International Zeolite Association (IZA). When the diameter is a pore and the shape of the pore is an ellipse, the short diameter is indicated.

Among aluminosilicates, those having a SiO ₂ / Al ₂ O ₃ molar ratio of 10 or more are preferred. If the SiO ₂ / Al ₂ O ₃ molar ratio is too low, the durability of the catalyst is lowered, which is not preferable. The upper limit of the molar ratio of SiO ₂ / Al ₂ O ₃ is usually 10,000 or less. If the molar ratio of SiO ₂ / Al ₂ O ₃ is too high, the catalytic activity is lowered, which is not preferable. The molar ratio can be determined by a conventional method such as fluorescent X-ray or chemical analysis.
The aluminum content in the catalyst can be controlled by the amount of raw material charged during catalyst preparation, and Al can be reduced by steaming after the preparation. Further, a part of Al may be replaced with other elements such as boron and gallium, and it is particularly preferable to substitute with boron.

  These catalysts may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  In the present invention, the above-mentioned catalytically active components may be used as they are in the reaction as a catalyst, or they are granulated / molded using a substance or binder inactive to the reaction, or mixed with these. You may use for reaction. Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica gel, quartz, and a mixture thereof.

  The catalyst composition described above is a composition of only a catalytically active component that does not contain a substance inactive to these reactions, a binder, and the like. Thus, when the catalyst according to the present invention includes a substance or binder inactive to these reactions, the catalyst active component and the substance inactive to these reactions are combined with the catalyst. In the case where a substance inactive to these reactions, a binder, or the like is not included, it is referred to as a catalyst with only catalytically active components.

  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 μm to 500 μm as the average particle diameter. If the particle size of the catalyst is too large, the surface area showing 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 diameter can be determined by SEM observation or the like.

The method for preparing the catalyst used in the present invention is not particularly limited, and the catalyst can be prepared by a known method generally called hydrothermal synthesis. It is also possible to change the composition after the hydrothermal synthesis by modification such as ion exchange, dealumination treatment, impregnation or loading.
The catalyst used in the present invention may be any catalyst as long as it has the above physical properties or composition when subjected to the reaction, and may be prepared by any method.

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

<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, those produced from petroleum feedstock by catalytic cracking or steam cracking (BB fraction, C4 raffinate-1, C4 raffinate-2, etc.), hydrogen / CO mixed gas obtained by coal gasification as raw material Obtained by performing FT (Fischer-Tropsch) synthesis, obtained by oligomerization reaction including ethylene dimerization, obtained by dehydrogenation or oxidative dehydrogenation of paraffins having 4 or more carbon atoms, MTO 4 or more carbon atoms, particularly 4 carbon atoms, obtained by various known methods such as those obtained by reaction, those obtained by dehydration reaction of alcohol, or those obtained by hydrogenation reaction of diene compounds having 4 or more carbon atoms. -10 olefins can be used arbitrarily. At this time, the number of carbons resulting from each production method It may be used as it is more than the state in which compounds other than olefins are mixed optionally may be used purified olefins.

Among these, when an olefin raw material containing paraffins having 4 or more carbon atoms is used, the reaction temperature can be easily controlled because paraffin serves as a dilution gas, and paraffin-containing raw materials are available at low cost. It is preferable because there are many cases. More preferred is an olefin raw material containing normal butane and / or isobutane.
These preferable raw materials include the above-mentioned BB fraction, C4 raffinate-1 and C4 raffinate-2.
These raw materials usually contain butadiene. Since butadiene is easily converted into an aromatic compound by reaction, it is very important to extract at least a part of the produced aromatic compound without recycling 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 is brought into contact with a hydrogenation catalyst to lower the butadiene concentration as a raw material.

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

[Reaction operations / conditions: steps (1) and (1C) in the first to third embodiments]
Hereinafter, the operation and conditions of the propylene production reaction of the present invention using the above-described catalyst and reaction raw materials will be described.

<Reactor>
In the present invention, the reaction of an olefin having 4 or more carbon atoms with methanol and / or dimethyl ether is a gas phase reaction. Although there is no restriction | limiting in particular in the form of this gas phase reactor, Usually, it selects from a continuous type fixed bed reactor and a fluidized bed reactor. A fixed bed reactor is preferred.

  In addition, when packing the above-mentioned catalyst in a fixed bed reactor, in order to suppress the temperature distribution of the catalyst layer to be small, particulates inert to the reaction such as quartz sand, alumina, silica, silica-alumina, etc. And may be mixed and filled. In this case, there is no particular limitation on the amount of granular material inactive 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.

Further, the reactor may be composed of two or more reaction parts 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.
Further, the reaction substrate (reaction raw material) may be divided and supplied for the purpose of dispersing heat generation. Preferably, methanol and / or dimethyl ether are divided and supplied to the first-stage reaction section (reactor or reaction chamber) and the second-stage and subsequent reaction sections (reactor or reaction chamber).

Under the reaction conditions used in the present invention, the catalyst has little coking and the rate of catalyst deterioration is slow, but when performing continuous operation for more than one year, it is necessary to regenerate the catalyst during operation.
For example, when selecting a fixed bed reactor, it is desirable to install at least two reactors in parallel and operate while switching 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 regeneration operation of the catalyst include a method of regenerating the catalyst deteriorated by coking by treating it with nitrogen gas or water vapor containing oxygen. The regeneration operation in the fixed bed reactor is preferably performed by removing volatile organic compounds adhering to the catalyst with nitrogen gas, then burning and removing the coke with nitrogen gas containing a low concentration of oxygen, and then nitrogen gas. The method of removing the molecular oxygen contained in a catalyst layer by processing by is mentioned.

<Concentration ratio of olefin and methanol and / or dimethyl ether supplied to the reactor>
In the present invention, the amount of the olefin having 4 or more carbon atoms supplied to the reactor is 0.2 in terms of a molar ratio with respect to the sum of the number of moles of methanol supplied to the reactor and twice the number of moles of dimethyl ether. Above, preferably 0.5 or more, 10 or less, preferably 5 or less.
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 0. .5 to 5 times.
If this supply concentration ratio is too low or too high, the reaction will be slow, which is not preferable. In particular, if this supply concentration ratio is too low, the consumption of olefin as a raw material will decrease, which is not preferable.

Here, the supply concentration ratio can be known by quantifying the composition of each fluid supplied to the reactor or the fluid after mixing by a general analytical method such as gas chromatography.
When the olefin having 4 or more carbon atoms and methanol and / or dimethyl ether are supplied to the reactor, they may be supplied separately, or may be supplied after mixing a part or all of them in advance.

<Substrate concentration supplied to the reactor>
In the present invention, the total concentration (substrate concentration) of the olefin having 4 or more carbon atoms, methanol and dimethyl ether in all the feeds supplied to the reactor is preferably 20% by volume to 80% by volume, more preferably 30% by volume. % To 70% by volume.
Here, the substrate concentration can be known by quantifying the composition of each fluid supplied to the reactor or the fluid after mixing by a general analytical technique such as gas chromatography.

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 further, 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.

<Concentration of impurities in the gas supplied to the 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, which will be described later. The concentration is preferably 2.0% by volume or less. If the concentration of butadiene in the raw material is high, the production of aromatic compounds is increased, and deterioration due to catalyst coking is accelerated, which is not preferable.

Here, the butadiene concentration can be known by quantifying the composition of each fluid supplied to the reactor or the fluid after mixing by a general analytical method such as gas chromatography.
Examples of the 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.

In addition, the hydrocarbon-containing fluid described later recycled to the reactor may contain aromatic compounds, but the total amount of aromatic compounds contained in all raw materials supplied to the reactor is It is preferable that the molar ratio is less than 0.05 with respect to the total amount of olefins having 4 or more carbon atoms contained in all the raw materials supplied to. When the concentration of the aromatic compound in the raw material is high, the reaction between the aromatic compound and the olefin having 4 or more carbon atoms or the reaction between the aromatic compound and methanol and / or dimethyl ether becomes remarkable in the reactor, which is more than necessary. This is not preferable because olefins having 4 or more carbon atoms, methanol and / or dimethyl ether are consumed.
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 that the aromatic compound present in the reactor outlet fluid is extracted from the system as much as possible to reduce the concentration of the aromatic compound in the fluid recycled to the reactor.

Here, the ratio of the total amount of the aromatic compound and the total amount of the olefin having 4 or more carbon atoms is determined by general analysis such as gas chromatography of the composition of each fluid supplied to the reactor or the fluid after mixing. It can be known by quantifying with a technique.
Examples of the method for reducing the concentration of the aromatic compound in the raw material include a separation method by distillation.

<Dilution gas>
In the reactor, in addition to olefins having 4 or more carbon atoms and methanol and / or dimethyl ether, paraffins, aromatics, water vapor, carbon dioxide, carbon monoxide, nitrogen, argon, helium, and mixtures thereof are used. A gas inert to the reaction can be present. Of these dilution gases, paraffins and aromatics may react slightly depending on the reaction conditions, but are defined as dilution gases because the reaction amount is small.
As such a dilution gas, impurities contained in the reaction raw material may be used as they are, or a separately prepared dilution gas may 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 for the present invention are paraffins having 4 or more carbon atoms, more preferably normal butane and / or isobutane. These paraffins are advantageous in that control of the reaction temperature is facilitated because they can be used in olefin raw materials and are relatively large heat capacities.

<Space velocity>
The space velocity mentioned here is the flow rate of the olefin having 4 or more carbon atoms, which is a reaction raw material per weight of the catalyst (catalytic active component). Here, the weight of the catalyst is an amount used for granulation / molding of the catalyst. This is the weight of the catalytically active component that does not contain the active component or binder. The flow rate is a flow rate (weight / hour) of an olefin having 4 or more carbon atoms.

The space velocity is preferably between 0.1 Hr ⁻¹ and 500 Hr ⁻¹ , and more preferably between 1.0 Hr ⁻¹ and 100 Hr ⁻¹ . If the space velocity is too high, the conversion of the raw material olefin and methanol and / or dimethyl ether is low, and sufficient propylene selectivity cannot be obtained. On the other hand, if the space velocity is too low, the amount of catalyst necessary to obtain a certain production amount increases, the reactor becomes too large, and undesirable by-products such as aromatic compounds and paraffin are produced, and propylene selection is performed. This is not preferable because the rate decreases.

<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. or lower. If the reaction temperature is too low, the reaction rate tends to be low, a large amount of unreacted raw material 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.

<Reaction pressure>
The upper limit of the reaction pressure is usually 2 MPa (absolute pressure, the same applies hereinafter), preferably 1 MPa or less, and more preferably 0.7 MPa or less. The lower limit of the reaction pressure is not particularly limited, but is usually 1 kPa or more, preferably 50 kPa or more. If the reaction pressure is too high, the amount of undesired 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.

<Consumption of raw materials by reaction>
The sum 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%.
If the consumption of methanol and dimethyl ether in the reactor is small and the amount of methanol and dimethyl ether at the reactor outlet is too large, it becomes difficult to purify the product olefin.
As a method for increasing the consumption of methanol and dimethyl ether, a method of increasing the reaction temperature or decreasing the space velocity can be mentioned.

In the present invention, the molar flow rate of the olefin having 4 or more carbon atoms at the outlet of the reactor is preferably 20% or more and less than 90% with respect to the molar flow rate of the olefin having 4 or more carbon atoms supplied to the reactor. To do. The molar flow rate ratio is more preferably 20% or more and less than 70%, and further 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 olefin 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, undesirable compounds such as paraffin and aromatic compounds are by-produced and the yield of propylene is lowered, which is not preferable.
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, space velocity, and the like.

  Here, the flow rate of methanol, dimethyl ether and olefin having 4 or more carbon atoms supplied to the reactor is determined by a general analytical method such as gas chromatography for the composition of each fluid supplied to the reactor or the fluid after mixing. The flow rate of each fluid can be determined by measuring the flow rate of methanol and dimethyl ether at the reactor outlet and the flow rate of olefins having 4 or more carbon atoms. It can be known by quantifying with a technique and measuring or calculating the flow rate of the reactor outlet fluid.

<Reaction product>
As the reactor outlet gas (reactor effluent), a mixed gas containing 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 an olefin having 4 or more carbon atoms. Depending on the reaction conditions, methanol and / or dimethyl ether may be included, but it is preferable to carry out the reaction under such reaction conditions that methanol and / or dimethyl ether does not remain. Thereby, separation of the reaction product and the unreacted raw material becomes easy.
By-products include ethylene, olefins having 4 or more carbon atoms, paraffins, aromatic compounds, and water.

[Separation process]
{Separation step in the first and second embodiments}
<Separation of hydrocarbons having 3 or less carbon atoms and water: Step (2)>
In the first and second embodiments, the reactor outlet gas is converted into a hydrocarbon-rich fluid having 3 or less carbon atoms and a hydrocarbon having 4 or more carbon atoms by a general separation process such as cooling, compression and distillation. It is separated into a rich fluid (A) and a fluid rich in water.

  As a first aspect of the general separation process of the above reactor outlet gas, after condensing and removing moisture by the cooling and compression process, a 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 having 3 or more carbon atoms is distilled by distillation of a fluid rich in hydrocarbons having 3 or more carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms (A) A method including a step of separating into two is applied.

  Further, as a second aspect of the general separation process of the reactor outlet gas described above, after condensing and removing moisture by the cooling and compression processes, a hydrocarbon-rich fluid having 3 or less carbon atoms and 4 carbon atoms by distillation. The above-mentioned hydrocarbon-rich fluid (A) is separated, and a fluid rich in hydrocarbons having 3 or less carbon atoms is distilled to enrich a fluid rich in hydrocarbons having 2 or less carbon atoms and rich in hydrocarbons having 3 carbon atoms. A method including a step of separating into a fluid is applied.

  In addition, as a third aspect of the general separation process of the reactor outlet gas described above, after condensing and removing moisture by the cooling and compression processes, hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms are obtained by distillation. And a fluid rich in hydrocarbons having 3 or more carbon atoms, and a fluid rich in hydrocarbons having 3 or more carbon atoms by distillation, and a fluid rich in hydrocarbons having 3 carbon atoms and carbonization having 4 or more carbon atoms. A method including a step of separating into a fluid (A) rich in hydrogen is applied.

  Further, as a fourth aspect of the general separation process of the reactor outlet gas described above, a water rich in hydrocarbon having 3 or less carbon atoms and 4 carbon atoms by distillation after condensing and removing water by cooling and compression processes. The above fluid rich in hydrocarbon (A) is separated, and a fluid rich in hydrocarbons having 3 or less carbon atoms is distilled to produce a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms and carbon number. A method comprising the step of separating into 3 hydrocarbon rich fluids is applied.

In the first to fourth aspects of the general separation process of the reactor outlet gas described above, it is preferable to perform treatments such as quenching, alkali washing, and dehydration 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 quenching process. When the reactor outlet gas contains an acidic gas such as carbon dioxide, at least a part of the acidic gas is removed by alkali cleaning.
Separation of water is possible mainly by condensation through compression and cooling. The remaining water is preferably removed with an adsorbent such as molecular sieve. The water removed by condensation and / or adsorption may be used for a wastewater treatment process such as activated sludge, but can also be used for process water or the like.
When the process of the present invention (hereinafter sometimes referred to as “the present process”) is in the vicinity of the steam cracking process, the water recovered from the reactor outlet gas is preferably utilized as a steam source for the cracker. Moreover, you may recycle to the reactor of this process and use it as dilution gas.

  In addition, it is preferable that hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms obtained from the outlet gas of the reactor obtain high-purity ethylene and propylene, respectively, by a purification process such as distillation. 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.

  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, and ethylene can be produced by, for example, ethylene oxide, ethylene glycol, For the production of ethanolamine, glycol ether, etc., for the production of vinyl chloride monomer, 1,1,1-trichloroethane, vinyl chloride resin, vinylidene chloride by chlorination, and for the production of α-olefin, low density or high by polymerization of ethylene It can be used to produce high density polyethylene and ethylbenzene by ethylation of benzene.

  Polyethylene terephthalate can be produced from ethylene glycol produced from ethylene as a raw material, and higher alcohol is obtained by oxo reaction and subsequent hydrogenation reaction using α-olefin as raw material, styrene monomer and ABS resin as raw material from ethylbenzene. Etc. can be manufactured. Also, vinyl acetate can be produced by reaction with acetic acid, and acetaldehyde and its derivative ethyl acetate can be produced by Wacker reaction.

  Propylene is produced by polymerization of propylene, for example, for the production of acrylonitrile by ammoxidation, for the production of acrolein, acrylic acid and acrylate by selective oxidation, for the production of oxo alcohols such as normal butyl alcohol and 2-ethylhexanol by oxo reaction. Can be applied to the production of polypropylene and the production of propylene oxide and propylene glycol by the selective oxidation of propylene. Further, acetone can be produced by Wacker reaction, and methyl isobutyl ketone can be produced from acetone. Acetone cyanohydrin can also be produced from acetone, which is ultimately converted to methyl methacrylate. Isopropyl alcohol can also be produced by propylene hydration. In addition, phenol, bisphenol A, and polycarbonate resin can be produced using a cumene produced by alkylating benzene as a raw material.

In addition, the fluid containing the hydrocarbon having 2 or less carbon atoms and the hydrocarbon having 3 carbon atoms obtained in the third and fourth aspects of the general separation step of the reactor outlet gas is other than this process. It is preferable to supply to the production process of ethylene and propylene and purify them. Other processes for producing ethylene and propylene include steam cracking processes such as naphtha and ethane. This can significantly reduce the capital investment of this process.
On the other hand, when 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 aspect or the second aspect of a general gas separation step.

{Separation step in the third aspect}
<Separation of gas component, liquid component and water: steps (2C), (3C)>
In the third embodiment, the reactor outlet gas is cooled, and the gas fluid (K) after the cooling is compressed by gas fluid (L), a liquid fluid rich in hydrocarbons having 4 or more carbon atoms and containing an aromatic compound ( M) and a water-rich fluid (step (2C)), and then the gas fluid (L) is separated by a general separation step such as distillation and a hydrocarbon-rich fluid having 3 or less carbon atoms and carbon. Separated into a hydrocarbon-rich fluid (N) of several 4 or more (step (3C)).

  In the step (2C), the reactor outlet gas is usually at a temperature of about 300 to 600 ° C., but the reactor outlet gas is cooled to about 20 to 200 ° C. This cooling is usually performed in a heat exchanger, but may be performed directly by mixing with a fluid having a temperature lower than that of the gas. The cooled fluid (K) is compressed by using a compressor, a knockout drum or an oil / water separator, etc., and is compressed into a gas fluid (L) and a liquid fluid rich in hydrocarbons having 4 or more carbon atoms and containing an aromatic compound. (M) 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 a plurality of fluids supplied to the reactor.

  The gas fluid (L) separated in this step (2C) contains hydrocarbons, and in step (3C), a fluid rich in hydrocarbons having 3 or less carbon atoms by a general separation step such as distillation. And a fluid (N) rich in hydrocarbons having 4 or more carbon atoms.

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

  As a second aspect of the general separation step of the fluid (L), separation is performed by distillation 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. And a method including a step of separating a fluid rich in hydrocarbons having 3 or less carbon atoms into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms by distillation. .

  As a third aspect of the general separation step of the fluid (L), a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms and rich in hydrocarbons having 3 or more carbon atoms are obtained by distillation. And separating the fluid rich in hydrocarbons having 3 or more carbon atoms into a fluid rich in hydrocarbons having 3 carbon atoms and a fluid (N) rich in hydrocarbons having 4 or more carbon atoms by distillation. The method including is applied.

  As a fourth aspect of the general separation step of the fluid (L), separation is performed by distillation 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. And separating a fluid rich in hydrocarbons having 3 or less carbon atoms into a fluid containing hydrocarbons having 2 or less carbon atoms, a hydrocarbon containing 3 carbon atoms, and a fluid rich in hydrocarbons having 3 carbon atoms by distillation. The method including is applied.

In the above-mentioned process, it is preferable to perform a treatment such as quenching, 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 quenching process. When the reactor outlet gas contains an acidic gas such as carbon dioxide, at least a part of the acidic gas is removed by alkali cleaning.
Separation of water is possible mainly by condensation through compression and cooling. The remaining water is preferably removed with an adsorbent such as molecular sieve. The water removed by condensation and / or adsorption may be used for a wastewater treatment process such as activated sludge, but can also be used for process water or the like.
When the process of the present invention (hereinafter sometimes referred to as “the present process”) is in the vicinity of the steam cracking process, the water recovered from the reactor outlet gas is preferably utilized as a steam source for the cracker. Moreover, you may recycle to the reactor of this process and use it as dilution gas.

  In addition, it is preferable that hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms obtained from the outlet gas of the reactor obtain high-purity ethylene and propylene, respectively, by a purification process such as distillation. 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.

  The ethylene and propylene thus obtained can be used for all of the ethylene and propylene derivatives that are generally produced. For example, ethylene is produced by chlorination to produce ethylene oxide, ethylene glycol, ethanolamine, glycol ether, etc. by oxidation reaction. For the production of vinyl chloride monomer, 1,1,1-trichloroethane, vinyl chloride resin, vinylidene chloride, for the production of α-olefin, low density or high density polyethylene by polymerization of ethylene, and ethylbenzene by ethylation of benzene Etc., respectively.

  Polyethylene terephthalate can be produced from ethylene glycol produced from ethylene as a raw material, and higher alcohol is obtained by oxo reaction and subsequent hydrogenation reaction using α-olefin as raw material, styrene monomer, ABS resin, etc. from ethylbenzene Can be manufactured. Also, vinyl acetate can be produced by reaction with acetic acid, and acetaldehyde and its derivative ethyl acetate can be produced by Wacker reaction.

  Propylene is produced by polymerization of propylene, for example, for the production of acrylonitrile by ammoxidation, for the production of acrolein, acrylic acid and acrylate by selective oxidation, for the production of oxo alcohols such as normal butyl alcohol and 2-ethylhexanol by oxo reaction. Can be applied to the production of polypropylene and the production of propylene oxide and propylene glycol by the selective oxidation of propylene. Further, acetone can be produced by Wacker reaction, and methyl isobutyl ketone can be produced from acetone. Acetone cyanohydrin can also be produced from acetone, which is ultimately converted to methyl methacrylate. Isopropyl alcohol can also be produced by propylene hydration. In addition, phenol, bisphenol A, and polycarbonate resin can be produced using a cumene produced by alkylating benzene as a raw material.

Further, the fluid containing the hydrocarbon having 2 or less carbon atoms and the hydrocarbon having 3 carbon atoms obtained in the third aspect and the fourth aspect of the general separation step of the fluid (L) is other than this process. It is preferable to supply to the production process of ethylene and propylene and purify them. Other processes for producing ethylene and propylene include steam cracking processes such as naphtha and ethane. This can significantly reduce the capital investment of this process.
On the other hand, when the fluid containing ethylene produced in this process cannot be supplied to ethylene and propylene production processes other than this process, it is necessary to purify ethylene in this process. It is preferable to adopt the first aspect or the second aspect of the general separation step (1).

[Recycling process]
{Separation / recycling process in the first and second embodiments}
<Separation and recycling of hydrocarbons with 4 or more carbon atoms: Process (3A), (3B)>
At least a part of the hydrocarbon-rich fluid (A) separated from the reactor outlet gas (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 may be supplied directly to other processes through piping, or once stored in a tank through piping. Things may be supplied to other processes. Moreover, you may use as a fuel, without supplying to another process.

  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 optionally removed from the process. The remaining fluid (C) is extracted by a general separation method such as distillation. A fluid (D) having a lower aromatic compound concentration (% by weight) than the fluid (C) and a hydrocarbon concentration of 4 carbon atoms are the fluid (C). A method is applied which comprises the steps of separating into a lower fluid (E), recycling the fluid (D) to the reactor and extracting the fluid (E) from the process.

  Further, as a second embodiment of the method of recycling the hydrocarbon fluid (A) having 4 or more carbon atoms to the reactor, the aromatic fluid is obtained by a general separation technique such as distillation of the hydrocarbon fluid (A) having 4 or more carbon atoms. A fluid (G) having a lower group compound concentration than the fluid (A) and a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (A), and at least a part of the fluid (F) is separated from the process. A method including a step of extracting at least a part of the fluid (G) to the reactor and extracting the remaining fluid (H) from the process is applied.

  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 aspect or the fluid (H) in the second aspect includes paraffin. Since the composition fluid contains a large amount, it is difficult to separate and purify active ingredients such as butene. Therefore, when the process is close to the steam cracking process, it is preferably supplied to the steam cracking process and effectively used as a cracker raw material.

  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 the fluid (H) is brought into contact with the hydrogenation catalyst, and a fluid having a paraffin concentration increased from the fluid (B) or the fluid (H) is supplied to the steam cracking process. preferable. Supplying a fluid having a high olefin concentration to the cracker of the steam cracking process is not preferable because carbon deposition tends to occur in the cracker.

  In this case, the total concentration of aromatic compounds contained in the fluid (B) or the fluid (H) is preferably less than 5.0% by volume, and more preferably less than 3.0% by volume. When the aromatic compound concentration is high, there is a large amount of carbon deposition when supplied to the cracker, and the ethylene yield tends to decrease, which is not preferable.

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

  The cracked gasoline referred to here is a fluid mainly containing paraffin, olefin, diene and aromatic compound having 5 to 10 carbon atoms, and an active ingredient can be recovered from the cracked gasoline as required. As an active ingredient, aromatic compounds, such as C5 hydrocarbon and benzene, toluene, xylene, are mentioned, for example.

  If 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 the fluid (F) mixed with the cracked gasoline fraction is less than 5% by weight. More preferably, it is less than 2% by weight.

  As a feature of the first aspect, it is possible to reduce the load of the separation process such as distillation by extracting the fluid (B), so that it is more advantageous than the second aspect in terms of utility cost and capital investment cost. is there. However, the fluid (B) is a fluid having the same composition as the fluid (A), and the concentration of the aromatic compound is higher than that of the fluid (H) obtained in the second embodiment. Therefore, the process is selected according to the application of the fluid to be extracted.

{Recycling step in the third embodiment}
<Recycling of hydrocarbons having 4 or more carbon atoms: Step (4C)>
Part (P) of the fluid (N) rich in hydrocarbons having 4 or more carbon atoms (hereinafter referred to as “hydrocarbon fluid (N) having 4 or more carbon atoms)” separated in step (3C) is removed from this process. The remaining fluid (Q) is withdrawn and recycled to the reactor, and at least a part of the liquid fluid (M) rich in hydrocarbons having 4 or more carbon atoms condensed in the compression step and containing aromatic compounds. Is extracted from this process.
Here, “extracted from this process” means that it is not recycled to the reactor of this process, and may be supplied directly to other processes through piping, or once stored in a tank through piping. Things may be supplied to other processes. Moreover, you may use as a fuel, without supplying to another process.

  The liquid fluid (M) is obtained by distillation. A fluid (R) having an aromatic compound concentration (wt%) lower than that of the liquid fluid (M) and a fluid (S) having a hydrocarbon concentration of 4 carbon atoms lower than that of the liquid fluid (M). May be separated. In this case, the fluid (R) is preferably returned to any one or a plurality of fluid circulation locations selected from the fluids (K), (L), (N), (P), and (Q). When the liquid fluid (M) contains a large amount of hydrocarbons having 4 or less carbon atoms, it is particularly preferable to perform this distillation operation.

  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) are composition fluids containing a large amount of paraffin. Therefore, it is difficult to separate and purify active ingredients such as butene. Therefore, when the process is close to the steam cracking process, one or more of these fluids (M), (P), and (R) are supplied to the steam cracking process and effectively used as a cracker raw material. It is preferable to do.

This can be a raw material for producing ethylene or propylene in steam cracking. At this time, at least 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 steam cracked. It is preferable to feed the process. This is not preferable because carbon deposition is likely to occur in the cracker that supplies a fluid having a high olefin concentration to the cracker of the steam cracking process.

  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%. When the aromatic compound concentration is high, there is a large amount of carbon deposition when supplied to the cracker, and the ethylene yield tends to decrease, which is not preferable.

  The fluid (S) is preferably mixed with a cracked gasoline fraction such as a steam cracking process. This makes it possible to effectively use the fluid (S). Further, when the concentration of hydrocarbons having 4 or less carbon atoms in the fluid (M) is low, the fluid (M) may be directly mixed with the cracked gasoline fraction.

  The cracked gasoline referred to here is a fluid mainly containing paraffin, olefin, diene and aromatic compound having 5 to 10 carbon atoms, and an active ingredient can be recovered from the cracked gasoline as required. As an active ingredient, aromatic compounds, such as C5 hydrocarbon and benzene, toluene, xylene, are mentioned, for example.

  If 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 the fluid (S) mixed with the cracked gasoline fraction is less than 5% by weight. More preferably, it is less than 2% by weight.

{Control of substrate concentration at reactor inlet in first to third embodiments}
In the first embodiment, the flow rate of the dilution gas such as paraffin contained in the fluid (D) recycled to the reactor can be controlled by controlling the flow rates of the fluid (B) and the fluid (E). Is possible.
In the second embodiment, 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.
In the third embodiment, the flow rate of the fluid (M) and the fluid (P), or the fluid (P), the fluid (R) and the fluid (S), and further, the fluid (K), (L), Fluid that is recycled to the reactor by controlling the flow rate of fluid (R) to be returned to one or more fluid locations selected from (N), (P), and (Q) and the return location thereof It is possible to control the flow rate of dilution gas such as paraffin contained in (Q).

  In any embodiment, in this way, the total concentration (substrate concentration) of the olefin having 4 or more carbon atoms, methanol and dimethyl ether in the total feed fed to the reactor is 20% by volume or more and 80% by volume. It is preferable to control to the following.

[Integration with the steam cracking process]
In the steam cracking process, a low-value fluid (mainly C4 raffinate-2) obtained by removing necessary components from the obtained hydrocarbon fluid having 4 carbon atoms (BB fraction) is hydrogenated and returned to the cracker. Many.
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 a very efficient process possible.

[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 invention, FIG. 2 shows a second embodiment, and FIG. 3 shows a third embodiment.

  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. 101-114 shows piping, respectively.

  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. Reference numerals 301 to 315 denote piping.

<Description of the first embodiment (FIG. 1)>
The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (D) having 4 or more carbon atoms from the second separation / purification system 30A, methanol and / or dimethyl ether are supplied to the reactor 10 via the pipes 101, 102, 103 and the pipe 104, respectively. To be supplied. 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 normal butane and isobutane. Moreover, the raw material fluid supplied to the reactor 10 via the pipe 104 may contain butadiene or an aromatic compound. As described above, the butadiene concentration in the raw material fluid 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 of the pipe 104. The ratio is usually less than 0.05. In addition, although the raw material fluid means the sum total of the fluid supplied via piping 101,102,103, these do not necessarily need to merge before entering the reactor 10, and supply to the reactor 10 separately. May be. The raw material gas supplied to the reactor 10 reacts in contact with the catalyst in the reactor 10 to obtain a reactor outlet gas containing propylene, other olefins, paraffins, aromatic compounds and water.

  The reactor outlet gas is supplied 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 hydrocarbon-rich fluid having 4 or less carbon atoms, 4 or more carbon atoms. The hydrocarbon-rich fluid (A) and the water-rich fluid are separated and taken out through the pipes 106, 108 and 107, respectively. Here, the fluid rich in hydrocarbons having 3 or less carbon atoms indicates one or more fluids. For example, it may be a single fluid containing all hydrocarbons having 3 or less carbon atoms, a fluid rich in hydrocarbons having 2 or less carbon atoms, a fluid rich in hydrocarbons having 3 carbon atoms, or a carbonization having 2 or less carbon atoms. Two fluids may be used, such as a fluid containing hydrogen and a C 3 hydrocarbon and a fluid rich in C 3 hydrocarbons. Furthermore, three or more fluids may be used.

  A part of the fluid (A) rich in hydrocarbons having 4 or more carbon atoms is extracted from the pipe 109 to the outside of the process, and the remaining fluid (C) is passed through the pipe 110 to a general separation and purification system 30A such as distillation. Supplied. 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.

  In the separation and purification system 30A, the fluid (D) is separated into a fluid (D) having a lower aromatic compound concentration than the fluid (C) and a fluid (E) having a hydrocarbon concentration of 4 or more carbon atoms lower than the fluid (C). Is recycled to the reactor 10 via the pipe 102, and the fluid (E) is extracted from the process through the pipe 111. The extraction fluid (E) may be mixed with a cracked gasoline fraction such as a steam cracking process. In that case, the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (E) is preferably less than 5% by weight.

  A part of the fluid (D) (hereinafter referred to as “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 extracted fluid (X) is preferably less than 5.0 mol%.

  Extraction of the fluid (B) and the fluid (X) out of the process is not always necessary, but it is preferable to extract at least a part of the fluid from the process in order to prevent the accumulation of paraffins.

<Description of Second Embodiment (FIG. 2)>
The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (I) having 4 or more carbon atoms from the second separation and purification system 30B, methanol and / or dimethyl ether are respectively supplied to the reactor 10 via the pipes 101, 102, 103 and the pipe 104. To be supplied. Thereafter, in the first separation and 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 (A) having 4 or more carbon atoms, and a fluid rich in water. Steps until the separation is the same as in FIG.

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

  The fluid (G) is taken out from the pipe 113, a part (H) thereof is extracted from the process through the pipe 114, and the remaining fluid (I) is recycled to the reactor 10 through the pipe 102. The extraction 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. It is preferable that the sum total of the aromatic compound density | concentration of the fluid (H) at this time is less than 5.0 volume%.

  Extraction of the fluid (H) out of the process is not necessarily required, but it is preferable to extract at least a part of the fluid from the process in order to prevent accumulation of paraffins.

<Third Embodiment (FIG. 3)>
The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (Q) having 4 or more carbon atoms from the first separation / purification system 53, methanol and / or dimethyl ether are respectively supplied to the reactor 13 via pipes 301, 302, 303 and pipe 304. To be supplied. 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 normal butane and isobutane. Further, the raw material fluid supplied to the reactor 13 through the pipe 304 may contain butadiene or an aromatic compound. As described above, the butadiene concentration in the raw material fluid 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. In addition, although the raw material fluid means the sum total of the fluid supplied via piping 301,302, and 303, these do not necessarily need to merge before entering into the reactor 13, and separately enter into the reactor 13. It may be supplied. The raw material gas supplied to the reactor 13 reacts with the catalyst in the reactor 13 to obtain a reactor outlet gas containing propylene, other olefins, paraffins, aromatic compounds and water.

  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. The condensed component is supplied to the oil / water separator 43 through the pipe 308 and separated into a liquid fluid (M) rich in hydrocarbons having 4 or more carbon atoms and a fluid rich in water. The liquid fluid (M) extracted and rich in hydrocarbons having 4 or more carbon atoms is supplied to the second separation and purification system 63 through the pipe 309.

  The gas fluid (L) separated by the knockout drum 33 is fed 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, It is separated into four or more hydrocarbon-rich fluids (N) and taken out via pipes 313 and 314, respectively. Here, the fluid rich in hydrocarbons having 3 or less carbon atoms indicates one or more fluids. For example, it may be a single fluid containing all hydrocarbons having 3 or less carbon atoms, a fluid rich in hydrocarbons having 2 or less carbon atoms, a fluid rich in hydrocarbons having 3 carbon atoms, or a carbonization having 2 or less carbon atoms. Two fluids may be used, such as a fluid containing hydrogen and a C 3 hydrocarbon and a fluid rich in C 3 hydrocarbons. Furthermore, three or more fluids may be used.

  A part (P) of the hydrocarbon-rich fluid (N) having 4 or more carbon atoms is extracted from the process through the pipe 315, and the remaining fluid (Q) is recycled to the reactor 13 through the pipe 302. . 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. It is preferable that the sum total of the aromatic compound density | concentration of the fluid (P) at this time is less than 5.0 volume%.

  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, but this may be 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 concentration of paraffin is increased by contacting the hydrogenation catalyst. It is preferable that the sum total of the aromatic compound density | concentration of the fluid (M) at this time is less than 5.0 volume%.

  Further, when the concentration of hydrocarbons having 4 carbon atoms 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, the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (M) is preferably less than 5% by weight.

  In addition, at least a part of the liquid fluid (M) is a second separation and purification system 63 that is a general separation step such as distillation, and the fluid (R) and carbon number of which the aromatic compound concentration is lower than that of the liquid fluid (M). 4 is preferably separated into a fluid (S) having a lower hydrocarbon concentration than the liquid fluid (M). The separated fluid (R) is extracted from the pipe 311. The fluid (R) is fluid (K), fluid (L), fluid (N), fluid (P), and fluid (Q). It is preferable to return to one place or a plurality of places among the pipes 305, 307, 314, 315, 302.

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

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

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Catalyst preparation]
The catalysts used in the following examples and comparative examples were prepared as follows.

<Catalyst preparation example>
26.6 g of tetra-n-propylammonium bromide (TPABr) and 4.8 g of sodium hydroxide are sequentially dissolved in 280 g of water, and then colloidal silica (SiO ₂ = 40 wt%, Al <0.1 wt%). A mixed solution of 75 g and 35 g of water was slowly added and sufficiently stirred to obtain an aqueous gel. Next, this gel was charged into a 1000 ml autoclave, and hydrothermal synthesis was performed at 170 ° C. for 72 hours while stirring at 300 rpm under a self-pressure. The product was subjected to pressure filtration to separate solid components, sufficiently washed with water, and then 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.

  2.0 g of this Na-type aluminosilicate 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, sufficiently washed with water, then suspended again 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, sufficiently washed with water, and then dried at 100 ° C. for 24 hours. The dried catalyst was calcined at 500 ° C. for 4 hours under air flow to obtain an H-type aluminosilicate.

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 ₃ = 1100 (molar ratio).

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

<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 0.10 g of the catalyst and 1.0 g of quartz sand. In this reactor, isobutene (40% by volume), methanol (20% by volume), benzene (0.8% by volume) were used as simulated gases corresponding to the composition of the reactor inlet gas (pipe 104 in FIG. 1 or 2) in the present invention. %), Butadiene (0.1% by volume) and isobutane (39.1% by volume) were fed through an evaporator. 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.
Propylene selectivity was 54.8%, a very high level.
Further, the reaction was continued, and the time until the methanol conversion rate fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 312 hours.

<Example 2>
The reaction was carried out in the same manner as in Example 1 except that the concentration of benzene in the gas supplied to the reactor was 1.6 vol% and the isobutane concentration was 38.3 vol%. 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.
Propylene selectivity was 54.4%, a very high level.
Further, the reaction was continued, and the time until the methanol conversion rate fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 305 hours.

<Comparative Example 1>
The reaction was performed in the same manner as in Example 1 except that the concentration of benzene in the gas 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. The reaction conditions and reaction results at that time are shown in Table 1.
The selectivity for propylene was 51.4%, which was a very low level compared to Examples 1 and 2.
This is due to the wasteful consumption of butene and / or methanol that should be originally used for propylene production due to the reaction of butene and / or methanol as a raw material with benzene to produce alkylated benzene.
Further, the reaction was continued, and the time until the methanol conversion rate fell below 99% was evaluated as the catalyst life. As a result, the catalyst life was 221 hours, which was very short compared to Example 1 and Example 2. This is presumed to be because the alkylated benzene blocks the pores of the catalyst and promotes coking.

  From the above results, in accordance with the method of the present invention, reducing the aromatic compound concentration at the reactor inlet by extracting at least a part of the aromatic compound in the reactor outlet gas without recycling can increase the propylene yield. It can be seen that it is very effective in achieving and suppressing catalyst coking degradation.

It is a systematic diagram which shows an example of embodiment of the manufacturing method of the propylene of this invention. It is a systematic diagram which shows the other example of embodiment of the manufacturing method of the propylene of this invention. It is a systematic diagram which shows the other example of embodiment of the manufacturing method of the propylene of this invention.

DESCRIPTION OF SYMBOLS 10 Reactor 20 1st separation and purification system 30A, 30B 2nd separation and purification system 13 Reactor 23 Compressor 33 Knockout drum 43 Oil-water separator 53 1st separation and purification system 63 2nd separation and purification system

Claims (56)

In a method for producing propylene by contacting a raw material containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), (2) and (3A) The process for producing propylene is characterized by comprising a process comprising:
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (D) recycled from the step (3A), and methanol and / or dimethyl ether are supplied to the reactor, and the number of carbon atoms at the reactor outlet is 4 or more. The olefin is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor. Step (2) for obtaining a gas (reactor outlet gas) containing a kind, an aromatic compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, Step (3A) of separation into fluid (A) rich in hydrocarbons having 4 or more carbon atoms and fluid rich in water: Fluid (C) of at least part of fluid (A) in step (2) ) Is separated into a fluid (D) having a lower aromatic compound concentration than the fluid (C) and a fluid (E) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (C), and the fluid (D) Recycling to the reactor and extracting the fluid (E) from the process In a method for producing propylene by contacting a raw material containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), (2) and (3A) The process for producing propylene is characterized by comprising a process comprising:
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (D) recycled from the step (3A), and methanol and / or dimethyl ether are supplied to the reactor, and the number of carbon atoms at the reactor outlet is 4 or more. The olefin is brought into contact with the catalyst under reaction conditions such that the molar flow rate of olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor. Step (2) for obtaining a gas (reactor outlet gas) containing a kind, an aromatic compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, Step (3A) of separation into a fluid (A) rich in hydrocarbons having 4 or more carbon atoms and a fluid rich in water: A part (B) of the fluid (A) in the step (2) The remaining fluid (C) is separated into a fluid (D) having a lower aromatic compound concentration than the fluid (C) and a fluid (E) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (C). The fluid (D) is recycled to the reactor and the fluid (E) is withdrawn from the process.   In Claim 1 or 2, 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, a recycled hydrocarbon-containing fluid (D), In addition, a method for producing propylene, characterized in that at least one of methanol and / or dimethyl ether is divided and supplied to a first-stage reaction section and a second-stage reaction section and thereafter. The method for producing propylene according to claim 2 , wherein the fluid (B) is supplied to a steam cracking process and used as a cracker raw material.   The method for producing propylene according to claim 4, 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. The method for producing propylene according to any one of claims 2, 4, and 5, wherein the total concentration of the aromatic compounds contained in the fluid (B) is less than 5.0% by volume.   The method for producing propylene according to any one of claims 1 to 6, wherein the fluid (E) is mixed with a cracked gasoline fraction of a steam cracking process.   The method for producing propylene according to any one of claims 1 to 7, wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (E) is less than 5% by weight. The number of carbon atoms contained in all raw materials supplied to the reactor according to any one of claims 2, 4, 5, and 6 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 the olefin, methanol and dimethyl ether is controlled to 20 vol% or more and 80 vol% or less. In a method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), (2) and (3B The process for producing propylene is characterized by comprising a process comprising:
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (I) recycled from the step (3B), and methanol and / or dimethyl ether are supplied to the reactor, and the reactor has 4 or more carbon atoms at the outlet of the reactor. The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor, and propylene, other olefins, paraffins, aroma Step (2) for obtaining a gas (reactor outlet gas) containing a group compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, 4 or more carbon atoms The step (3B) of separating the hydrocarbon-rich fluid (A) and the water-rich fluid into the fluid (A) in the step (2), the aromatic compound concentration from the fluid (A) A step of separating a low fluid (G) into a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than that of the fluid (A), and recycling at least a part (I) of the fluid (G) to the reactor. In a method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), (2) and (3B The process for producing propylene is characterized by comprising a process comprising:
Step (1): The olefin raw material having 4 or more carbon atoms, the hydrocarbon fluid (I) recycled from the step (3B), and methanol and / or dimethyl ether are supplied to the reactor, and the reactor has 4 or more carbon atoms at the outlet of the reactor. The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the reactor inlet, and propylene and other olefins, paraffins, aromas Step (2) for obtaining a gas (reactor outlet gas) containing a group compound and water: The reactor outlet gas from the step (1) is a fluid rich in hydrocarbons having 3 or less carbon atoms, 4 or more carbon atoms The step (3B) of separating the hydrocarbon-rich fluid (A) and the water-rich fluid into the fluid (A) in the step (2), the aromatic compound concentration from the fluid (A) The fluid (G) is separated into a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than that of the fluid (A), the fluid (F) is withdrawn from the process, and a part of the fluid (G) ( I) is recycled to the reactor and the remaining fluid (H) is withdrawn from the process   In Claim 10 or 11, 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, a recycled hydrocarbon-containing fluid (I), In addition, a method for producing propylene, characterized in that at least one of methanol and / or dimethyl ether is divided and supplied to a first-stage reaction section and a second-stage reaction section and thereafter. 12. The method for producing propylene according to claim 11 , wherein the fluid (H) is supplied to a steam cracking process and used as a cracker raw material.   The method for producing propylene according to claim 13, 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. The method for producing propylene according to any one of claims 11, 13, and 14, wherein the total concentration of aromatic compounds contained in the fluid (H) is less than 5.0% by volume.   The method for producing propylene according to any one of claims 10 to 15, wherein the fluid (F) is mixed with a cracked gasoline fraction of a steam cracking process.   The method for producing propylene according to any one of claims 10 to 16, wherein a total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (F) is less than 5% by weight. The carbon number of 4 or more contained in all raw materials supplied to the reactor according to any one of claims 11, 13, 14, and 15 by controlling the flow rates of the fluid (F) and the fluid (H). The total concentration (substrate concentration) of olefin, methanol and dimethyl ether is controlled to be 20 vol% or more and 80 vol% or less.   In any one of Claims 1 thru | or 18, after the said process (2) condensed and removed the water | moisture content by the cooling and the compression process from the said reactor exit gas, it was rich in the C2 or less hydrocarbon by distillation. The fluid 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 separated into a fluid rich in hydrocarbons having 3 carbon atoms and 4 or more carbon atoms by distillation. A process for producing propylene, comprising a step of separating into a fluid rich in hydrocarbons.   19. The process (2) according to any one of claims 1 to 18, wherein the step (2) is enriched with hydrocarbons having 3 or less carbon atoms by distillation after the moisture is condensed and removed from the reactor outlet gas by a cooling and compression step. The fluid is separated into a fluid rich in hydrocarbons having 4 or more carbon atoms, and the fluid rich in hydrocarbons having 3 or less carbon atoms is separated from the fluid rich in hydrocarbons having 2 or less carbon atoms and 3 carbon atoms by distillation. A process for producing propylene, comprising a step of separating into a fluid rich in hydrocarbons.   19. The hydrocarbon and the number of carbon atoms having 2 or less carbon atoms by distillation after the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, according to any one of claims 1 to 18. 3 fluids containing 3 hydrocarbons and fluids rich in hydrocarbons having 3 or more carbon atoms, and the fluids rich in hydrocarbons having 3 or more carbon atoms are fluids rich in hydrocarbons having 3 carbon atoms by distillation. And a process for separating propylene into a hydrocarbon-rich fluid having 4 or more carbon atoms.   19. The process (2) according to any one of claims 1 to 18, wherein the step (2) is enriched in hydrocarbons having 3 or less carbon atoms by distillation after the moisture is condensed and removed from the reactor outlet gas by a cooling and compression step. The fluid is separated into a fluid rich in hydrocarbons having 4 or more carbon atoms, and the fluid rich in hydrocarbons having 3 or less carbon atoms includes hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms by distillation. A method for producing propylene, comprising a step of separating a fluid and a fluid rich in hydrocarbons having 3 carbon atoms.   23. The method for producing propylene according to any one of claims 1 to 22, wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.   The method for producing propylene according to claim 23, wherein the paraffins contain normal butane and / or isobutane.   The method for producing propylene according to any one of claims 1 to 24, wherein the raw material supplied to the reactor contains butadiene.   26. In any one of Claims 1 thru | or 25, the total amount of the aromatic compound contained in all the raw materials supplied to the said reactor is with respect to the total amount of C4 or more olefins contained in all the said raw materials. A method for producing propylene, wherein the molar ratio is less than 0.05.   27. The amount of olefins having 4 or more carbon atoms fed to the reactor according to any one of claims 1 to 26 is the sum of the number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether. On the other hand, the manufacturing method of propylene characterized by being 0.2-10 in molar ratio.   The production of propylene according to any one of claims 1 to 27, wherein the olefin raw material having 4 or more carbon atoms supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained by a steam cracking process. Method. In the method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1C), (2C), (3C ) And (4C).
Step (1C): Olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (Q) recycled from step (4C), and methanol and / or dimethyl ether are supplied to the reactor, and 4 or more carbon atoms at the outlet of the reactor The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor, and propylene, other olefins, paraffins from the reactor outlet Step of obtaining a gas (reactor outlet gas) containing an aromatic compound and water Step (2C): Cooling the reactor outlet gas from the step (1C), gas fluid (L), having 4 or more carbon atoms Separating into a liquid fluid (M) rich in hydrocarbons and containing an aromatic compound, and a fluid rich in water Step (3C): The gas fluid (L) in the step (2C) Separating into a hydrocarbon-rich fluid having a prime number of 3 or less and a hydrocarbon-rich fluid having a carbon number of 4 or more (N) Step (4C): At least part of the fluid (Q) of the fluid (N) Recycling process to reactor In the method for producing propylene by contacting a mixture containing an olefin having 4 or more carbon atoms and methanol and / or dimethyl ether in a reactor in the presence of a catalyst, the following steps (1C), (2C), (3C ) And (4C).
Step (1C): Olefin raw material having 4 or more carbon atoms, hydrocarbon fluid (Q) recycled from step (4C), and methanol and / or dimethyl ether are supplied to the reactor, and 4 or more carbon atoms at the outlet of the reactor The catalyst is brought into contact with the catalyst under reaction conditions such that the molar flow rate of the olefin is 20% or more and less than 90% with respect to the molar flow rate of the olefin at the inlet of the reactor, and propylene, other olefins, paraffins from the reactor outlet Step of obtaining a gas (reactor outlet gas) containing an aromatic compound and water Step (2C): The reactor outlet gas from the step (1C) is cooled, and the cooled gas fluid (K) is compressed. Separating into a gas fluid (L), a liquid fluid (M) rich in hydrocarbons having 4 or more carbon atoms and containing an aromatic compound, and a fluid rich in water Step (3C): Step of separating the gas fluid (L) in (2C) into a hydrocarbon-rich fluid having 3 or less carbon atoms and a fluid (N) rich in hydrocarbon having 4 or more carbon atoms Step (4C): the fluid (N A part of (P) is extracted from the process and the remaining fluid (Q) is recycled to the reactor.   31. The fluid (M) according to claim 29 or 30, wherein the liquid (M) has a concentration of an aromatic compound lower than that in the liquid fluid (M) and a hydrocarbon concentration of 4 carbon atoms by liquid distillation. And a lower fluid (S). 30. The fluid (M) according to claim 30 , wherein the liquid (M) has a concentration of an aromatic compound lower than that in the liquid fluid (M) and a hydrocarbon having 4 carbon atoms than the liquid fluid (M) by distillation. The fluid (R) is separated into a low fluid (S), and the fluid (R) is any one or more fluids selected from the fluids (K), (L), (M), (P), and (Q) The production method of propylene characterized by being returned to the distribution location of   33. The process (3C) according to any one of claims 29 to 32, wherein the step (3C) converts the gas fluid (L) into a hydrocarbon-rich fluid having 2 or less carbon atoms and a hydrocarbon having 3 or more carbon atoms by distillation. A fluid rich in hydrocarbons having 3 or more carbon atoms is separated by distillation 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 And a process for separating it into a propylene.   33. The process (3C) according to any one of claims 29 to 32, wherein the step (3C) converts the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms and a hydrocarbon having 4 or more carbon atoms by distillation. A fluid rich in hydrocarbons having a carbon number of 3 or less and a fluid rich in hydrocarbons having a carbon number of 2 or less and rich in hydrocarbons of a carbon number 3 by distillation. A method for producing propylene, which comprises a step of separating into a fluid.   33. The fluid according to any one of claims 29 to 32, wherein the step (3C) is performed by distilling the gas fluid (L) into a hydrocarbon containing a hydrocarbon having 3 or less carbon atoms and a hydrocarbon having 2 or less carbon atoms by distillation. It is separated into a fluid rich in hydrocarbons having a carbon number of 3 or more, and further, a fluid rich in hydrocarbons having a carbon number of 3 or more is distilled into a fluid rich in hydrocarbons having a carbon number of 3 and carbonized with a carbon number of 4 or more. A method for producing propylene, comprising a step of separating the fluid into a fluid (N) rich in hydrogen.   33. The process (3C) according to any one of claims 29 to 32, wherein the step (3C) converts the gas fluid (L) into a hydrocarbon-rich fluid having 3 or less carbon atoms and a hydrocarbon having 4 or more carbon atoms by distillation. A fluid rich in hydrocarbons having a carbon number of 3 or less is separated by distillation into a fluid containing hydrocarbons having a carbon number of 2 or less and hydrocarbons having a carbon number of 3 and carbon number 3 A process for producing propylene, comprising the step of separating into a hydrocarbon-rich fluid.   37. The olefin raw material having 4 or more carbon atoms to be supplied to the reactor, the recycled hydrocarbon containing, the reactor comprising two or more reaction parts connected in series. A method for producing propylene, characterized in that at least one of a fluid and methanol and / or dimethyl ether is divided and supplied to a first-stage reaction section and a second-stage reaction section or later.   38. The method for producing propylene according to any one of claims 29 to 37, wherein the olefin raw material having 4 or more carbon atoms contains paraffins having 4 or more carbon atoms.   39. The method for producing propylene according to claim 38, wherein the paraffins contain normal butane and / or isobutane.   40. The method for producing propylene according to any one of claims 29 to 39, wherein the raw material supplied to the reactor contains butadiene.   In any one of Claims 29 thru | or 40, the total amount of the aromatic compound contained in all the raw materials supplied to the said reactor is with respect to the total amount of C4 or more olefins contained in this all raw materials. A method for producing propylene, wherein the molar ratio is less than 0.05.   The method for producing propylene according to any one of claims 29 to 41, wherein the fluid (M) and / or the fluid (P) is supplied to a steam cracking process and used as a cracker raw material.   43. The method for producing propylene according to claim 42, wherein at least a part of the fluid (M) and / or the fluid (P) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.   44. The propylene according to claim 29, wherein the total concentration of aromatic compounds contained in the fluid (M) and / or the fluid (P) is less than 5.0% by volume. Production method.   The method for producing propylene according to any one of claims 29 to 44, wherein the fluid (M) is mixed with a cracked gasoline fraction of a steam cracking process.   The method for producing propylene according to any one of claims 29 to 45, wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (M) is less than 5 wt%.   In any one of Claims 29 thru | or 46, by controlling the flow volume of the said fluid (M) and the said fluid (P), C4 or more olefin contained in all the raw materials supplied to the said reactor, A method for producing propylene, characterized in that the total concentration of methanol and dimethyl ether (substrate concentration) is controlled to 20 vol% or more and 80 vol% or less.   48. The method for producing propylene according to any one of claims 31 to 47, wherein the fluid (R) is supplied to a steam cracking process and used as a cracker raw material.   49. The method for producing propylene according to claim 48, wherein at least a part of the fluid (R) is brought into contact with a hydrogenation catalyst and then supplied to a steam cracking process.   The method for producing propylene according to any one of claims 31 to 49, wherein the total concentration of aromatic compounds contained in the fluid (R) is less than 5.0% by volume.   The method for producing propylene according to any one of claims 31 to 50, wherein the fluid (S) is mixed with a cracked gasoline fraction of a steam cracking process.   52. The method for producing propylene according to any one of claims 31 to 51, wherein the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (S) is less than 5% by weight.   53. The carbon number 4 contained in all raw materials supplied to the reactor according to any one of claims 31 to 52, by controlling the flow rates of the fluid (P), the fluid (R), and the fluid (S). A method for producing propylene, characterized in that the total concentration (substrate concentration) of the olefin, methanol and dimethyl ether is controlled to 20 vol% or more and 80 vol% or less.   54. The fluid (R) according to any one of claims 31 to 53, wherein the fluid (R) is one or more selected from the fluids (K), (L), (N), (P), and (Q). The total concentration of olefin, methanol and dimethyl ether having 4 or more carbon atoms contained in all raw materials supplied to the reactor is controlled by controlling the return position of the fluid (R) and its flow rate when returning to the position of the fluid. (Substrate concentration) is controlled to 20% by volume or more and 80% by volume or less, and a method for producing propylene.   55. The amount of olefin having 4 or more carbon atoms fed to the reactor according to any one of claims 29 to 54 is the sum of the number of moles of methanol fed to the reactor and twice the number of moles of dimethyl ether. On the other hand, the manufacturing method of propylene characterized by being 0.2-10 in molar ratio.   The propylene production according to any one of claims 29 to 55, wherein the olefin raw material having 4 or more carbon atoms supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained by a steam cracking process. Method.

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