KR20090059123A - Process for production of propylene - Google Patents

Abstract

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

Description

Process for producing propylene {PROCESS FOR PRODUCTION OF PROPYLENE}

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

As a method for producing propylene, steam cracking of naphtha and ethane and fluid catalytic cracking of vacuum gas have been generally performed, and in recent years, a metathesis reaction based on ethylene and 2-butene and an olefin having 4 or more carbon atoms Contact cracking of and MTO processes using at least one of methanol and dimethyl ether as a raw material are also attracting attention. On the other hand, the method of manufacturing a lower olefin using the C4 or more olefin and oxygen compounds, such as methanol, as a raw material is also known (patent document 1).

Patent Document 1: US Patent No. 6888038

Disclosure of Invention

Problems to be Solved by the Invention

Conventionally, many proposals have been made as a method for producing propylene, and most of them have been disclosed for reactions and purification, respectively. For a method using as a raw material oxygen-containing compounds such as olefins having 4 or more carbon atoms and methanol, Although a proposal of its own has been made, a process involving a purification system on the downstream side of the reactor has not been proposed.

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

On the other hand, in the current steam cracking process for producing ethylene or propylene, the ratio of ethylene and propylene to be produced cannot be greatly changed, but the ratio of ethylene and propylene can be significantly changed by integrating the process of the present invention with steam cracking. In addition, by integrating these two processes, it becomes possible to effectively use the fluids which are unnecessary in each other's processes, and thus the synergistic effect is expected to make the process construction remarkably efficient.

It is therefore a second object of the present invention to provide a novel and economical process incorporating the present process and steam cracking.

Means to solve the problem

As a result of the present inventors examining a reaction for obtaining propylene by reacting at least one of olefins having 4 or more carbon atoms with methanol and dimethyl ether, the following findings were obtained.

When the amount of olefins consumed by the reaction is too large, by-products of undesirable compounds such as aromatic compounds and paraffins become remarkable. On the other hand, when the amount of olefins consumed is too small, the yield of propylene is too low. By setting reaction conditions, such as temperature, a pressure, partial pressure, and space velocity suitably, and controlling the amount of olefins consumed in a specific range, propylene is obtained by high selectivity and high yield. When the reaction is carried out under such conditions, it is preferable that these compounds are recycled to the reactor in view of the fact that the reactor outlet fluid contains many olefins having 4 or more carbon atoms which can be used as a reaction raw material.

On the other hand, in the reaction of at least one of olefins having 4 or more carbon atoms with methanol and dimethyl ether, aromatic compounds and paraffins are also produced as traces 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, when recycled to the reactor together with olefins having 4 or more carbon atoms, paraffin is concentrated and accumulated in the system. For this reason, it is preferable to extract a part of the fluid containing paraffins from system. In this case, the fluid to be extracted is preferably a fluid having a composition that can be effectively used.

In addition, when an aromatic compound exists in a specific concentration or more in the olefin fluid of 4 or more carbon atoms recycled, the reaction of these aromatic compounds and an olefin having 4 or more carbon atoms, or the reaction of at least one of the aromatic compound, methanol and dimethyl ether becomes significant, and the supplied carbon number At least one of four or more olefins, methanol and dimethyl ether is consumed more than necessary and is not preferable.

In addition, when the aromatic compound is supplied to the reactor, since the compound produced by the reaction with the olefin having 4 or more carbon atoms occludes the pores of the catalyst, deterioration of the catalyst is also promoted, so that the aromatic compound present in the reactor outlet fluid is possible. It is preferable to lower the concentration of the aromatic compound in the fluid discharged from within the system and recycled to the reactor. Also in this case, the fluid to be extracted is preferably a fluid having a composition that can be effectively used.

As described above, the present inventors have found out various problems in the method for producing propylene using olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether as raw materials, thereby establishing a process that can solve these problems. It was found that propylene can be produced in high yield while suppressing the deterioration of the catalyst by using less raw materials.

In addition, by supplying the fluid discharged from the present process to steam cracking and supplying the fluid in the steam cracking process to the present process, it is possible to effectively use a low-value fluid and realize a remarkably efficient process. Figured out.

This invention was achieved based on such knowledge, and makes the following a summary.

[1] A method for producing propylene by contacting a olefin having at least 4 carbon atoms with at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, in a reactor outlet effluent gas (reactor outlet gas). At least a portion of the aromatic compound contained together with the extraction,

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

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

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

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

[5] The total amount of the aromatic compounds contained in all the raw materials supplied to the reactor is less than 0.05 in the molar ratio according to any one of [1] to [4], relative to the total amount of the C4 or more olefins contained in the total raw materials. Process for producing propylene, characterized in that.

[6] The content of any one of [1] to [5], wherein the amount of olefins having 4 or more carbon atoms supplied to the reactor is a sum of twice the number of moles of methanol and the number of moles of dimethyl ether supplied to the reactor. It is 0.2 or more and 10 or less by molar ratio, The manufacturing method of propylene characterized by the above-mentioned.

[7] The volume of any one of [1] to [6], wherein the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in all the raw materials supplied to the reactor is 20% by volume to 80% by volume. The manufacturing method of propylene characterized by the following control.

[8] A method for producing propylene by contacting a raw material containing at least one of olefins having 4 or more carbon atoms with methanol and dimethyl ether in the presence of a catalyst, in the following steps (1), (2) and A process for producing propylene, comprising a process comprising (3A).

Process (1): The olefin raw material of C4 or more C4, the hydrocarbon fluid (D) recycled from the process (3A), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the C4 or more C4 olefin in a reactor outlet is A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with said catalyst at reaction conditions that are at least 20% and less than 90% relative to the molar flow rate of said olefin at the reactor inlet. Reactor outlet gas)

Step (2): A step of separating the reactor outlet gas from the above step (1) into a hydrocarbon rich hydrocarbon having at most 3 carbon atoms, a fluid rich hydrocarbon having at least 4 carbon atoms (A), and a fluid rich in water.

Step (3A): At least a part of the fluid (C) of the fluid (A) in the step (2) is a fluid (D) having a lower aromatic compound concentration than the fluid (C) and a hydrocarbon concentration of 4 carbon atoms. Separating into fluid (E) lower than fluid (C), said fluid (D) being recycled to a reactor, and withdrawing said fluid (E) from the process

[9] A method for producing propylene by contacting a olefin having at least 4 carbon atoms with at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, comprising the following steps (1), (2) and A process for producing propylene, comprising a process comprising (3A).

Process (1): The olefin raw material of C4 or more C4, the hydrocarbon fluid (D) recycled from the process (3A), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the C4 or more C4 olefin in a reactor outlet is A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with said catalyst at reaction conditions that are at least 20% and less than 90% relative to the molar flow rate of said olefin at the reactor inlet. Reactor outlet gas)

Step (2): A step of separating the reactor outlet gas from the above step (1) into a hydrocarbon rich hydrocarbon having at most 3 carbon atoms, a fluid rich hydrocarbon having at least 4 carbon atoms (A), and a fluid rich in water.

Step (3A): A part (B) of the fluid (A) in the step (2) is extracted from the process, and the remaining fluid (C) is a fluid (D) having an aromatic compound concentration lower than that of the fluid (C). ) And 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 discharged from the process.

[10] The olefin raw material according to [8] or [9], wherein the reactor includes two or more reaction units connected in series and is supplied to the reactor; At least one of methanol and dimethyl ether; And at least one of the fluid (D) containing the recycled hydrocarbon is divided and supplied into the reaction section in the first stage and the reaction section in the second stage and later.

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

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

[13] The method for producing propylene according to any one of [8] to [12], wherein the total of the aromatic compound concentrations contained in the fluid (B) is less than 5.0 vol%.

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

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

[16] The monomer according to any one of [8] to [15], wherein the flow rate of the fluid (B) and the fluid (E) is controlled so that the olefins having 4 or more carbon atoms and methanol contained in all the raw materials supplied to the reactor; The total concentration (substrate concentration) of dimethyl ether is controlled to 20 volume% or more and 80 volume% or less, The manufacturing method of propylene characterized by the above-mentioned.

[17] A process for producing propylene by bringing a mixture of olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether into contact with each other in the presence of a catalyst in the following steps (1), (2) and A process for producing propylene, comprising the process comprising (3B).

Process (1): The olefin raw material of carbon number 4 or more, the hydrocarbon fluid (I) recycled from process (3B), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the carbon number 4 or more olefins of a reactor exit is reactor A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst under reaction conditions of 20% or more and less than 90% relative to the molar flow rate of the olefin at the inlet (reactor outlet Gas)

Step (2): A step of separating the reactor outlet gas from the step (1) into a hydrocarbon rich hydrocarbon having at most 3 carbon atoms, a hydrocarbon rich hydrocarbon having at least 4 carbon atoms, and a fluid rich in water.

Step (3B): The fluid (A) in the step (2) includes a fluid (G) having an aromatic compound concentration lower than the fluid (A) and a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (A). Separating at least a portion (I) of the fluid (G) into the reactor and withdrawing the remaining fluid (H) in the process.

[18] A method for producing propylene by bringing a mixture of olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether into contact with each other in the presence of a catalyst in the following steps (1), (2) and A process for producing propylene, comprising the process comprising (3B).

Process (1): The olefin raw material of carbon number 4 or more, the hydrocarbon fluid (I) recycled from process (3B), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the carbon number 4 or more olefins of a reactor exit is reactor A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst under reaction conditions of 20% or more and less than 90% relative to the molar flow rate of the olefin at the inlet (reactor outlet Gas)

Step (2): A step of separating the reactor outlet gas from the step (1) into a hydrocarbon rich hydrocarbon having at most 3 carbon atoms, a hydrocarbon rich hydrocarbon having at least 4 carbon atoms, and a fluid rich in water.

Step (3B): The fluid (A) in the step (2) includes a fluid (G) having an aromatic compound concentration lower than the fluid (A) and a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (A). The fluid F is withdrawn from the process, and a portion I of the fluid G is recycled to the reactor and the remaining fluid H is withdrawn from the process.

[19] The olefin raw material according to [17] or [18], wherein the reactor includes two or more reaction units connected in series and is supplied to the reactor; At least one of methanol and dimethyl ether; And at least one of the fluid (I) containing the recycled hydrocarbon is dividedly supplied into the reaction section in the first stage and the reaction section in the second and subsequent stages, thereby producing propylene.

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

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

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

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

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

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

[26] The process according to any one of [8] to [25], wherein the step (2) is rich in hydrocarbons having 2 or less carbon atoms by distillation after condensation of water from the reactor outlet gas by a cooling and compression step. Separating the fluid into a fluid rich in hydrocarbons having at least 3 carbon atoms, and separating the fluid rich in hydrocarbons having at least 3 carbon atoms into a fluid rich in hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having at least 4 carbon atoms by distillation. The manufacturing method of propylene made into.

[27] The process according to any one of [8] to [25], wherein the step (2) is enriched with hydrocarbons having 3 or less carbon atoms by distillation after condensation of water from the reactor outlet gas by a cooling and compression step. Separating the fluid into a fluid rich in hydrocarbons having 4 or more carbon atoms, and separating the 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. Process for producing propylene, characterized in that.

[28] The hydrocarbon according to any one of [8] to [25], wherein the step (2) is carried out by condensation of water from the reactor outlet gas by a cooling and compression step, followed by distillation of hydrocarbons having 2 or less carbon atoms, and Separated into a fluid containing a hydrocarbon containing 3 carbon atoms and a fluid rich in hydrocarbons containing 3 or more carbon atoms, the fluid rich in hydrocarbons containing 3 or more carbon atoms is separated into a fluid rich in hydrocarbons containing 3 carbon atoms and a fluid rich in hydrocarbons containing 4 or more carbon atoms by distillation. Process for producing propylene, comprising the step of.

[29] The method according to any one of [8] to [25], wherein the step (2) is rich in hydrocarbons having 3 or less carbon atoms by distillation after condensation of water 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 distilled into a fluid containing hydrocarbons having 2 or less carbon atoms and 3 hydrocarbons and a hydrocarbon rich hydrocarbon having 3 or less carbon atoms. A process for producing propylene, comprising the step of separating.

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

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

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

[33] The method according to any one of [8] to [32], wherein the total amount of the aromatic compounds contained in all the raw materials supplied to the reactor is less than 0.05 in molar ratio with respect to the total amount of the C4 or more olefins contained in the total raw materials. Process for producing propylene, characterized in that.

[34] The method according to any one of [8] to [33], wherein the amount of olefins having 4 or more carbon atoms supplied to the reactor is about twice the sum of the number of moles of methanol and the number of moles of dimethyl ether supplied to the reactor. It is 0.2 or more and 10 or less in molar ratio, The manufacturing method of propylene characterized by the above-mentioned.

[35] The method for producing propylene according to any one of [8] to [34], wherein the olefin raw material having at least 4 carbon atoms supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained by steam cracking.

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

Process (1C): At least one of a olefin raw material having at least 4 carbon atoms, a hydrocarbon fluid (Q) recycled from step (4C), and methanol and dimethyl ether is supplied to the reactor, and the molar flow rate of the at least 4 carbon olefins at the reactor outlet is increased. A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst at reaction conditions that are at least 20% and less than 90% relative to the molar flow rate of the olefin at the reactor inlet. Process of obtaining outlet gas)

Step (2C): The reactor outlet gas from the step (1C) is cooled and separated into a gas fluid (L), a liquid fluid (M) rich in C4 or more hydrocarbons, containing an aromatic compound and a fluid rich in water. Process

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

Step 4C: recycling at least a portion of the fluid Q of the fluid N to the reactor

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

Process (1C): At least one of a olefin raw material having at least 4 carbon atoms, a hydrocarbon fluid (Q) recycled from step (4C), and methanol and dimethyl ether is supplied to the reactor, and the molar flow rate of the at least 4 carbon olefins at the reactor outlet is increased. A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst at reaction conditions of 20% or more and less than 90% relative to the molar flow rate of the olefin at the reactor inlet. Process of obtaining outlet gas)

Step (2C): The reactor outlet gas from the step (1C) is cooled, and the gas fluid (K) after cooling is rich in the gas fluid (L) and a hydrocarbon having 4 or more carbon atoms, and a liquid containing an aromatic compound. Process to separate into fluid (M) and water rich fluid

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

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

[38] The liquid fluid M according to [36] or [37], wherein distillation of the liquid fluid M results in distillation of the liquid R having a lower aromatic compound concentration in the liquid fluid M and a hydrocarbon concentration of 4 carbon atoms. Process for producing propylene, characterized in that it is separated into a fluid (S) lower than (M).

[39] The method of [38], wherein the fluid (R) is a flow point of any one or two or more fluids selected from the fluids (K), (L), (M), (P), and (Q). A method for producing propylene, which is characterized by returning.

[40] The process according to any one of [36] to [39], wherein the step (3C) converts the gas fluid (L) into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms. Separating and further separating the fluid rich in hydrocarbons having at least 3 carbon atoms into a fluid rich in hydrocarbons having 3 carbon atoms and fluid rich in hydrocarbons having at least 4 carbon atoms (N) by distillation. Way.

[41] The process of any one of [36] to [39], wherein the step (3C) distills the gas fluid (L) into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms. Separating into (N) and further 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. Process for the preparation of propylene.

[42] The fluid and carbon number according to any one of [36] to [39], wherein the step (3C) comprises distilling the gas fluid (L) to contain a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms. Separating into a fluid rich in three or more hydrocarbons, and further separating a fluid rich in hydrocarbons having three or more carbon atoms into a fluid rich in hydrocarbons having three carbon atoms and a fluid rich in hydrocarbons having four or more carbon atoms (N) by distillation. Process for producing propylene, characterized in that.

[43] The process of any one of [36] to [39], wherein the step (3C) is performed by distilling the gas fluid (L) into a fluid rich in hydrocarbons having 3 or less carbon atoms and rich in hydrocarbons having 4 or more carbon atoms. Separating into a fluid (N), and further distilling a fluid rich in hydrocarbons having 3 or less carbon atoms into a fluid containing hydrocarbons having 2 or less carbon atoms and 3 carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms. Propylene manufacturing method comprising a.

[44] The olefin raw material according to any one of [36] to [43], wherein the reactor includes two or more reaction units connected in series and is supplied to the reactor; At least one of methanol and dimethyl ether; And at least one of the fluid containing the recycled hydrocarbon is divided and supplied into the reaction section in the first stage and the reaction section in the second stage and later.

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

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

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

[48] The method according to any one of [36] to [47], wherein the total amount of the aromatic compounds contained in all the raw materials supplied to the reactor is 0.05 in molar ratio relative to the total amount of the C4 or more olefins contained in the total raw materials. It is less than the manufacturing method of propylene characterized by the above-mentioned.

[49] The production of propylene according to any one of [36] to [48], wherein at least one of the fluid (M) and the fluid (P) is supplied to steam cracking and used as a cracker raw material. Way.

[50] The method for producing propylene according to [49], wherein at least one of the fluid (M) and at least one of the fluid (P) is brought into contact with a hydrogenation catalyst and then supplied to steam cracking.

[51] The propylene according to any one of [36] to [50], wherein the sum of the concentrations of the aromatic compounds contained in at least one of the fluid (M) and the fluid (P) is less than 5.0% by volume. Manufacturing method.

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

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

[54] The olefin and methanol having at least 4 carbon atoms contained in all the raw materials supplied to the reactor by controlling the flow rates of the fluid M and the fluid P according to any one of [36] to [53]. And a total concentration (substrate concentration) of dimethyl ether to 20% by volume or more and 80% by volume or less.

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

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

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

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

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

[60] The carbon number 4 according to any one of [38] to [59], wherein the flow rate of the fluid (P), the fluid (R), and the fluid (S) is controlled so as to contain 4 carbon atoms contained in all the raw materials supplied to the reactor. The total concentration (substrate concentration) of the above olefin, methanol, and dimethyl ether is controlled to 20 volume% or more and 80 volume% or less, The manufacturing method of propylene characterized by the above-mentioned.

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

[62] The sum of any one of [36] to [61], wherein the amount of olefins having 4 or more carbon atoms supplied to the reactor is twice the number of moles of methanol and the number of moles of dimethyl ether supplied to the reactor. It is 0.2 or more and 10 or less in molar ratio, The manufacturing method of propylene characterized by the above-mentioned.

[63] The method for producing propylene according to any one of [36] to [62], wherein the olefin raw material having at least 4 carbon atoms supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained by steam cracking.

Effects of the Invention

According to the present invention, in the presence of a catalyst, a method of producing propylene by reacting at least one of an olefin raw material having 4 or more carbon atoms with methanol and dimethyl ether, using propylene in a high yield while suppressing deterioration of the catalyst by using the raw material highly. Can be prepared.

In addition, the method of the present invention can be integrated with steam cracking to provide an economical process.

BRIEF DESCRIPTION OF THE DRAWINGS It is a system diagram which shows an example of embodiment of the manufacturing method of the propylene of this invention.

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

3 is a system diagram showing another example of the embodiment of the process for producing propylene of the present invention.

Explanation of the sign

10 reactor

20 First Separation Purification System

30A, 30B Second Separation Purification System

13 reactor

23 compressor

33 knockout drum

43 Oil Water Separator

53 First Separation Purification System

63 Second Separation Purification System

Implement the invention  Best form for

Hereinafter, although the typical aspect for implementing this invention is demonstrated concretely, 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 contacting a raw material containing at least one of olefins having 4 or more carbon atoms with methanol and dimethyl ether in a reactor, in the reactor outlet effluent gas. At least a part of the aromatic compound contained therein is characterized in that, together with the extraction, at least a part of the C4 or more olefins contained in the reactor outlet gas is brought into contact with the catalyst in the reactor again.

More specific first and second embodiments comprising three steps (1), (2), (3A) or (1), (2), (3B) as described above, and as a third embodiment Although it includes 4 steps (1C), (2C), (3C), and (4C) of 4 as mentioned above, in order to solve the subject of this invention, excepting the presence of other processes is not excluded. Instead, other steps may exist before and after the four steps, and different steps may exist between the steps.

In addition, in this invention, "rich" means that the purity of a target object is 50 mol% or more, Preferably it is 70 mol% or more, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more. For example, "the fluid (N) rich in hydrocarbons having 4 or more carbon atoms" means 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, and even more preferably "hydrocarbons having 4 or more carbon atoms". Is a fluid containing 95 mol% or more.

[catalyst]

First, the catalyst used by this invention is demonstrated.

The catalyst used in the reaction according to the present invention is not particularly limited as long as it is a solid phase having a Bronsted acid point, and conventionally known catalysts are used, for example, clay minerals such as kaolin; Impregnated and supported with acids such as sulfuric acid and phosphoric acid in a carrier such as clay mineral; Acidic ion exchange resins; Zeolites; Aluminum phosphates; Solid acid catalysts, such as mesoporous silica alumina, such as Al-MCM41, are mentioned.

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

As the structure of zeolites or aluminum phosphates having a molecular sieve effect among the solid acid catalysts, 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 Can be. Especially, the catalyst whose framework density of a catalyst is 18.0T / nm <3> or less is preferable, As such a thing, Preferably it is MFI, MEL, MOR, MWW, FAU, BEA, CHA, More preferably, MFI, MEL, MOR, MWW, CHA, and particularly preferably MFl, MEL, MWW, CHA.

Here, the framework density (unit T / nm 3) means 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, and this The value is determined by the structure of the zeolite.

As the solid acid catalyst, more preferably, crystalline aluminosilicate having 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 0.5 g / ml. And metallosilicates or crystalline aluminum phosphates are preferred. In addition, the pore diameter here refers to the crystallographic free diameter of the channels defined by the International Zeolite Association (IZA), and when the shape of the pores (channels) is a round shape, the pore diameter refers to the pore diameter. When the shape is elliptical, it represents a short diameter.

Further, in the aluminosilicate, preferably at least a molar ratio of _{SiO 2 / Al 2 O 3 10} . If the SiO ₂ / Al ₂ O ₃ molar ratio is too low, it is not preferable because the durability of the catalyst is lowered. The upper limit of the molar ratio of SiO ₂ / Al ₂ O ₃ is usually 10000 or less. If the molar ratio of SiO ₂ / Al ₂ O ₃ is too high than this, the catalytic activity is lowered, which is not preferable. The molar ratio can be obtained by conventional methods such as fluorescence X-rays and chemical analysis.

The aluminum content in the catalyst can be controlled by the amount of raw material injected during preparation of the catalyst, and Al can be reduced by steaming or the like after preparation. In addition, a part of Al may be substituted with another element such as boron or gallium, and in particular, it is preferable to substitute with boron.

These catalysts may be used individually by 1 type, and may mix and use 2 or more types.

In the present invention, the catalytically active component as described above may be used for the reaction as it is as a catalyst, granulated and molded using a substance or binder which is inert to the reaction, or a mixture thereof may be used for the reaction. Examples of the substance or binder inert to the reaction include alumina or alumina sol, silica, silica gel, quartz, and mixtures thereof.

Incidentally, the above catalyst composition is a composition only of the catalytically active component which does not contain a substance, a binder or the like which is inert to these reactions. However, when the catalyst according to the present invention contains a substance, a binder, or the like which is inert to these reactions, all of the above-described catalytically active components and the substance, the binder, and the like which are inert to these reactions are called catalysts and are inert to these reactions. When it does not contain a substance, a binder, etc., it is called a catalyst only by a catalytically active component.

The particle diameter of the catalytically active component used in the present invention varies depending on the conditions at the time of synthesis, but is usually 0.01 µm to 500 µm as the average particle diameter. If the particle diameter of the catalyst is too large, the surface area showing the catalytic activity is small, and if the particle size is too small, the handleability is inferior, which is not preferable in any case. This average particle diameter can be calculated | required by SEM observation etc.

The preparation method of the catalyst used by this invention is not specifically limited, It can prepare by the well-known method generally called hydrothermal synthesis. In addition, after hydrothermal synthesis, the composition can be changed by modification such as ion exchange, dealumination treatment, impregnation, or supporting.

The catalyst used by this invention should just have what was said physical property or composition, when providing to reaction, and what was prepared by any method may be sufficient as it.

[Reaction raw material]

Next, the C4 or more olefin, methanol, and dimethyl ether which are used as a reaction raw material in this invention are demonstrated.

 <Olefin raw material>

It does not specifically limit as a C4 or more olefin used as a raw material of reaction. For example, those produced by catalytic cracking or steam cracking from petroleum feedstocks (BB fraction, C4 raffinate-1, C4 raffinate-2, etc.), and hydrogen / CO mixed gas obtained by gasification of coal as a raw material. Obtained by carrying out FT (Fischerthrop) synthesis, obtained by oligomerization reaction containing a dimerization reaction of ethylene, obtained by dehydrogenation or oxidative dehydrogenation of paraffins having 4 or more carbon atoms, by MTO reaction Olefin having 4 or more carbon atoms, particularly 4 to 10 carbon atoms, which are obtained by various known methods, such as those obtained, those obtained by dehydration of alcohols, and those obtained by hydrogenation of diene compounds having 4 or more carbon atoms can be optionally used. In this case, compounds having a state in which a compound other than a C4 or more olefins resulting from each production method is optionally mixed And it may be used as may be used a purified olefin.

Among these, when using an olefin raw material containing paraffins having 4 or more carbon atoms, paraffin plays a role as a diluent gas, so that the reaction temperature can be easily controlled, and raw materials containing paraffin can be obtained at low cost. It is preferable because there are many cases. More preferably, it is an olefin raw material containing at least one of normal butane and 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 the 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. Moreover, since BB fraction contains a lot of butadiene, it is preferable to use as a raw material the fluid which contacted the hydrogenation catalyst and reduced the butadiene concentration.

 <Methanol, Dimethyl Ether>

The origin of manufacture of at least one of methanol and dimethyl ether used as a raw material for the reaction is not particularly limited. For example, those obtained by hydrogenation of a mixed gas of hydrogen / CO derived from coal and natural gas and by-products in the steelmaking industry, those obtained by reforming reactions of alcohols derived from plants, and by fermentation methods What is obtained, what is obtained from organic substances, such as recycled plastics and municipal waste, etc. are mentioned. Under the present circumstances, the thing in which the compound other than methanol and dimethyl ether resulting from each manufacturing method is arbitrarily mixed may be used as it is, or the refined thing may be used.

[Reaction Operation and Conditions: Step (1) (1C) in First to Third Embodiments]

The operation and conditions of the propylene production reaction of the present invention using the catalyst and the reaction raw material described above will be described below.

 <Reactor>

In the present invention, the reaction of at least one of olefins having 4 or more carbon atoms with methanol and 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 fixed bed reactor or a fluidized bed reactor. Preferably it is a fixed bed reactor.

In addition, in the case of filling the above-mentioned catalyst in the fixed bed reactor, in order to suppress the temperature distribution of the catalyst layer small, granular materials inert to the reaction of quartz sand, alumina, silica, silica-alumina, and the like may be mixed with the catalyst and filled. In this case, the amount of the granular material inert to the reaction of quartz sand or the like is not particularly limited. Moreover, it is preferable that this granular material is the particle diameter of the same grade as a catalyst from a uniform mixing property with a catalyst.

Moreover, the reactor may consist of two or more reaction parts connected in series. In this case, one reactor may be partitioned into a plurality of reaction chambers, or two or more reactors may be connected in series.

In the case where two or more reactors are connected in series in this manner, a heat exchanger may be disposed between the reactor and the reactor for the purpose of removing heat generated by the reaction.

Moreover, you may divide and supply a reaction substrate (reactive raw material) for the purpose of disperse | distributing heat_generation | fever. Preferably, at least one of methanol and dimethyl ether is dividedly supplied into the first stage reaction unit (reactor or reaction chamber) and the second stage subsequent reaction unit (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. However, when the continuous operation for one year or more is performed, it is necessary to perform catalyst regeneration during the operation.

For example, when selecting a fixed bed reactor, it is preferable to install at least two reactors in parallel, and to operate while switching reaction and regeneration. As the fixed bed reactor, a multi-tubular reactor or adiabatic reactor is selected.

On the other hand, when selecting a fluidized bed reactor, it is preferable to send a catalyst continuously to a regeneration tank, and to perform reaction, returning a catalyst regenerated in a regeneration tank to a reactor continuously.

Here, as a regeneration operation of the catalyst, a method of regenerating the catalyst deteriorated by caulking may be performed by treating with oxygen containing nitrogen gas or water vapor. In the regeneration operation in the fixed bed reactor, preferably, after removing the volatile organic compounds adhering to the catalyst with nitrogen gas, the coke powder is burned off with nitrogen gas containing a low concentration of oxygen, and then nitrogen And a method of removing molecular oxygen contained in the catalyst layer by treating with gas.

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

In the present invention, the amount of olefins having 4 or more carbon atoms to be supplied to the reactor is 0.2 or more, preferably 0.5 or more and 10 or less in terms of mole ratio with respect to a total of twice the number of moles of methanol and the number of moles of dimethyl ether supplied to the reactor. , Preferably it is 5 or less.

That is, when the supply molar amount of C4 or more olefins is Mc4, the supply molar amount of methanol is Mm, and the supply molar amount of dimethyl ether is Mdm, Mc4 is 0.2-10 times (Mm + 2Mdm), Preferably it is 0.5-5 times.

Even if this feed concentration ratio is too low, even if it is too high, reaction will become slow and it is unpreferable. Especially, when this feed concentration ratio is too low, it is unpreferable since the consumption of olefin of a raw material reduces.

Here, the supply concentration ratio can be known by quantifying the composition of each fluid supplied to the reactor or the mixed fluid by general analytical methods such as gas chromatography.

In addition, when supplying a C4 or more olefin and at least 1 of methanol and dimethyl ether to a reactor, you may supply these separately, and you may supply, after mixing a part or all previously.

 <Substrate concentration fed to the reactor>

In the present invention, the total concentration (substrate concentration) of olefins having 4 or more carbon atoms and methanol and dimethyl ether in the total feedstock supplied to the reactor is preferably 20% by volume or more and 80% by volume or less, more preferably 30 It is more than 70% by volume.

Here, the substrate concentration can be known by quantifying the composition of each fluid supplied to the reactor or the mixed fluid by general analytical methods such as gas chromatography.

When the substrate concentration is too high, the production of aromatic compounds and paraffins becomes remarkable, and the selectivity of propylene tends to decrease. On the contrary, when the substrate concentration is too low, a large amount of catalyst is required because the reaction rate is slowed, and the cost of refining the product and the construction cost of the reaction equipment are large, which is not economical.

In the present invention, the reaction substrate is diluted with the dilution gas described below so as to achieve such a substrate concentration. In this case, as a method of controlling a substrate concentration, the method of controlling the flow volume of the fluid discharged | emitted from a process is mentioned. In other words, by changing the flow rate of the fluid discharged from the process, the flow rate of the dilution gas recycled to the reactor can be changed, and the substrate concentration can be changed.

 Impurity concentration in the gas supplied to the reactor

In the present invention, butadiene may be contained in an olefin raw material having at least 4 carbon atoms and / or in a hydrocarbon-containing fluid to be recycled, but the concentration of butadiene in the total feedstock supplied to the reactor is 2.0% by volume or less. desirable. A high butadiene concentration in the raw material is not preferable because the production of aromatic compounds increases and deterioration due to caulking of the catalyst is accelerated.

Here, the butadiene concentration can be known by quantifying the composition of each fluid supplied to the reactor or the mixed fluid by general analytical methods such as gas chromatography.

As a method of reducing the butadiene concentration in a raw material, the partial hydrogenation method which contacts the fluid with a hydrogenation catalyst and converts into olefins is mentioned.

Moreover, although the aromatic compound may be contained in the hydrocarbon-containing fluid mentioned later recycled to a reactor, the total amount of the aromatic compound contained in all the raw materials supplied to a reactor contains 4 or more carbon atoms contained in all the raw materials supplied to a reactor. It is preferable that it is less than 0.05 in molar ratio with respect to the total amount of olefin. When the concentration of aromatic compounds in the raw materials is high, the reaction between the aromatic compound and the olefin having 4 or more carbon atoms in the reactor or the reaction of the aromatic compound with at least one of methanol and dimethyl ether becomes remarkable and more than necessary the olefin with 4 or more carbon atoms, methanol and dimethyl ether. It is not preferable because at least one of them is consumed.

In addition, when the aromatic compound is supplied to the reactor, since the compound produced by the reaction with the olefin having 4 or more carbon atoms occludes the pores of the catalyst, deterioration of the catalyst is also promoted, so that the aromatic compound present in the reactor outlet fluid is possible. It is preferable to lower the concentration of the aromatic compound in the fluid discharged from within the system and recycled to the reactor.

The ratio of the total amount of the above-mentioned aromatic compound to the total amount of olefins having 4 or more carbon atoms can be known by quantifying the composition of each fluid supplied to the reactor or the mixed fluid by general analytical methods such as gas chromatography.

The distillation method by distillation is mentioned as a method of reducing the aromatic compound concentration in a raw material.

 <Dilution gas>

In the reactor, there are gases inert to the reaction, such as paraffins, aromatics, water vapor, carbon dioxide, carbon monoxide, nitrogen, argon, helium, and mixtures thereof, in addition to olefins having 4 or more carbon atoms and at least one of methanol and dimethyl ether. You can. Moreover, among these diluent gases, although paraffins and aromatics may react slightly depending on reaction conditions, they are defined as a dilution gas from the point that reaction amount is small.

As such a dilution gas, the impurity contained in the reaction raw material may be used as it is, or the dilution gas prepared separately may be mixed with the reaction raw material and used.

Moreover, before diluting gas into a reactor, you may mix with a reaction raw material, and you may supply with a reaction raw material, respectively.

Preferred diluent gases are paraffins having 4 or more carbon atoms. More preferably, it is at least one of normal butane and isobutane. While these paraffins can be used in the olefin raw material, they are easy to control the reaction temperature because they are compounds having a relatively large heat capacity.

 <Space velocity>

The space velocity here refers to a flow rate of olefins having 4 or more carbon atoms as the reaction raw material per weight of the catalyst (catalyst active component), and the weight of the catalyst is a catalytically active component that does not contain an inert component or a binder used for assembling and forming the catalyst. Is the weight. In addition, a flow volume is a flow volume (weight / hour) of a C4 or more olefin.

The space velocity is preferably between 0.1Hr ^-1 500Hr to ^-1, and is between 1.0Hr ^{-1 -1} to 100Hr more preferred. If the space velocity is too high, the conversion ratio of at least one of the olefin of the raw material, methanol and dimethyl ether is low, and sufficient propylene selectivity cannot be obtained. In addition, if the space velocity is too low, the amount of catalyst required to obtain a constant yield increases, the reactor becomes too large, and undesirable by-products such as aromatic compounds and paraffin are generated, and the propylene selectivity is lowered, which is not preferable.

 <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. When reaction temperature is too low, reaction rate will be low, it will tend to leave many unreacted raw materials, and the yield of propylene will also fall. On the other hand, when reaction temperature is too high, the yield of propylene will fall remarkably.

 <Reaction pressure>

The upper limit of the reaction pressure is usually 2 MPa (absolute pressure, below), preferably 1 MPa or less, and more preferably 0.7 MPa or less. Moreover, the minimum in particular of reaction pressure is although it does not restrict | limit, Usually, it is 1 kPa or more, Preferably it is 50 kPa or more. When 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 Material by Reaction>

The sum of the molar flow rate of methanol at the reactor outlet and the molar flow rate of methanol at the outlet of the reactor and the doubling molar flow rate of dimethyl ether are preferably less than 1%. More preferably less than 0.1%.

When the consumption of methanol and dimethyl ether in the reactor is small and the amount of methanol and dimethyl ether at the outlet of the reactor is excessively increased, purification of the product olefin becomes difficult.

As a method of increasing the consumption amount of methanol and dimethyl ether, the method of raising reaction temperature or decreasing space velocity is mentioned.

In the present invention, the molar flow rate of the C4 or more olefins at the outlet of the reactor is 20% or more and less than 90% to the mole flow rate of the C4 or more olefins supplied to the reactor. This molar flow rate ratio is preferably 20% or more and less than 70%, more preferably 25% or more and less than 60%. If the consumption amount of olefins having 4 or more carbon atoms in the reactor is too small, unreacted olefins increase, and the flow rate of the fluid recycled to the reactor becomes too large, which is not preferable. On the contrary, when the consumption is too large, undesirable compounds such as paraffin and aromatic compounds are by-produced and the propylene yield is lowered, which is not preferable.

As a method of adjusting the consumption amount of a C4 or more olefin in a reactor, the method of setting reaction temperature, a space velocity, etc. suitably is mentioned.

Here, the flow rates of methanol, dimethyl ether, and olefins having 4 or more carbon atoms, which are supplied to the reactor, quantify the composition of each fluid or the mixed fluids supplied to the reactor by a general analysis method such as gas chromatography, and the flow rate of each fluid The flow rate of methanol, dimethyl ether and olefins having 4 or more carbon atoms at the outlet of the reactor can be determined by measuring the composition of the reactor outlet fluid by a general method such as gas chromatography, and measuring or calculating the flow rate of the reactor outlet fluid. have.

 <Reaction product>

As the reactor outlet gas (reactor effluent), a mixed gas containing propylene as the reaction product, unreacted raw materials, by-products and diluents 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, at least one of methanol and dimethyl ether is contained, but the reaction is preferably carried out under reaction conditions in which at least one of methanol and dimethyl ether does not remain. This facilitates separation of the reaction product and the unreacted raw material.

By-products include ethylene, olefins having 4 or more carbon atoms, paraffins, aromatic compounds and water.

Separation Process

Separation process in 1st and 2nd aspect

 <Separation of hydrocarbons and water having 3 or less carbon atoms: Process (2)>

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

As a first aspect of the above general separation process, after condensation and dehydration of water by the cooling and compression process, distillation separates into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms, A method comprising the step of separating the rich fluid into a hydrocarbon rich hydrocarbon having 3 carbon atoms and a fluid rich in hydrocarbon (A) having 4 or more carbon atoms is applied.

As a second aspect of the general separation step, the water is condensed and removed by the cooling and compression step, and then separated into a fluid rich in hydrocarbons having 3 or less carbon atoms and fluid rich in hydrocarbons (C) having 4 or more carbon atoms by distillation, and having 3 or less carbon atoms. A method comprising a step of separating a hydrocarbon-rich fluid into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms by distillation is applied.

As a third aspect of the general separation process, the water is condensed and removed by the cooling and compression process, and then separated by distillation into a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms. A method comprising a step of separating a fluid rich in three or more hydrocarbons into a fluid rich in C 3 hydrocarbons and a fluid rich in C 4 or more hydrocarbons (A) by distillation is applied.

As a fourth aspect of the general separation step, after condensation and dehydration of the water by the cooling and compression step, the mixture is separated into a fluid rich in hydrocarbons having 3 or less carbon atoms and fluid rich in hydrocarbons (C) having 4 or more carbon atoms by distillation, and having 3 or less carbon atoms. A method including a step of separating a hydrocarbon-rich fluid into a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 carbon atoms and a fluid rich in hydrocarbon having 3 carbon atoms is applied.

In the 1st-4th aspect of the said general separation process, it is preferable to perform processes, such as quenching, alkali washing, dehydration, as needed. When the oxygen compound is contained in the reactor outlet gas, at least a part of the oxygen compound is removed by the quenching step. When acidic gas, such as carbon dioxide, is contained in a reactor outlet gas, at least one part of acidic gas is removed by alkali washing.

Separation of water is possible mainly by condensation by compression and cooling. The remaining water is preferably removed with an adsorbent such as molecular sieve. Although water removed by condensation and / or adsorption may be provided to wastewater treatment processes, such as activated sludge, it can also be used for process water etc.

When the process (henceforth "this process" may be called hereafter) of this invention is near steam cracking, it is preferable to use the water collect | recovered from the reactor outlet gas as a steam source of a cracker. Moreover, you may recycle to the reactor of this process and use it as a dilution gas.

In addition, it is preferable that the C2 or less hydrocarbons and C3 hydrocarbons obtained from the reactor outlet gas further 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 as raw materials for ethylene and propylene derivatives that are generally produced, even from the viewpoint of the quality of impurities and the like, and ethylene is, for example, ethylene oxide, ethylene glycol, For the production of ethanolamine, glycol ether and the like, for the production of vinyl chloride monomer, 1,1,1-trichlorethane, vinyl chloride resin, vinylidene chloride by chlorination, and for the polymerization of ethylene, αolefin, low density Or it can be used for manufacture of ethylbenzene, etc. by the ethylation of benzene for manufacture of a high density polyethylene, respectively.

From ethylene glycol made of ethylene, polyethylene terephthalate can also be produced using this as a raw material, and styrene monomer, ABS using higher alcohols as ethylbenzene by oxo reaction and subsequent hydrogenation reaction using αolefin as a raw material. Resins and the like can be produced. Moreover, vinyl acetate by reaction with acetic acid, acetaldehyde, ethyl acetate etc. which are derivatives thereof, etc. can also be manufactured by a walker reaction.

In addition, propylene may be used for the production of acrylonitrile, for example, by ammoxidation, in the production of acrolein, acrylic acid and acrylic acid esters by selective oxidation, and in the production of oxo alcohols such as normal butyl alcohol and 2-ethylhexanol by an oxo reaction. It is applicable to the production of polypropylene by the polymerization of propylene for the production and to the production of propylene oxide and propylene glycol by the selective oxidation of propylene. Moreover, acetone can be manufactured by a worker reaction and methyl isobutyl ketone can be manufactured from acetone. Acetone can also be prepared from acetonecyanhydrin, which is finally converted to methyl methacrylate. Moreover, isopropyl alcohol can also be manufactured by propylene hydration. Moreover, phenol, bisphenol A, and polycarbonate resin can be manufactured from the cumene produced by alkylating benzene as a raw material.

In addition, the fluid containing the C2 or less hydrocarbon and the C3 hydrocarbon obtained in the 3rd and 4th aspect of the said general separation process is supplied to refine | purifying process of manufacturing ethylene and propylene other than this process, and refine | purifying. desirable. Steam cracking, such as naphtha and ethane, is mentioned as a manufacturing process of ethylene and propylene other than this process. This can significantly reduce the equipment investment in this process.

On the other hand, when the fluid containing ethylene produced in the present process cannot be supplied to the ethylene and propylene manufacturing processes other than the present process, ethylene must be purified in the present process. It is preferable to employ the aspect or the second aspect.

Separation process in 3rd aspect

Separation Process

 <Separation of gas component, liquid component and water: process (2C), (3C)>

In the present invention, the reactor outlet gas is cooled and the gas fluid (K) after cooling is enriched by gas fluid (L), hydrocarbons having 4 or more carbon atoms, liquid liquid (M) containing aromatic compounds, and rich in water. Separating into a fluid (step (2C)), and then separating the gas fluid (L) into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons (C) having 4 or more carbon atoms by general separation processes such as distillation. (Step (3C)).

In 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 by a heat exchanger, but may be directly cooled by mixing with a fluid lower than the gas. The cooled fluid (K) is enriched with a gaseous fluid (L) rich in hydrocarbons having 6 or less carbon atoms and hydrocarbons having 4 or more carbon atoms by compression using a compressor, knockout drum or oil / water separator, and containing aromatic compounds. The liquid fluid (M) is separated into a water-rich fluid. In addition, although the counterpart fluid which heat-exchanges with a reactor outlet gas in the said heat exchanger is not specifically limited, It is preferable that it is one or some fluid supplied to a reactor.

The gas fluid L rich in hydrocarbons having 6 or less carbon atoms separated in this step (2C) contains hydrocarbons, and in the step (3C), hydrocarbons having 3 or less carbon atoms are enriched by general separation processes such as distillation. The fluid and the hydrocarbon having 4 or more carbon atoms are separated into a fluid (N).

As a first aspect of the above general separation process, distillation separates into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms, and distillates a fluid rich in hydrocarbons having 3 or more carbon atoms by distillation. A method comprising the step of separating a rich fluid and a hydrocarbon rich in hydrocarbons having at least 4 carbon atoms (N) is applied.

As a 2nd aspect of a separation process, distillation isolate | separates into the fluid rich in C3 or less hydrocarbons, and the fluid rich in C4 or more hydrocarbons (N), The fluid rich in C3 or less hydrocarbons is distilled, A method is included that includes a process that separates a hydrocarbon rich fluid and a C 3 hydrocarbon rich fluid.

As a third aspect of the separation step, a fluid containing a hydrocarbon having 2 or less carbon atoms and a hydrocarbon having 3 or more carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms are separated by distillation. A method comprising the step of separating the hydrocarbon-rich fluid and the hydrocarbon-rich fluid (N) having 4 or more carbon atoms is applied.

As a fourth aspect of the separation step, a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons (C) having 4 or more carbon atoms are separated by distillation, and the fluid rich in hydrocarbons having 3 or less carbon atoms is 2 or less carbon atoms by distillation. A method comprising a process comprising separating a hydrocarbon containing a hydrocarbon and a C 3 hydrocarbon and a C 3 hydrocarbon rich fluid is applied.

In the above process, it is preferable to carry out treatment of quenching, alkali washing, dehydration, etc. as needed. When the oxygen compound is contained in the reactor outlet gas, at least a part of the oxygen compound is removed by the quenching step. When acidic gas, such as carbon dioxide, is contained in a reactor outlet gas, at least one part of acidic gas is removed by alkali washing.

Separation of water is possible mainly by condensation by 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 in wastewater treatment processes such as activated sludge, but may also be used in process water and the like.

When the process (henceforth "this process" may be called hereafter) of this invention is near steam cracking, it is preferable to use the water collect | recovered from the reactor outlet gas as a steam source of a cracker. Moreover, you may recycle to the reactor of this process and use it as a dilution gas.

In addition, it is preferable that the C2 or less hydrocarbons and C3 hydrocarbons obtained from the reactor outlet gas further 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 obtained in this way can be used for all ethylene and propylene derivatives generally produced, and ethylene is produced by chlorination in the production of ethylene oxide, ethylene glycol, ethanolamine, glycol ether, etc., for example, by an oxidation reaction. In the production of vinyl chloride monomer, 1,1,1-trichlorethane, vinyl chloride resin, vinylidene chloride, and in the production of α-olefin, low-density or high-density polyethylene by polymerization of ethylene, in the ethylation of benzene It can be used for production of ethylbenzene, etc., respectively.

Ethylene glycol made of ethylene can further be used as a raw material to produce polyethylene terephthalate, and by the oxo reaction and the subsequent hydrogenation reaction using α olefin as a raw material, the higher alcohol is used as the raw material of ethylbenzene and styrene monomer, ABS Resins and the like can be produced. Moreover, vinyl acetate by reaction with acetic acid, acetaldehyde, ethyl acetate etc. which are derivatives thereof, etc. can also be manufactured by a walker reaction.

In addition, propylene may be used for the production of acrylonitrile, for example, by ammoxidation, in the production of acrolein, acrylic acid and acrylic acid esters by selective oxidation, and in the production of oxo alcohols such as normal butyl alcohol and 2-ethylhexanol by an oxo reaction. It is applicable to the production of polypropylene by the polymerization of propylene for the production and to the production of propylene oxide and propylene glycol by the selective oxidation of propylene. Moreover, acetone can be manufactured by a walker reaction, and methyl isobutyl ketone can be manufactured with acetone. Acetone can also prepare acetonecyanhydrin, which is finally converted to methyl methacrylate. Moreover, isopropyl alcohol can also be manufactured by propylene hydration. Moreover, phenol, bisphenol A, and polycarbonate resin can be manufactured from the cumene produced by alkylating benzene as a raw material.

Moreover, it is preferable that the fluid containing C2 or less hydrocarbon and C3 hydrocarbon obtained in the 3rd aspect and 4th aspect of the said separation process is supplied to and refine | purified to the manufacturing processes of ethylene and propylene other than this process. Do. Steam cracking, such as naphtha and ethane, is mentioned as a manufacturing process of ethylene and propylene other than this process. As a result, the capital investment of the process can be significantly reduced.

On the other hand, when the fluid containing ethylene produced in the present process cannot be supplied to the ethylene and propylene manufacturing processes other than the present process, ethylene must be purified in the present process. It is preferable to employ the aspect or the second aspect.

First and second aspect

 <Separation and recycling of hydrocarbons having 4 or more carbon atoms: steps (3A) and (3B)>

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

Here, "outgoing from this process" means that it is not recycled to the reactor of this process, and may supply directly to another process via piping, and may supply what was once stored in the tank to another process via piping. . Moreover, you may use as a fuel, without supplying to another process.

As a first aspect of a method of recycling a hydrocarbon fluid (A) having at least 4 carbon atoms to a reactor, a part (B) of the hydrocarbon fluid having at least 4 carbon atoms (A) is extracted from the process, and the remaining fluid (C) is generally distilled or the like. By the separation method, the aromatic compound concentration (% by weight) is separated into the fluid (D) having a lower concentration than the fluid (C) and the fluid (E) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (C), and the fluid (D) is separated into the reactor. The method including the process of recycling and extracting the fluid (E) from the process is applied.

As a second aspect, a fluid having a lower aromatic compound concentration (G) than a fluid (A) and a hydrocarbon having a hydrocarbon concentration of 4 carbon atoms are lower than a fluid (A) by a general separation method such as distillation of a hydrocarbon fluid (A) having at least 4 carbon atoms. At least a portion of the fluid F is recycled to the reactor and at least a portion of the fluid F is withdrawn from the process, and the remaining fluid H is recycled to the reactor. A method comprising the step of extracting from the is applied.

When using the raw material containing a C4 or more paraffin as a C4 or more olefin raw material, the fluid (B) in said 1st aspect or the fluid (H) in a 2nd aspect contain many paraffins. In view of the fact that it is a composition fluid, it is difficult to separate and purify an active ingredient such as butene. Therefore, when the process is in the vicinity of steam cracking, it is preferable that it is supplied to steam cracking and used effectively as a cracker raw material.

Thereby, these fluids (B) and (H) can be a raw material for ethylene and propylene manufacture in steam cracking. At this time, it is preferable that at least part of the fluid (B) or the fluid (H) is brought into contact with the hydrogenation catalyst to supply the steam cracking with a fluid having a paraffin concentration higher than the fluid (B) or the fluid (H). Supplying a fluid having a high olefin concentration to a cracker of steam cracking is not preferable because carbon precipitation is likely to occur in the cracker.

Moreover, in this case, it is preferable that the sum total of the aromatic compound concentration contained in the fluid (B) or the fluid (H) is less than 5.0 volume%, More preferably, it is less than 3.0 volume%. If the aromatic compound concentration is high, it is not preferable because the carbon precipitation is large and the ethylene yield tends to decrease when supplied to the cracker.

Moreover, it is preferable to mix the fluid (E) in said 1st aspect, or the fluid (F) in a 2nd aspect with decomposition gasoline fraction, such as steam cracking. Thereby, the fluid E or the fluid F can be used effectively.

The decomposition gasoline here is a fluid mainly containing paraffins, olefins, dienes and aromatic compounds having 5 to 10 carbon atoms, and an active ingredient can be recovered from the decomposition gasoline as necessary. As an active component, aromatic compounds, such as a C5 hydrocarbon, benzene, toluene, xylene, are mentioned, for example.

When the cracked gasoline contains hydrocarbons of 4 carbon atoms, the hydrocarbons of carbon 4 are mixed in the carbon 5 hydrocarbon fluid recovered from the cracked gasoline, which is not preferable. Therefore, the hydrocarbon having 4 carbon atoms in the fluid (E) or the fluid (F) mixed with the cracked gasoline fraction is preferably less than 5% by weight. More preferably less than 2% by weight.

As a characteristic of the 1st aspect, since the load of the separation process, such as distillation, can be reduced by extracting the fluid (B), it is advantageous over the 2nd aspect from both a service cost and an equipment investment cost. However, the fluid (B) is a fluid having the same composition as the fluid (A), and the concentration of the aromatic compound is higher as compared with the fluid (H) obtained in the second embodiment. Therefore, the process is selected according to the use of the fluid to be drawn out.

3rd aspect

 <Recycling of C4 or More Hydrocarbons: Process (4C)>

Part (P) of the hydrocarbon-rich fluid (N) having at least 4 carbon atoms separated in step (3C) (hereinafter referred to as "hydrocarbon fluid (N) having at least 4 carbon atoms) is extracted from this process, and the remaining fluid (Q) is Recycled in the reactor. In addition, at least a part of the liquid fluid M which is rich in C4 or more hydrocarbons condensed in the compression step and contains an aromatic compound is extracted from this process.

Here, "outgoing from this process" means that it is not recycled to the reactor of this process, and may be supplied directly to another process via piping, or may supply what was once stored in the tank to another process via piping. . Moreover, you may use as a fuel, without supplying to another process.

Even if the liquid fluid (M) is separated by distillation into a fluid (R) having an aromatic compound concentration (% by weight) lower than the liquid fluid (M) and a hydrocarbon (C) having a hydrocarbon concentration of 4 carbon atoms lower than the liquid fluid (M) do. In this case, the fluid R is preferably returned to any one point selected from the fluids K, (L), (N), (P), and (Q) or the circulation point of the plurality of fluids. When many C4 or less hydrocarbons are contained in liquid fluid M, it is especially preferable to perform this distillation operation.

When using the raw material containing a C4 or more paraffin as a C4 or more olefin raw material, since said fluid (M), (P), (R) is a composition fluid containing many paraffins, butene etc. It is difficult to separate and purify the active ingredient. Therefore, when the process is in the vicinity of steam cracking, it is preferable to supply at least one of these fluids (M), (P), and (R) to steam cracking and effectively use it as a cracker raw material. .

This can be used as a raw material for the production of ethylene or propylene in steam cracking. At this time, at least a part of the fluids (M), (P), and (R) is brought into contact with the hydrogenation catalyst to supply the steam cracking fluid having a paraffin concentration higher than the fluids (M), (P), and (R). It is desirable to. Supplying a fluid having a high olefin concentration to a cracker of steam cracking is not preferable because carbon precipitation is likely to occur in the cracker.

Moreover, in this case, it is preferable that the sum total of the aromatic compound concentration contained in fluid (M), (P), (R) is less than 5.0 volume%. More preferably, it is less than 3.0 volume%. If the concentration of the aromatic compound is high, it is not preferable because there is a lot of carbon precipitation and the ethylene yield tends to decrease when supplied to the cracker.

Moreover, it is preferable to mix said fluid S with the decomposition gasoline fraction, such as steam cracking. Thereby, the fluid S can be used effectively. In addition, when the hydrocarbon concentration of 4 or less carbon atoms in the fluid M is low, the fluid M may be directly mixed with the decomposition gasoline fraction.

The decomposition gasoline here is a fluid mainly containing paraffins, olefins, dienes and aromatic compounds having 5 to 10 carbon atoms, and an active ingredient can be recovered from the decomposition gasoline as necessary. As an active component, aromatic compounds, such as a C5 hydrocarbon, benzene, toluene, xylene, are mentioned, for example.

When the cracked gasoline contains hydrocarbons of 4 carbon atoms, the hydrocarbons of carbon 4 are mixed in the carbon 5 hydrocarbon fluid recovered from the cracked gasoline, which is not preferable. Therefore, the hydrocarbon having 4 carbon atoms in the fluid M or the fluid S mixed with the cracked gasoline fraction is preferably less than 5% by weight. More preferably less than 2% by weight.

 Control of substrate concentration at reactor inlet

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

Moreover, in 2nd aspect, the flow volume of diluent gas, such as paraffin contained in the fluid (I) recycled to a reactor, can be controlled by controlling the flow volume of the fluid (F) and the fluid (H).

In the third aspect described above, the flow rates of the fluid M and the fluid P, or the fluid P, the fluid R and the fluid S, and further, the fluids K, L, and N Paraffin contained in the fluid (Q) recycled to the reactor by controlling the flow rate of the fluid (R) returned to the point of any one or two or more fluids selected from), (P) and (Q), or the return point thereof. The dilution gas flow rate of can be controlled.

Thereby, it is preferable to control the total concentration (substrate concentration) of C4 or more olefins, methanol, and dimethyl ether in 20 mass% or more and 80 volume% or less of all the feedstocks supplied to a reactor.

[Integration with Steam Cracking]

In steam cracking, the low value fluid (mainly C4 raffinate-2) from which the required component was removed from the obtained C4 hydrocarbon fluid (BB fraction) is often hydrogenated and returned to a cracker.

In this process, since this low-value fluid can be used as a raw material and unnecessary fluid can be used in steam cracking in this process, it is a very efficient process that can effectively use each other's low-value fluids.

[Embodiment of the Process]

EMBODIMENT OF THE INVENTION Below, embodiment of the process of this invention is described with reference to drawings.

1 shows a first aspect of the process of the invention and FIG. 2 shows a second aspect.

1 and 2, 10 is a reactor, 20 is a 1st separation purification system, 30A, 30B is a 2nd separation purification system. 101-114 represent a piping, respectively.

 <Description of 1st aspect (FIG. 1)>

At least one of an olefin raw material having at least 4 carbon atoms, a hydrocarbon fluid having at least 4 carbon atoms from the second separation purification system 30A, methanol and dimethyl ether is passed through the reactors 101, 102, 103 and 104, respectively. Supplied to (10). The C4 or more olefin raw material supplied to the reactor 10 may contain C4 or more paraffins, for example, normal butane, isobutane, and the like. In addition, butadiene and an aromatic compound may be contained in the raw material fluid supplied to the reactor 10 via the piping 104. As described above, the butadiene concentration in the raw material fluid is usually 2.0% by volume or less, and the total amount of the aromatic compounds is usually less than 0.05 in molar ratio with respect to the total amount of the C4 or more olefins contained in the raw material fluid of the pipe 104. . In addition, although the raw material fluid means the sum total of the fluid supplied through piping 101, 102, and 103, these do not necessarily need to be joined before entering the reactor 10, and may be supplied to the reactor 10, respectively. . The source gas supplied to the reactor 10 reacts with the catalyst in the reactor 10, and a reactor outlet gas containing propylene, other olefins, paraffins, aromatic compounds and water is obtained.

The reactor outlet gas is fed to a general separation and purification system 20 such as cooling, compression, and distillation via a pipe 105, and in this separation and purification system 20, a fluid rich in hydrocarbons having 3 or less carbon atoms and hydrocarbons having 4 or more carbon atoms The abundant fluid (A) and the water-rich fluid are separated and taken out through the pipes 106, 108, and 107, respectively. Here, a fluid rich in hydrocarbons having 3 or less carbon atoms represents at least one fluid. For example, one fluid containing all hydrocarbons having 3 or less carbon atoms may be used, and a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms, or containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms Two fluids, such as a fluid and a fluid rich in C3 hydrocarbons, may be used. Moreover, three or more fluids may be sufficient.

A part of the hydrocarbon (A) rich in hydrocarbons having 4 or more carbon atoms is drawn out of the process from the pipe 109, and the remaining fluid C is supplied to the general separation and purification system 30A such as distillation via the pipe 110. A part of fluid B of fluid A may be taken out of a process. At this time, the extraction fluid B may be used as a cracker raw material for steam cracking. In that case, it is preferable that the extraction fluid B is brought into contact with the hydrogenation catalyst and supplied to steam cracking as a fluid having a high paraffin concentration. It is preferable that the sum total of the aromatic compound concentration of the extraction fluid (B) at this time is less than 5.0 volume%.

In the separation purification system 30A, at least a part of the fluid (D) is separated into a fluid (D) having an aromatic compound concentration lower 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 piping 102, and the fluid E is discharged from the process from the piping 111. The extraction fluid E may be mixed with decomposition gasoline fraction such as steam cracking. In that case, it is preferable that the total concentration of hydrocarbons of 4 carbon atoms contained in the fluid (E) is less than 5% by weight.

Some fluid (hereinafter, "fluid X") of the fluid D may be extracted out of the process. At this time, the extraction fluid X may be used as a cracker raw material for steam cracking. In that case, it is preferable that the extraction fluid (X) is brought into contact with the hydrogenation catalyst and supplied to the steam cracking as a fluid having a high paraffin concentration. It is preferable that the sum total of the aromatic compound concentration of extraction liquid X at this time is less than 5.0 mol%.

The fluid (D) and the fluid (X) are not necessarily required, but at least any fluid is preferably extracted from the process in order to prevent accumulation of paraffins.

 <Description of 2nd aspect (FIG. 2)>

At least one of the olefin raw material having at least 4 carbon atoms, the hydrocarbon fluid having at least 4 carbon atoms (I) from the second separation purification system 30B, methanol and dimethyl ether is passed through the reactors 101, 102, 103 and 104, respectively. Supplied to (10). Thereafter, in the first separation purification system 20, the separation gas is separated from the outlet gas of the reactor 10 into a fluid rich in hydrocarbons having 3 or less carbon atoms, hydrocarbon fluids (A) having 4 or more carbon atoms, and fluid rich in water. Since the process of is the same as FIG. 1, description is abbreviate | omitted.

The hydrocarbon fluid A having 4 or more carbon atoms is supplied from the piping 108 to a general separation purification system 30B such as distillation. In the separation purification system 30B, a fluid G having an aromatic compound concentration lower than the fluid A and a fluid F having a hydrocarbon concentration of 4 or more carbon atoms lower than the fluid A are separated. Fluid F is drawn out of the process from piping 112. The extraction fluid F may be mixed with decomposition gasoline fraction such as steam cracking. In that case, it is preferable that the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid F is less than 5% by weight.

The fluid G is withdrawn from the pipe 113, the part H is withdrawn from the process via the pipe 114, and the remaining fluid I is recycled to the reactor 10 via the pipe 102. . The extraction fluid H may be used as a cracker raw material for steam cracking. In that case, it is preferable that the fluid H is brought into contact with the hydrogenation catalyst and supplied to steam cracking as a fluid having a high paraffin concentration. It is preferable that the sum total of the aromatic compound 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 necessary, but in order to prevent the accumulation of paraffins, it is preferable to eject at least a part of the fluid from the process.

[Embodiment of the Process]

 Third Embodiment (FIG. 3)

EMBODIMENT OF THE INVENTION Below, embodiment of the process of this invention is described with reference to drawings.

3 illustrates one aspect of the process of the present invention.

In Fig. 3, reference numeral 13 denotes a reactor, 23 a compressor, 33 a knockout drum, 43 a oil / water separator, 53 a first separation refining system, and 63 a second separation refining system. to be. 301 to 315 each represent a pipe.

At least one of an olefin raw material having at least 4 carbon atoms, a hydrocarbon fluid having at least 4 carbon atoms from the first separation refining system (53), methanol and dimethyl ether is passed through the reactors 301, 302, 303 and 304 to the reactor, respectively. It is supplied to 13. The C4 or more olefin raw material supplied to the reactor 13 may contain C4 or more paraffins, for example, normal butane, isobutane, and the like. In addition, butadiene and an aromatic compound may be contained in the raw material fluid supplied to the reactor 13 via the piping 304. As described above, the butadiene concentration in the raw material fluid is usually 2.0% by volume or less, and the total amount of the aromatic compound is usually less than 0.05 in molar ratio with respect to the total amount of the C4 or more olefins contained in the raw material fluid of the pipe 304. . 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 be joined before entering the reactor 13, and may be supplied to the reactor 13, respectively. . The source gas supplied to the reactor 13 is reacted in contact 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, for example, via a heat exchanger, and the gas fluid K after cooling is boosted by the compressor 23 from the pipe 305. Although one compressor 23 may be sufficient, it is preferable that it is a plurality. After each compressor 23, a heat exchanger and a knockout drum 33 are provided, and after cooling the gas after compression, it isolate | separates into gas fluid L and a condensation component. The condensation component is fed to the oil / water separator 43 via the piping 308, and is separated into the liquid fluid M rich in hydrocarbons having at least 4 carbon atoms and the fluid rich in water, and the fluid rich in water is discharged from the piping 310. The liquid fluid M rich in hydrocarbon having 4 or more carbon atoms is fed from the pipe 309 to the second separation purification system 63.

The gas fluid L separated from the knockout drum 33 is fed to a general first separation purification system 53 such as distillation via a pipe 307, and a fluid rich in hydrocarbons having 3 or less carbon atoms and hydrocarbons having 4 or more carbon atoms Separated into the abundant fluid (N), it is taken out through the pipes (313, 314), respectively. Here, a fluid rich in hydrocarbons having 3 or less carbon atoms represents at least one fluid. For example, one fluid containing all hydrocarbons having 3 or less carbon atoms may be used, and a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms, or containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms Two fluids, such as a fluid and a fluid rich in C3 hydrocarbons, may be used. Furthermore, three or more fluids may be sufficient.

The portion P of the fluid N rich in hydrocarbon having 4 or more carbon atoms is extracted from the process via 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 steam cracking. In that case, it is preferable that the fluid P is brought into contact with the hydrogenation catalyst and supplied to steam cracking as a fluid having a high paraffin concentration. It is preferable that the sum total of the aromatic compound 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, which may be extracted from the process as it is, in which case the liquid fluid M ) May be used as a cracker raw material for steam cracking. In that case, it is preferable that the fluid M is brought into contact with a hydrogenation catalyst and supplied to steam cracking as a fluid having a high paraffin concentration. It is preferable that the sum total of the aromatic compound concentration of the fluid M at this time is less than 5.0 volume%.

Moreover, when the C4 hydrocarbon concentration in a liquid fluid M is low, you may mix with decomposition gasoline fractions, such as steam cracking. In that case, it is preferable that the total concentration of C4 hydrocarbons contained in the fluid M is less than 5% by weight.

In addition, at least a part of the liquid fluid (M) has a hydrocarbon concentration of 4 (C) having a lower aromatic compound concentration than the liquid fluid (M) and a hydrocarbon of 4 carbon atoms in the second separation purification system 60 which is a general separation process such as distillation. It is preferable to separate into the fluid S lower than the liquid fluid M. Here, the separated fluid R is discharged from the pipe 111, but the fluid R is a pipe through which the fluid K, the fluid L, the fluid N, the fluid P, and the fluid Q flow. It is preferable to return to one or a plurality of points 305, 307, 314, 315, and 302.

On the other hand, the fluid S may be drawn out from the pipe 312, and the fluid S may be mixed with cracked gasoline fraction such as steam cracking. In that case, it is preferable that the total concentration of hydrocarbons having 4 carbon atoms contained in the fluid S is less than 5% by weight.

Extraction of the fluid P out of the process is not necessary, but in order to prevent accumulation of paraffins, it is preferable to eject at least a part of the fluid from the process.

Although an Example is given to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example at all.

[Catalyst preparation]

The catalyst used by the following example and the comparative example was prepared as follows.

 <Catalyst preparation>

26.6 g of tetra-n-propylammonium bromide (TPABr) and 4.8 g of sodium hydroxide were sequentially dissolved in 280 g of water, followed by 75 g of colloidal silica (SiO ₂ = 40 wt%, Al <0.1 wt%) and 35 g of water. The mixture was added slowly and stirred for 10 minutes to obtain an aqueous gel. Next, this gel was poured into a 1000 ml autoclave, and hydrothermal synthesis was carried out at 170 ° C. for 72 hours while stirring at 300 rpm under magnetic pressure. The product was separated by solid filtration, washed with water sufficiently and then dried at 100 ° C. for 24 hours. The catalyst after drying baked at 550 degreeC for 6 hours under air circulation, and obtained Na type aluminosilicate.

This Na type aluminosilicate-2.0g was suspended in 40 ml of 1-M ammonium nitrate aqueous solution, and it stirred at 80 degreeC for 2 hours. The liquid after treatment separated the solid component by suction filtration, and after fully washing with water, it was suspended in 40 ml of 1 M ammonium nitrate aqueous solution again, and it stirred at 80 degreeC for 2 hours. The liquid after treatment separated the solid component by suction filtration, and after wash | cleaning enough, it dried at 100 degreeC for 24 hours. The catalyst after drying baked at 500 degreeC for 4 hours under air circulation, and obtained H type aluminosilicate.

This catalyst confirmed that the structure of zeolite was MFI type by XRD (X-ray diffraction). The composition of the catalyst was quantified by chemical analysis, and the result was SiO ₂ / Al ₂ O ₃ = 1100 (molar ratio).

[Production of propylene]

The production example and the comparative example of propylene which used the said catalyst are shown above.

<Example 1>

Propylene was produced using the above catalyst.

In the reaction, a mixture of 0.10 g of the catalyst and 1.0 g of quartz was charged into a quartz reaction tube having an internal diameter of 6 mm using an atmospheric pressure fixed bed flow reactor. In this reactor, a simulated gas corresponding to the composition of the reactor inlet gas (pipe 104 of FIG. 1 or FIG. 2) in the present invention isobutene (40% by volume), methanol (20% by volume), benzene ( 0.8 vol.%), Butadiene (0.1 vol.%) And isobutane (39.1 vol.%) Were supplied via an evaporator. Reaction temperature (reactor inlet gas temperature) was 550 degreeC. 70 minutes after the start of the reaction, the product was analyzed by gas chromatography. The reaction conditions and reaction results at that time are shown in Table 1.

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

Moreover, reaction was continued and the time until the conversion ratio of methanol fell below 99% was evaluated as 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 benzene concentration 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.

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

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

Comparative Example 1

The reaction was carried out in the same manner as in Example 1 except that the benzene concentration supplied to the reactor was 3.2 vol% and the isobutane concentration was 36.7 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.

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 originally used for propylene production by the reaction of butene and / or methanol and benzene in the raw material to produce alkylated benzene.

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

Thus, according to the method of the present invention, lowering the aromatic compound concentration at the reactor inlet by extracting at least a portion of the aromatic compound without recycling is very effective for achieving high propylene yield and suppressing catalyst coking deterioration.

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

This application is based on the JP Patent application (Japanese Patent Application 2006-255503) filed on September 21, 2006, and the Japanese Patent Application (Japanese Patent Application 2006-255504) filed on September 21, 2006, The content is taken here as a reference.

The present invention can provide a novel and economical process for producing propylene by reacting olefins having 4 or more carbon atoms with at least one of methanol and dimethyl ether, and a novel and economical process integrating the process and steam cracking. .

Claims (63)

In a method for producing propylene by contacting a olefin having at least 4 carbon atoms with at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, At least a part of the aromatic compounds contained in the reactor outlet effluent gas (reactor outlet gas) is withdrawn and A method for producing propylene, wherein at least a part of the olefins having 4 or more carbon atoms contained in the reactor outlet effluent gas (reactor outlet gas) is brought into contact with the catalyst in the reactor again. The method of claim 1, The said C4 or more olefin raw material contains C4 or more paraffins, The manufacturing method of propylene characterized by the above-mentioned. The method of claim 2, Said paraffins contain at least one of normal butane and isobutane, The manufacturing method of propylene characterized by the above-mentioned. The method according to any one of claims 1 to 3, Butadiene is contained in the raw material supplied to the said reactor, The manufacturing method of the propylene characterized by the above-mentioned. The method according to any one of claims 1 to 4, The total amount of the aromatic compound contained in the whole raw material supplied to the said reactor is less than 0.05 in molar ratio with respect to the total amount of a C4 or more olefin contained in the whole raw material, The manufacturing method of propylene characterized by the above-mentioned. The method according to any one of claims 1 to 5, A method for producing propylene, wherein the amount of olefins having 4 or more carbon atoms supplied to the reactor is 0.2 or more and 10 or less in molar ratio with respect to a total of twice the number of moles of methanol and the number of moles of dimethyl ether supplied to the reactor. The method according to any one of claims 1 to 6, A method for producing propylene, characterized by controlling the total concentration (substrate concentration) of olefins having 4 or more carbon atoms and methanol and dimethyl ether contained in all the raw materials supplied to the reactor to 20 vol% or more and 80 vol% or less. In the method for producing propylene by contacting a olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), (2) and (3A) Process for producing propylene comprising a process comprising a. Process (1): The olefin raw material of C4 or more C4, the hydrocarbon fluid (D) recycled from the process (3A), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the C4 or more C4 olefin in a reactor outlet is A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with said catalyst at reaction conditions that are at least 20% and less than 90% relative to the molar flow rate of said olefin at the reactor inlet. Reactor outlet gas) Step (2): A step of separating the reactor outlet gas in the step (1) into a hydrocarbon rich hydrocarbon having 3 or less carbon atoms, a fluid rich hydrocarbon of 4 or more carbon atoms, and a fluid rich in water. Step (3A): At least a part of the fluid (C) of the fluid (A) in the step (2) is a fluid (D) having a lower aromatic compound concentration than the fluid (C) and a hydrocarbon concentration of 4 carbon atoms. Separating into fluid (E) lower than fluid (C), said fluid (D) being recycled to a reactor, and withdrawing said fluid (E) from the process. In the method for producing propylene by contacting a olefin having 4 or more carbon atoms and at least one of methanol and dimethyl ether in a reactor in the presence of a catalyst, the following steps (1), (2) and (3A) Process for producing propylene comprising a process comprising a. Process (1): The olefin raw material of C4 or more C4, the hydrocarbon fluid (D) recycled from the process (3A), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the C4 or more C4 olefin in a reactor outlet is A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with said catalyst at reaction conditions that are at least 20% and less than 90% relative to the molar flow rate of said olefin at the reactor inlet. Reactor outlet gas) Step (2): A step of separating the reactor outlet gas from the above step (1) into a hydrocarbon-rich hydrocarbon-containing fluid, a hydrocarbon-rich hydrocarbon (A), and a water-rich fluid. Step (3A): A part (B) of the fluid (A) in the step (2) is extracted from the process, and the remaining fluid (C) is a fluid having an aromatic compound concentration lower than that of the fluid (C) ( D) and separating the hydrocarbon concentration of 4 carbon atoms into a fluid (E) lower than the fluid (C), the fluid (D) is recycled to the reactor, and the fluid (E) is discharged from the process. The method according to claim 8 or 9, An olefin raw material having 4 or more carbon atoms, wherein the reactor is composed of two or more reaction units connected in series; At least one of methanol and dimethyl ether; And at least one of the fluid (D) containing the recycled hydrocarbon is divided and supplied into the reaction section in the first stage and the reaction section in the second stage and later. The method according to any one of claims 8 to 10, The fluid (B) is supplied to a steam cracking process and used as a cracker raw material, The manufacturing method of propylene. The method of claim 11, At least a portion of the fluid (B) is brought into contact with a hydrogenation catalyst and then fed to a steam cracking process. The method according to any one of claims 8 to 12, The sum total of the aromatic compound concentration contained in the said fluid (B) is less than 5.0 volume%, The manufacturing method of propylene characterized by the above-mentioned. The method according to any one of claims 8 to 13, The said fluid (E) is mixed with the decomposition gasoline fraction of a steam cracking process, The manufacturing method of propylene characterized by the above-mentioned. The method according to any one of claims 8 to 14, The total concentration of C 4 hydrocarbons contained in the fluid (E) is less than 5% by weight. The method according to any one of claims 8 to 15, By controlling the flow rates of the fluid (B) and the fluid (E), the total concentration (substrate concentration) of olefins having 4 or more carbon atoms and methanol and dimethyl ether contained in all the raw materials supplied to the reactor is 20% by volume or more and 80% by volume. A method for producing propylene, which is controlled at% or less. In the method for producing propylene by contacting a mixture containing at least one of olefins having 4 or more carbon atoms and methanol and dimethyl ether in the reactor in the presence of a catalyst, the following steps (1), (2) and (3B) Process for producing propylene comprising a process comprising a. Process (1): The olefin raw material of carbon number 4 or more, the hydrocarbon fluid (I) recycled from process (3B), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the carbon number 4 or more olefins of a reactor exit is reactor A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst under reaction conditions of 20% or more and less than 90% relative to the molar flow rate of the olefin at the inlet (reactor outlet Gas) Step (2): A step of separating the reactor outlet gas from the step (1) into a hydrocarbon rich in hydrocarbon having 3 or less carbon atoms, a fluid rich in hydrocarbon having 4 or more carbon atoms, and a fluid rich in water. Step (3B): The fluid (A) in the step (2) includes a fluid (G) having an aromatic compound concentration lower 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 portion (I) of said fluid (G) is recycled to the reactor. In the method for producing propylene by contacting a mixture containing at least one of olefins having 4 or more carbon atoms and methanol and dimethyl ether in the reactor in the presence of a catalyst, the following steps (1), (2) and (3B) Process for producing propylene comprising a process comprising a. Process (1): The olefin raw material of carbon number 4 or more, the hydrocarbon fluid (I) recycled from process (3B), and at least one of methanol and dimethyl ether are supplied to a reactor, and the molar flow rate of the carbon number 4 or more olefins of a reactor exit is reactor A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst under reaction conditions of 20% or more and less than 90% relative to the molar flow rate of the olefin at the inlet (reactor outlet Gas) Step (2): A step of separating the reactor outlet gas from the above step (1) into a hydrocarbon-rich hydrocarbon-rich fluid, a hydrocarbon-rich hydrocarbon (A), and a water-rich fluid. Step (3B): The fluid (A) in the step (2) includes a fluid (G) having an aromatic compound concentration lower than the fluid (A) and a fluid (F) having a hydrocarbon concentration of 4 carbon atoms lower than the fluid (A). And the fluid (F) is withdrawn from the process, a part (I) of the fluid (G) is recycled to the reactor and the remaining fluid (H) is withdrawn from the process. The method of claim 17 or 18, An olefin raw material having at least 4 carbon atoms, which is composed of two or more reaction units connected in series with the reactor; At least one of methanol and dimethyl ether; And at least one of the fluid (I) containing the recycled hydrocarbon is dividedly supplied into the reaction section in the first stage and the reaction section in the second and subsequent stages, thereby producing propylene. The method according to any one of claims 17 to 19, The fluid (H) is supplied to a steam cracking process and used as a cracker raw material, The manufacturing method of propylene characterized by the above-mentioned. The method of claim 20, At least a part of the fluid (H) is brought into contact with a hydrogenation catalyst and then fed to a steam cracking process. The method according to any one of claims 17 to 21, The sum total of the aromatic compound concentration contained in the said fluid (H) is less than 5.0 volume%, The manufacturing method of the propylene characterized by the above-mentioned. The method according to any one of claims 17 to 22, The fluid (F) is mixed with the cracked gasoline fraction of a steam cracking process. The method according to any one of claims 17 to 23, The total concentration of C 4 hydrocarbons contained in the fluid (F) is less than 5% by weight. The method according to any one of claims 17 to 24, By controlling the flow rates of the fluid (F) and the fluid (H), the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in all the raw materials supplied to the reactor, is 20% by volume or more and 80% by volume The manufacturing method of propylene characterized by the following control. The method according to any one of claims 8 to 25, After the step (2) condenses and removes water from the reactor outlet gas by a cooling and compression step, the gas 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 process for producing propylene, comprising the step of separating the above-hydrocarbon-rich fluid into a fluid rich in C 3 hydrocarbons and a fluid rich in C 4 or more hydrocarbons by distillation. The method according to any one of claims 8 to 25, After the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, the gas is separated into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms by distillation. A process for producing propylene, comprising the steps of separating a fluid rich in hydrocarbons below into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms. The method according to any one of claims 8 to 25, After the step (2) condenses and removes water from the reactor outlet gas by a cooling and compression step, the fluid contains a hydrocarbon having 2 or less carbon atoms and 3 hydrocarbons and a fluid rich in hydrocarbons having 3 or more carbon atoms by distillation. Separating 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 rich in hydrocarbons having 4 or more carbon atoms by distillation. The method according to any one of claims 8 to 25, After the step (2) condenses and removes moisture from the reactor outlet gas by a cooling and compression step, the gas is separated into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms by distillation. A process for producing propylene, comprising distilling a fluid rich in hydrocarbons below into a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms. The method according to any one of claims 8 to 29, The said C4 or more olefin raw material contains C4 or more paraffins, The manufacturing method of propylene characterized by the above-mentioned. The method of claim 30, Said paraffins contain at least one of normal butane and isobutane, The manufacturing method of propylene characterized by the above-mentioned. The method according to any one of claims 8 to 31, Butadiene is contained in the raw material supplied to the said reactor, The manufacturing method of the propylene characterized by the above-mentioned. The method according to any one of claims 8 to 32, The total amount of the aromatic compound contained in the whole raw material supplied to the said reactor is less than 0.05 in molar ratio with respect to the total amount of a C4 or more olefin contained in the whole raw material, The manufacturing method of propylene characterized by the above-mentioned. The method according to any one of claims 8 to 33, A method for producing propylene, wherein the amount of olefins having 4 or more carbon atoms supplied to the reactor is 0.2 or more and 10 or less in molar ratio with respect to a total of twice the number of moles of methanol and the number of moles of dimethyl ether supplied to the reactor. The method according to any one of claims 8 to 34, The method for producing propylene, wherein the olefin raw material having at least 4 carbon atoms supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained in a steam cracking process. In a method of producing propylene by bringing a mixture containing at least one of olefins having 4 or more carbon atoms and methanol and dimethyl ether into the reactor in the presence of a catalyst, the following steps (1C), (2C) and (3C) And (4C) a process comprising the step of producing propylene. Process (1C): At least one of a olefin raw material having at least 4 carbon atoms, a hydrocarbon fluid (Q) recycled from step (4C), and methanol and dimethyl ether is supplied to the reactor, and the molar flow rate of the at least 4 carbon olefins at the reactor outlet is increased. A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst at reaction conditions that are at least 20% and less than 90% relative to the molar flow rate of the olefin at the reactor inlet. Process of obtaining outlet gas) Step (2C): The reactor outlet gas from the step (1C) is cooled, and a gas fluid (L), a liquid fluid (M) rich in hydrocarbons having 4 or more carbon atoms, containing aromatic compounds, and a fluid rich in water are used. Separating process Step (3C): The step of separating the gas fluid (L) in the step (2C) into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons (N) having 4 or more carbon atoms. Step (4C): a step of recycling at least part of the fluid Q of the fluid N to the reactor. In a method of producing propylene by bringing a mixture containing at least one of olefins having 4 or more carbon atoms and methanol and dimethyl ether into the reactor in the presence of a catalyst, the following steps (1C), (2C) and (3C) And (4C) a process comprising the step of producing propylene. Process (1C): At least one of a olefin raw material having at least 4 carbon atoms, a hydrocarbon fluid (Q) recycled from step (4C), and methanol and dimethyl ether is supplied to the reactor, and the molar flow rate of the at least 4 carbon olefins at the reactor outlet is increased. A gas containing propylene and other olefins, paraffins, aromatic compounds and water from the reactor outlet, in contact with the catalyst at reaction conditions of 20% or more and less than 90% relative to the molar flow rate of the olefin at the reactor inlet. Process of obtaining outlet gas) Step (2C): A liquid containing an aromatic compound that is rich in gaseous fluid (L) and C4 or more hydrocarbons by cooling the reactor outlet gas from the step (1C) and compressing the gas fluid (K) after cooling. Process to separate into fluid (M) and water rich fluid Step (3C): The step of separating the gas fluid (L) in the step (2C) into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons (N) having 4 or more carbon atoms. Step (4C): A step of extracting a part (P) of the fluid (N) from the process and recycling the remaining fluid (Q) to the reactor. 38. The liquid (M) having a lower aromatic compound concentration in the liquid fluid (M) and a hydrocarbon concentration of 4 carbon atoms in the liquid fluid (M) according to claim 36 or 37, by distilling the liquid fluid (M). Process for producing propylene characterized by separating into lower fluid (S). The method of claim 38, Producing propylene characterized in that the fluid (R) is returned to the distribution point of any one or two or more fluids selected from the fluids (K), (L), (M), (P) and (Q). Way. The method according to any one of claims 36 to 39, The step (3C) separates the gas fluid (L) into distillation, a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms, and further distills a fluid rich in hydrocarbons having 3 or more carbon atoms. And a step of separating into a hydrocarbon-rich fluid and a hydrocarbon-rich fluid (N) containing at least 4 carbon atoms. The method according to any one of claims 36 to 39, The step (3C) separates the gas fluid (L) into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons (N) having 4 or more carbon atoms by distillation, and further contains a hydrocarbon rich in hydrocarbons having 3 or less carbon atoms. A process for producing propylene, comprising the step of separating by distillation into a fluid rich in hydrocarbons having 2 or less carbon atoms and a fluid rich in hydrocarbons having 3 carbon atoms. The method according to any one of claims 36 to 39, The step (3C) separates the gas fluid (L) into a fluid containing hydrocarbons having 2 or less carbon atoms and hydrocarbons having 3 or more carbon atoms and a fluid rich in hydrocarbons having 3 or more carbon atoms by distillation. A process for producing propylene, comprising the step of separating a rich fluid into a fluid rich in hydrocarbons having 3 carbon atoms and a fluid rich in hydrocarbons having 4 or more carbon atoms (N). The method according to any one of claims 36 to 39, The step (3C) separates the gas fluid (L) into a fluid rich in hydrocarbons having 3 or less carbon atoms and a fluid rich in hydrocarbons (N) having 4 or more carbon atoms by distillation, and further rich in hydrocarbons having 3 or less carbon atoms. And distilling the fluid into a fluid containing a hydrocarbon having 2 or less carbon atoms, a hydrocarbon containing 3 carbon atoms, and a fluid rich in hydrocarbons containing 3 carbon atoms. The method according to any one of claims 36 to 43, An olefin raw material having 4 or less carbon atoms, wherein the reactor is composed of two or more reaction units connected in series; At least one of methanol and dimethyl ether; And at least one of the fluid containing the recycled hydrocarbon is dividedly supplied into the reaction section in the first stage and the reaction section in the second stage and later. The method according to any one of claims 36 to 44, The said C4 or more olefin raw material contains C4 or more paraffins, The manufacturing method of propylene characterized by the above-mentioned. The method of claim 45, The method for producing propylene, wherein the paraffins include at least one of normal butane and isobutane. The method according to any one of claims 36 to 46, Butadiene is contained in the raw material supplied to the said reactor, The manufacturing method of the propylene characterized by the above-mentioned. The method according to any one of claims 36 to 47, The total amount of the aromatic compound contained in the whole raw material supplied to the said reactor is less than 0.05 in molar ratio with respect to the total amount of a C4 or more olefin contained in the whole raw material, The manufacturing method of propylene characterized by the above-mentioned. 49. The method of any of claims 36 to 48, At least one of the fluid (M) and the fluid (P) is supplied to a steam cracking process and used as a cracker raw material. The method of claim 49, At least a portion of the fluid (M) and at least one of the fluid (P) is contacted with a hydrogenation catalyst and then fed to a steam cracking process. The method according to any one of claims 36 to 50, The sum total of the aromatic compound concentration contained in at least one of the said fluid (M) and the said fluid (P) is less than 5.0 volume%, The manufacturing method of the propylene characterized by the above-mentioned. The method according to any one of claims 36 to 51, Mixing the fluid (M) to the cracked gasoline fraction of the steam cracking process. The method of any one of claims 36-52, The total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (M) is less than 5% by weight. The method of any one of claims 36 to 53, wherein By controlling the flow rates of the fluid (M) and the fluid (P), the total concentration (substrate concentration) of olefins having 4 or more carbon atoms and methanol and dimethyl ether contained in all the raw materials supplied to the reactor is 20% by volume or more and 80% by volume. A method for producing propylene, which is controlled at% or less. The method of any one of claims 38-54, The fluid (R) is supplied to a steam cracking process and used as a cracker raw material, The manufacturing method of propylene characterized by the above-mentioned. The method of claim 55, At least a part of the fluid (R) is brought into contact with a hydrogenation catalyst and then fed to a steam cracking process. The method of any one of claims 38-56, wherein The sum total of the aromatic compound concentration contained in the said fluid (R) is less than 5.0 volume%, The manufacturing method of the propylene characterized by the above-mentioned. The method according to any one of claims 38 to 57, Mixing the fluid (S) to the cracked gasoline fraction of the steam cracking process. The method according to any one of claims 38 to 58, The total concentration of hydrocarbons having 4 carbon atoms contained in the fluid (S) is less than 5% by weight. The method according to any one of claims 38 to 59, By controlling the flow rates of the fluid (P), the fluid (R) and the fluid (S), the total concentration (substrate concentration) of olefins having 4 or more carbon atoms, methanol and dimethyl ether contained in all the raw materials supplied to the reactor is 20 vol. A method for producing propylene, wherein the content is controlled to not less than 80% by volume. 61. The method of any of claims 38-60, Return of the fluid R when the fluid R is returned to the point of any one or two or more fluids selected from the fluids K, L, N, P, and Q. By controlling the point and the flow rate, the total concentration (substrate concentration) of olefins having 4 or more carbon atoms and methanol and dimethyl ether contained in all the raw materials supplied to the reactor is controlled to 20 volume% or more and 80 volume% or less. Process for the preparation of propylene. The method of any one of claims 36 to 61, A method for producing propylene, characterized in that the amount of olefins having 4 or more carbon atoms to be supplied to the reactor is 0.2 to 10 or less in molar ratio with respect to the sum of the number of moles of methanol and the number of moles of dimethyl ether supplied to the reactor. 63. The method of any of claims 36 to 62, The method for producing propylene, wherein the olefin raw material having at least 4 carbon atoms supplied to the reactor contains a hydrocarbon fluid having 4 carbon atoms obtained in a steam cracking process.

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