WO2009145280A1 - Method of producing mono(lower alkyl)monoalkanolamine and apparatus therefor - Google Patents

Method of producing mono(lower alkyl)monoalkanolamine and apparatus therefor Download PDF

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WO2009145280A1
WO2009145280A1 PCT/JP2009/059819 JP2009059819W WO2009145280A1 WO 2009145280 A1 WO2009145280 A1 WO 2009145280A1 JP 2009059819 W JP2009059819 W JP 2009059819W WO 2009145280 A1 WO2009145280 A1 WO 2009145280A1
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reaction
mono
lower alkyl
raw material
producing
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PCT/JP2009/059819
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French (fr)
Japanese (ja)
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晋也 立花
達也 辻内
剛司 大石
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三菱重工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins

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  • the present invention relates to a method and an apparatus for producing a mono-lower alkyl monoalkanolamine obtained by reacting a mono-lower alkyl monoalkanolamine having a high commercial demand by the reaction of a mono-lower alkyl amine and an alkylene oxide.
  • Mono lower alkyl monoalkanolamines are common organic synthetic intermediate materials, such as cationic flocculants, intermediates for medical and agricultural chemicals, etching solutions for resins, softeners for synthetic fibers, corrosion inhibitors, petroleum refining or petroleum processes. It is a useful compound with high commercial demand such as a neutralizing agent and a dispersing agent.
  • zeolite catalyst method using zeolite as a catalyst has been proposed as a method for producing mono-lower alkyl monoalkanolamine by reacting mono-lower alkylamine and alkylene oxide (Patent Document 1).
  • reference numeral 1 denotes a liquid / liquid reaction tower as a reactor, which is filled with a zeolite catalyst, and is supplied with raw material I (mono-lower alkylamine) and raw material II (alkylene oxide),
  • reaction is performed by a zeolite catalyst method to obtain a product 2 containing unreacted raw materials.
  • the product 2 containing the unreacted raw material contains unreacted mono-lower alkylamine (unreacted raw material I) and alkylene oxide (unreacted raw material II) as the unreacted raw material, these and the reaction product 3 Are separated by the unreacted raw material recovery distillation column 4 and the separated and recovered unreacted mono-lower alkylamine (raw material I) and alkylene oxide (raw material II) are sent back to the reactor 1 as unreacted raw materials 5. Yes.
  • non-water distillation column 6 removes water and light components 7 from the reaction product 3 derived from the unreacted raw material recovery distillation column 4 by distillation, and the reaction after these water and light components 7 are removed.
  • the product 3a is sent to the purification distillation column 8.
  • non-water indicates a state where the amount of water contained in the component is 1000 ppm or less.
  • reaction product 3a after removing the water and the light component 7 is sent to the purification distillation column 8, where mono-lower alkyl monoalkanolamine and mono-lower alkyl dialkanolamine (residue dimer) produced by the reaction. Are separated by distillation to recover the mono-lower alkyl monoalkanolamine as the target reaction product 9.
  • Patent Document 2 a method of producing under supercritical conditions (temperature conditions of 100 to 200 ° C. and pressure conditions of 17 to 24 MPa) has been proposed (Patent Document 2).
  • Patent Document 3 a method for producing monomethylaminoethanol from monomethylamine and ethylene oxide is disclosed (Patent Document 3).
  • unreacted monomethylamine is recovered by mixing the crude liquid with alcohol in an amine recovery distillation column or by charging the crude liquid and alcohol in a separate line.
  • JP 2004-275933 A JP 59-13751 A JP-A-8-333310
  • the “zeolite catalyst method” according to Patent Document 1 has a problem in that the reaction rate and selectivity are lowered due to catalyst deterioration. Moreover, since it is difficult to keep the temperature in the reactor 1 uniform, there is a problem that the product cannot be stably produced. Further, the zeolite catalyst method has a problem that it is necessary to use a cooling facility such as a condenser in the distillation column for separating the mono-lower alkylamine in the distillation step, resulting in an increase in energy consumption.
  • the “supercritical method” according to Patent Document 2 has a problem that the temperature condition needs to be 100 to 200 ° C. and the pressure condition needs to be 17 to 24 MPa, which increases the power and cost required for operation.
  • the present invention is to provide a production method and apparatus for a mono-lower alkyl monoalkanolamine capable of producing a mono-lower alkyl monoalkanol amine with energy saving.
  • the first invention of the present invention for solving the above-mentioned problem is a method for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine (AA) with an alkylene oxide (AO).
  • a mono-lower alkylamine (AA) and an alkylene oxide (AO) are supplied, and the reaction product is reacted in a gas-liquid mixed phase in the reaction column, and the reaction product is separated from the reaction column in a liquid state. It exists in the manufacturing method of mono lower alkyl monoalkanolamine.
  • the second invention is the method for producing mono-lower alkyl monoalkanolamine according to the first invention, wherein the reaction tower is a reaction / distillation tower.
  • the third invention is the method for producing a mono-lower alkyl monoalkanolamine according to the second invention, wherein the reaction / distillation tower is a multistage type.
  • the reaction temperature of the reaction / distillation tower is 40 to 200 ° C.
  • the top temperature of the reaction / distillation tower is 40 to 100 ° C.
  • the method for producing a mono-lower alkyl monoalkanolamine is characterized in that the column bottom temperature is 120 to 200 ° C. and the pressure in the reaction / distillation column is 0.45 to 1.3 MPa.
  • the fifth invention is the method for producing mono-lower alkylmonoalkanolamine according to the first invention, wherein the reaction tower is a gas-liquid mixed phase reaction tower.
  • a mono-lower alkylamine (AA) and an alkylene oxide (AO) are reacted in a gaseous state at a reaction temperature of 80 to 200 ° C. and a pressure of 0.2 to 0.8 MPa.
  • the method for producing a mono-lower alkylmonoalkanolamine is characterized in that the reaction product is used as a liquid and the reaction product is separated from the liquid phase.
  • a mono lower alkyl monoalkanolamine according to the second or fifth aspect, wherein the mono lower alkyl amine (AA) is separated and recovered from the top of the reaction / distillation tower and reused. In the manufacturing method.
  • the separated unreacted raw material is returned to the raw material main supply part, or the separated unreacted raw material is returned to the top of the reaction / distillation column from the supply position of the raw material main supply part.
  • the present invention provides a method for producing a mono-lower alkyl monoalkanolamine, characterized in that the mono lower alkyl monoalkanolamine is supplied into the inside from the side portion.
  • the ninth invention is the invention according to the second or fifth invention, wherein the supply ratio of the alkylene oxide (AO) is divided and a part of the divided alkylene oxide (AO) is supplied from the raw material main supply section into the reaction / distillation column. And the remainder is fed into the reaction / distillation column from the sub-feeding portion located on the top side of the column from the feed position of the raw material main feeding portion.
  • the supply ratio of the alkylene oxide (AO) is divided and a part of the divided alkylene oxide (AO) is supplied from the raw material main supply section into the reaction / distillation column. And the remainder is fed into the reaction / distillation column from the sub-feeding portion located on the top side of the column from the feed position of the raw material main feeding portion.
  • a tenth aspect of the invention is an apparatus for producing a mono-lower alkyl monoalkanolamine by reaction of a mono-lower alkyl amine and an alkylene oxide, and supplies the mono-lower alkyl amine (AA) and the alkylene oxide (AO),
  • the reaction product is reacted in a liquid mixed phase and the reaction product is separated from the bottom of the column in a liquid state, and the reaction / distillation tower recovers the unreacted raw material in a gas state, and the product separated in the liquid state is purified to produce a target product.
  • a purification distillation column for distilling the product.
  • An eleventh aspect of the invention is that in the tenth aspect of the invention, the reaction temperature of the reaction / distillation column is 40 to 200 ° C., and the top temperature of the reaction / distillation column is 40 to 100 ° C.
  • the mono-lower alkyl monoalkanolamine production apparatus is characterized in that the column bottom temperature is 120 to 200 ° C. and the pressure in the reaction / distillation column is 0.45 to 1.3 MPa.
  • the twelfth invention is characterized in that, in the tenth or eleventh invention, the ratio of the mono-lower alkylamine raw material to the alkylene oxide raw material (alkylene oxide raw material / mono-lower alkylamine raw material) is 0.05 to 0.5.
  • the ratio of the mono-lower alkylamine raw material to the alkylene oxide raw material is 0.05 to 0.5.
  • a thirteenth aspect of the present invention is the apparatus for producing a mono-lower alkyl monoalkanolamine according to any one of the tenth to twelfth aspects of the present invention, wherein the amount of water supplied to the reaction / distillation column is 20% or less. It is in.
  • a fourteenth aspect of the invention is the mono lower alkyl monoalkanolamine according to the tenth aspect of the invention, wherein the reaction / distillation column is filled with a zeolite catalyst and the raw material is supplied in a non-aqueous state. In production equipment.
  • a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
  • FIG. 1 is a schematic view of an apparatus for producing a mono-lower alkyl monoalkanolamine according to Example 1.
  • FIG. 2 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 2.
  • FIG. 3 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 3.
  • FIG. 4 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 4.
  • FIG. 5 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 5.
  • FIG. 6 is a relationship diagram between the molar fraction and the number of stages of the reaction tower.
  • FIG. 7 is a schematic view of a mono-lower alkyl monoalkanolamine production apparatus according to a test example.
  • FIG. 8 is a view showing an example of an apparatus for producing a mono-lower alkyl monoalkanolamine using a conventional zeolite catalyst.
  • the method for producing a mono-lower alkyl monoalkanolamine according to the present invention is a method for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkylamine (raw material I: AA) and an alkylene oxide (raw material II: AO).
  • the raw material I (AA) and the raw material II (AO) are supplied to the reaction tower and reacted in a gas-liquid mixed phase in the reaction tower, and the reaction product (amine monomer) is separated from the reaction tower in a liquid state.
  • the reaction tower that is reacted in a gas-liquid mixed phase state in the reaction tower is preferably a reaction / distillation tower or a gas-liquid mixed phase reaction tower.
  • the reaction product is reacted in a gas-liquid mixed phase state in the reaction tower to obtain the target product in the liquid state, so that the reaction yield is improved.
  • the ratio of the alkylene oxide raw material to the mono-lower alkylamine raw material is not reduced, the amount of reboiler recovered as an unreacted raw material can be reduced. Become.
  • reaction columns specific examples of a reaction / distillation column and a gas-liquid mixed phase reaction column will be described in detail as reaction columns.
  • FIG. 1 is a schematic view of an apparatus for producing a mono-lower alkyl monoalkanolamine according to Example 1.
  • a mono-lower alkylmonoalkanolamine production apparatus 10-1 according to Example 1 is a mixed raw material 11 of mono-lower alkylamine (AA: raw material I) and alkylene oxide (AO: raw material II).
  • reaction-distillation column 12 which is formed by supplying a raw material main supply line L 0, separating the desired reaction products 20 by distilling the reaction product 13 which is separated in liquid form (monomer), and a residue (dimer) 21 And a refining distillation column 19.
  • Reference numeral 18 denotes a reboiler.
  • reaction-distillation column 12 as well as separating the unreacted raw materials 16 through a line L 1 from the top of the column 12a, to separate the reaction product 13 via the line L 2 from the bottom 12b Is.
  • the unreacted raw material 16 is cooled by the cooler 14 interposed in the line L 1 , becomes liquid in the flash drum 15, and is sent to the storage tank 17 for temporary storage through the line L 3 . . And since most of the raw material I is from the storage tank 17 via the line L 4 , it is returned to the supply line side of the raw material I.
  • the reaction / distillation tower of this example is a multistage type, and it is, for example, about 10 to 20 stages depending on the scale of the distillation amount.
  • the reaction temperature of the reaction / distillation column 12 is preferably set to 40 to 200 ° C., for example.
  • the top temperature of the reaction / distillation column 12 is, for example, 40 to 100 ° C., preferably 70 to 80 ° C.
  • the bottom temperature of the reaction / distillation column 12 is, for example, 120 to 200 ° C., preferably 140 to 180 ° C.
  • the pressure of the reaction / distillation column 12 is, for example, preferably 0.45 to 1.3 MPa, and more preferably 0.6 to 1.0 MPa. This is defined because the reaction does not proceed efficiently if the reaction temperature and the pressure are outside the above ranges.
  • the mono-lower alkylamine of the raw material I used in the present invention is not particularly limited.
  • monomethylamine, monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, monosec Linear or branched monoalkylamines having 1 to 6 carbon atoms, such as -butylamine, mono-t-butylamine, mono-n-pentylamine, isopentylamine, mono-n-hexylamine can be used .
  • Monomethylamine, monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, mono-t-butylamine can be preferably used, and monomethylamine, monoethylamine, monon are particularly preferred.
  • -Propylamine, monoisopropylamine, mono-n-butylamine can be used.
  • the alkylene oxide of the raw material II used in the present invention is not particularly limited, but an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide can be preferably used, and particularly preferably. Ethylene oxide and propylene oxide can be used.
  • the water concentration in the raw material supplied to the reactor is preferably in the range of 1 to 40% by weight.
  • a preferable water concentration range is 5 to 30% by weight, and a particularly preferable water concentration is 5 to 20% by weight.
  • the reaction rate varies depending on the water concentration, and the higher the water concentration, the greater the reaction rate.
  • the supply ratio of raw materials is also specified. That is, the molar ratio of alkylene oxide raw material to mono-lower alkylamine raw material (alkylene oxide (AO: raw material II) / mono-lower alkylamine (AA: raw material I)) is in the range of 0.05 to 0.5, more preferably A range of 0.1 to 0.3 is preferable.
  • the purification distillation column 19 is provided to remove the residue (dimer) 21, but the residue (dimer) 21 may be mixed in the monomer of the target reaction product 20. Alternatively, only the reaction / distillation column 12 may be used.
  • a cooling means may be provided inside or outside the reaction / distillation column 12 to remove heat to a predetermined temperature.
  • the reaction / distillation tower 12 reacts the raw material in the gas-liquid mixed phase state in the reaction tower, and the reaction product 13 in the liquid state.
  • the unreacted raw material is separated in a gaseous state, so that there is no need to provide a separate distillation column as in the prior art, and mono-lower alkyl monoalkanolamine is produced with high yield and energy saving. Can do.
  • the reaction between the monomer and the unreacted raw material 16 is suppressed, and the production of dimer as the residue 21 is suppressed. This also contributes to an improvement in the yield of the target reaction product 20.
  • FIG. 2 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 2.
  • the production apparatus 10-2 for mono-lower alkyl monoalkanolamine according to Example 2 is a reaction / mixture of a raw material 11 and a raw material II supplied from a raw material main supply line L 0.
  • the reaction of the raw material in the gas-liquid mixed phase state in the reaction column in the reaction / distillation column and the distillation of the supply of the raw material II -Since the reaction is divided into the reaction towers, the reaction efficiency is improved, and the mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
  • FIG. 3 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 3.
  • the production apparatus 10-3 for mono-lower alkylmonoalkanolamine according to Example 3 is the same as the production apparatus 10-1 for mono-lower alkylmonoalkanolamine according to Example 1 in the reaction product 13.
  • a non-aqueous distillation column 22 for removing water mixed in is provided, and the reaction product 13a from which water 23 has been removed is sent to the purification distillation column 19 to obtain the target reaction product 20. Thereby, the target reaction product 20 from which moisture has been removed can be obtained.
  • the non-aqueous distillation tower 22 is provided to remove moisture, so that the mono-lower alkyl monoalkanol amine in the non-aqueous state is removed. Can be produced with high yield and energy saving.
  • FIG. 4 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 4.
  • the mono-lower alkyl monoalkanolamine production apparatus 10-4 according to Example 4 is the same as the reaction / distillation column 12 in the mono-lower alkyl monoalkanolamine production apparatus 10-1 according to Example 1.
  • the catalyst filling tanks 30a and 30b are filled therein, and the reaction product 13 is generated by the catalytic reaction filled in the catalyst filling tanks 30a and 30b.
  • examples of the catalyst filled in the catalyst filling tank include ZSM-5 known as a known synthetic zeolite used in the zeolite catalyst method.
  • ZSM is an abbreviation of ZAOlItAOf Socony MobIl derived from the name of the developed company.
  • Examples of those having a MEL structure include ZSM-11, also known as a synthetic zeolite.
  • the catalyst is a non-aqueous reaction
  • the raw material I is an aqueous solution (for example, 40% moisture)
  • a non-aqueous distillation column 31 is provided to remove the moisture 23 in advance. It is necessary to.
  • the reaction / distillation tower is filled with the zeolite catalyst and the raw material is reacted in the gas-liquid mixed phase state in the reaction tower by the zeolite method. Therefore, the reaction efficiency is improved, and a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
  • FIG. 5 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 5.
  • the production apparatus 10-5 for mono-lower alkylmonoalkanolamine according to Example 5 is a gas-liquid produced by supplying a mixed raw material 11 of a raw material I and a raw material II through a raw material main supply line L 0. It comprises a mixed phase reaction column 40 and a purification distillation column 19 for separating the target reaction product 20 (monomer) and the residue (dimer) 21 by distilling the reaction product 13 separated in liquid form.
  • the a raw material I and the raw material II is reacted in gaseous state inside the reaction products it by the line L 2 because the reaction product 13 obtained is accumulated in the bottom portion The product 13 is separated.
  • the reaction temperature of the gas-liquid mixed phase reaction tower is, for example, 80 to 200 ° C.
  • the pressure is, for example, 0.2 to 0.8 MPa.
  • the unreacted raw material 16 is cooled by the cooler 14 interposed in the line L 1 , converted into liquid in the flash drum 15, and sent to the storage tank 17 for temporary storage through the line L 3 . . And since most of the raw material I is from the storage tank 17 via the line L 4 , it is returned to the supply line side of the raw material I.
  • the raw material I and the raw material are mixed in the gas-liquid mixed phase reaction column 40 using the gas-liquid mixed phase reaction column 40. Since the mixed raw material 11 with II is reacted, the reaction efficiency is improved, and a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
  • the amine production apparatus 10-3 having the same configuration as in Example 3 shown in FIG. 7 was used.
  • the operating conditions (temperature, pressure) of the reaction / distillation column 12, the nonaqueous distillation column 22, and the purification distillation column 19 are shown in FIG. In FIG. 7, the temperature (° C.) is enclosed by a square, and the pressure (MPa) is enclosed by a circle.
  • the amount of reboiler was reduced by about 20% compared to the conventional case, thereby reducing the amount of reboiler.
  • the temperature at the bottom outlet of the reaction / distillation tower 12 was 173 ° C. (pressure 1.02 MPa), and the temperature at the top outlet of the tower 40 was 40 ° C. (pressure 1.0 MPa).
  • a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.

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Abstract

An apparatus for producing a mono(lower alkyl)monoalkanolamine provided with a reaction/distillation column (12) into which a material mixture (11) consisting of a mono(lower alkyl)amine (AA: starting material I) and an alkylene oxide (AO: starting material II) is supplied via a main material-supplying line (L0), and a purification/distillation column (19) in which a reaction product (13) separated as a liquid is distilled and thus the target reaction product (20) (monomer) is separated from the residue (dimer)(21), wherein the unreacted starting materials (16) are separated from the column top (12a) via a line (L1) and the reaction product (13) is separated from the column bottom (12b) via another line (L2) at the same time.

Description

モノ低級アルキルモノアルカノールアミンの製造方法及び装置Method and apparatus for producing mono-lower alkyl monoalkanolamine
　本発明は、商業的需要が高いモノ低級アルキルモノアルカノールアミンをモノ低級アルキルアミンとアルキレンオキシドとの反応により得るモノ低級アルキルモノアルカノールアミンの製造方法及び装置に関するものである。 The present invention relates to a method and an apparatus for producing a mono-lower alkyl monoalkanolamine obtained by reacting a mono-lower alkyl monoalkanolamine having a high commercial demand by the reaction of a mono-lower alkyl amine and an alkylene oxide.
　モノ低級アルキルモノアルカノールアミンは、一般的な有機合成の中間原料、例えば、カチオン系凝集剤や医農薬中間体、樹脂用エッチング液、合成繊維用の柔軟剤、腐蝕防止剤、石油精製又は石油プロセス用中和剤、分散剤など商業的需要が高い有用な化合物である。 Mono lower alkyl monoalkanolamines are common organic synthetic intermediate materials, such as cationic flocculants, intermediates for medical and agricultural chemicals, etching solutions for resins, softeners for synthetic fibers, corrosion inhibitors, petroleum refining or petroleum processes. It is a useful compound with high commercial demand such as a neutralizing agent and a dispersing agent.
　モノ低級アルキルアミンとアルキレンオキシドの反応によるモノ低級アルキルモノアルカノールアミンの製造については古くから文献等で報告されている（例えば、非特許文献１）。
　モノ低級アルキルアミンとアルキレンオキシドとの反応では、モノ低級アルキルモノアルカノールアミンとモノ低級アルキルジアルカノールアミンとが並行して生成される。この反応において、モノ低級アルキルモノアルカノールアミンを選択的に得るためには、アルキレンオキシドに対しモノ低級アルキルアミンを大過剰に使用する必要がある。そのため、この反応では、未反応のモノ低級アルキルアミンが大量に残存する。 The production of mono-lower alkyl monoalkanolamines by the reaction of mono-lower alkyl amines and alkylene oxides has been reported in literature for a long time (for example, Non-Patent Document 1).
In the reaction of mono-lower alkylamine and alkylene oxide, mono-lower alkyl monoalkanolamine and mono-lower alkyl dialkanolamine are produced in parallel. In this reaction, in order to selectively obtain the mono-lower alkyl monoalkanolamine, it is necessary to use the mono-lower alkyl amine in a large excess relative to the alkylene oxide. Therefore, in this reaction, a large amount of unreacted mono-lower alkylamine remains.
　また、モノ低級アルキルアミンとアルキレンオキシドとを反応させて、モノ低級アルキルモノアルカノールアミンを製造する方法として、ゼオライトを触媒として用いるゼオライト触媒法が提案されている（特許文献１）。 Also, a zeolite catalyst method using zeolite as a catalyst has been proposed as a method for producing mono-lower alkyl monoalkanolamine by reacting mono-lower alkylamine and alkylene oxide (Patent Document 1).
　ここで、従来のゼオライト触媒を用いたモノ低級アルキルモノアルカノールアミンの製造装置の一例を図８に示す。図８に示すように、符号１は反応器である液・液反応塔であり、ゼオライト触媒が充填されており、原料Ｉ（モノ低級アルキルアミン）と原料ＩＩ（アルキレンオキシド）とが供給され、ここでゼオライト触媒法により反応して、未反応原料を含む生成物２を得る。この未反応原料を含む生成物２には、未反応の原料として未反応のモノ低級アルキルアミン（未反応原料Ｉ）及びアルキレンオキシド（未反応原料ＩＩ）を含むので、これらと反応生成物３とを未反応原料回収蒸留塔４により蒸留分離すると共に、前記分離回収した未反応のモノ低級アルキルアミン（原料Ｉ）及びアルキレンオキシド（原料ＩＩ）を未反応原料５として前記反応器１に送り戻している。 Here, an example of an apparatus for producing a mono-lower alkyl monoalkanolamine using a conventional zeolite catalyst is shown in FIG. As shown in FIG. 8, reference numeral 1 denotes a liquid / liquid reaction tower as a reactor, which is filled with a zeolite catalyst, and is supplied with raw material I (mono-lower alkylamine) and raw material II (alkylene oxide), Here, reaction is performed by a zeolite catalyst method to obtain a product 2 containing unreacted raw materials. Since the product 2 containing the unreacted raw material contains unreacted mono-lower alkylamine (unreacted raw material I) and alkylene oxide (unreacted raw material II) as the unreacted raw material, these and the reaction product 3 Are separated by the unreacted raw material recovery distillation column 4 and the separated and recovered unreacted mono-lower alkylamine (raw material I) and alkylene oxide (raw material II) are sent back to the reactor 1 as unreacted raw materials 5. Yes.
　そして、非水蒸留塔６により、前記未反応原料回収蒸留塔４から導出された反応生成物３から水及び軽質分７を蒸留法により除去し、これら水及び軽質分７を除去した後の反応生成物３ａを精製蒸留塔８に送るようにしている。ここで、非水とは、成分中に含まれる水分量が１０００ｐｐｍ以下となっている状態を示す。 Then, the non-water distillation column 6 removes water and light components 7 from the reaction product 3 derived from the unreacted raw material recovery distillation column 4 by distillation, and the reaction after these water and light components 7 are removed. The product 3a is sent to the purification distillation column 8. Here, non-water indicates a state where the amount of water contained in the component is 1000 ppm or less.
　その後、水及び軽質分７を除去した後の反応生成物３ａを精製蒸留塔８に送り、ここで、反応により生成したモノ低級アルキルモノアルカノールアミンとモノ低級アルキルジアルカノールアミン（残渣であるダイマー）とを蒸留法により分離して、前記モノ低級アルキルモノアルカノールアミンを目的反応生成物９として回収するようにしている。 Thereafter, the reaction product 3a after removing the water and the light component 7 is sent to the purification distillation column 8, where mono-lower alkyl monoalkanolamine and mono-lower alkyl dialkanolamine (residue dimer) produced by the reaction. Are separated by distillation to recover the mono-lower alkyl monoalkanolamine as the target reaction product 9.
　一方、前記ゼオライト触媒を用いない方法としては、例えば超臨界条件（温度条件が１００～２００℃、圧力条件が１７～２４ＭＰａ）で製造する方法が提案されている（特許文献２）。 On the other hand, as a method not using the zeolite catalyst, for example, a method of producing under supercritical conditions (temperature conditions of 100 to 200 ° C. and pressure conditions of 17 to 24 MPa) has been proposed (Patent Document 2).
　また、モノ低級アルキルアミンとアルキレンオキシドの反応によるモノ低級アルキルモノアルカノールアミンの製造方法としては、この反応を水の存在下で行う製造方法（水触媒法と称す。）が広く知られている。しかし、この方法には、精製系で大量の水を蒸留除去するために大きな熱負荷が必要であるという問題があった。 Further, as a method for producing a mono-lower alkyl monoalkanolamine by reaction of mono-lower alkyl amine and alkylene oxide, a production method (referred to as water catalyst method) in which this reaction is carried out in the presence of water is widely known. However, this method has a problem that a large heat load is required to distill off a large amount of water in the purification system.
　さらに、モノメチルアミンとエチレンオキサイドからモノメチルアミノエタノールを製造する方法が開示されている（特許文献３）。この特許文献３に記載の方法では、アミン回収系の蒸留塔に粗液をアルコールと混合後、または別ラインで粗液とアルコールを仕込むことによって、未反応のモノメチルアミンを回収している。 Furthermore, a method for producing monomethylaminoethanol from monomethylamine and ethylene oxide is disclosed (Patent Document 3). In the method described in Patent Document 3, unreacted monomethylamine is recovered by mixing the crude liquid with alcohol in an amine recovery distillation column or by charging the crude liquid and alcohol in a separate line.
特開２００４－２７５９３３号公報JP 2004-275933 A 特開昭５９－１３７５１号公報JP 59-13751 A 特開平８－３３３３１０号公報JP-A-8-333310
　しかしながら、特許文献１にかかる「ゼオライト触媒法」では、触媒の劣化により反応率の低下や選択率の低下が起こる、という問題がある。また、反応器１内の温度を均一に保持することが困難であるので、生成物を安定して製造することができない、という問題がある。さらに、ゼオライト触媒法では、蒸留工程にてモノ低級アルキルアミンを分離する蒸留塔において、コンデンサー等の冷却設備を使用する必要があり、エネルギー消費が大きくなる、という問題がある。これは、前記ゼオライト触媒法では、固体(ゼオライト触媒)と液体(原料)とが接触して反応が起こり、固体と液体が接触しない位置では反応が進行しないため、不均一反応となるからである。 However, the “zeolite catalyst method” according to Patent Document 1 has a problem in that the reaction rate and selectivity are lowered due to catalyst deterioration. Moreover, since it is difficult to keep the temperature in the reactor 1 uniform, there is a problem that the product cannot be stably produced. Further, the zeolite catalyst method has a problem that it is necessary to use a cooling facility such as a condenser in the distillation column for separating the mono-lower alkylamine in the distillation step, resulting in an increase in energy consumption. This is because, in the zeolite catalyst method, a solid (zeolite catalyst) and a liquid (raw material) come into contact with each other to cause a reaction, and the reaction does not proceed at a position where the solid and the liquid do not contact with each other, resulting in a heterogeneous reaction. .
　また、特許文献２にかかる「超臨界法」では、温度条件が１００～２００℃、圧力条件が１７～２４ＭＰａとする必要があり、運転に必要な動力・コストが大きくなる、という問題がある。 Further, the “supercritical method” according to Patent Document 2 has a problem that the temperature condition needs to be 100 to 200 ° C. and the pressure condition needs to be 17 to 24 MPa, which increases the power and cost required for operation.
　また、特許文献３にかかる技術では、モノメチルアミンを回収するために、アルコールと混合する必要があり、また、モノメチルアミンを再利用するためには、更なる蒸留塔が必要である等、工程が煩雑であり、しかも、設備費が高くなるという問題があった。
　そして、そのためのより効率的な製造方法及び装置が提供されることが要望される。 Moreover, in the technique concerning patent document 3, in order to collect | recover monomethylamine, it is necessary to mix with alcohol, and in order to recycle monomethylamine, a further distillation tower is needed, etc. There is a problem that it is complicated and the equipment cost is high.
And it is desired to provide a more efficient manufacturing method and apparatus therefor.
　また、前述した水触媒法によりモノ低級アルキルモノアルカノールアミンの収率を向上させるためには、モノ低級アルキルアミンとアルキレンオキシドとのモル比を小さくする必要があり、この場合モノ低級アルキルアミンを循環使用することになるため、蒸留塔のリボイラー負荷が増大し、エネルギー消費が大きくなる、という問題がある。 Further, in order to improve the yield of mono-lower alkyl monoalkanolamine by the water catalyst method described above, it is necessary to reduce the molar ratio of mono-lower alkyl amine to alkylene oxide, and in this case, the mono-lower alkyl amine is circulated. Since it is used, there is a problem that the reboiler load of the distillation column increases and the energy consumption increases.
　本発明は、前記問題に鑑み、省エネルギーでモノ低級アルキルモノアルカノールアミンを製造できるモノ低級アルキルモノアルカノールアミンの製造方法及び装置を提供することにある。 In view of the above problems, the present invention is to provide a production method and apparatus for a mono-lower alkyl monoalkanolamine capable of producing a mono-lower alkyl monoalkanol amine with energy saving.
　上述した課題を解決するための本発明の第１の発明は、モノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを反応させてモノ低級アルキルモノアルカノールアミンを製造する方法において、反応塔にモノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを供給すると共に、反応塔内において気液混相状態で反応させ、前記反応塔内から反応生成物を液体状態で分離することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 The first invention of the present invention for solving the above-mentioned problem is a method for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine (AA) with an alkylene oxide (AO). A mono-lower alkylamine (AA) and an alkylene oxide (AO) are supplied, and the reaction product is reacted in a gas-liquid mixed phase in the reaction column, and the reaction product is separated from the reaction column in a liquid state. It exists in the manufacturing method of mono lower alkyl monoalkanolamine.
　第２の発明は、第１の発明において、前記反応塔が、反応・蒸留塔であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 The second invention is the method for producing mono-lower alkyl monoalkanolamine according to the first invention, wherein the reaction tower is a reaction / distillation tower.
　第３の発明は、第２の発明において、前記反応・蒸留塔が多段式であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 The third invention is the method for producing a mono-lower alkyl monoalkanolamine according to the second invention, wherein the reaction / distillation tower is a multistage type.
　第４の発明は、第２の発明において、前記反応・蒸留塔の反応温度が４０～２００℃であると共に、反応・蒸留塔の塔頂温度が４０～１００℃であり、反応・蒸留塔の塔底温度が１２０～２００℃であり、反応・蒸留塔の圧力が０．４５～１．３ＭＰａであることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 According to a fourth invention, in the second invention, the reaction temperature of the reaction / distillation tower is 40 to 200 ° C., and the top temperature of the reaction / distillation tower is 40 to 100 ° C. The method for producing a mono-lower alkyl monoalkanolamine is characterized in that the column bottom temperature is 120 to 200 ° C. and the pressure in the reaction / distillation column is 0.45 to 1.3 MPa.
　第５の発明は、第１の発明において、反応塔が、気液混相反応塔であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 The fifth invention is the method for producing mono-lower alkylmonoalkanolamine according to the first invention, wherein the reaction tower is a gas-liquid mixed phase reaction tower.
　第６の発明は、第４の発明において、反応温度が８０～２００℃、圧力０．２～０．８ＭＰａにおいて、モノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを気体状態で反応させ、反応生成物を液体として、該反応生成物を液相から分離することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 According to a sixth invention, in the fourth invention, a mono-lower alkylamine (AA) and an alkylene oxide (AO) are reacted in a gaseous state at a reaction temperature of 80 to 200 ° C. and a pressure of 0.2 to 0.8 MPa. The method for producing a mono-lower alkylmonoalkanolamine is characterized in that the reaction product is used as a liquid and the reaction product is separated from the liquid phase.
　第７の発明は、第２又は５の発明において、モノ低級アルキルアミン（ＡＡ）を反応・蒸留塔の塔頂から分離・回収し、再利用することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 According to a seventh aspect of the present invention, there is provided a mono lower alkyl monoalkanolamine according to the second or fifth aspect, wherein the mono lower alkyl amine (AA) is separated and recovered from the top of the reaction / distillation tower and reused. In the manufacturing method.
　第８の発明は、第２又は５の発明において、分離した未反応原料を原料主供給部に戻すか、又は分離した未反応原料を反応・蒸留塔の原料主供給部の供給位置より塔頂側の箇所から内部に供給することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 According to an eighth invention, in the second or fifth invention, the separated unreacted raw material is returned to the raw material main supply part, or the separated unreacted raw material is returned to the top of the reaction / distillation column from the supply position of the raw material main supply part. The present invention provides a method for producing a mono-lower alkyl monoalkanolamine, characterized in that the mono lower alkyl monoalkanolamine is supplied into the inside from the side portion.
　第９の発明は、第２又は５の発明において、アルキレンオキシド（ＡＯ）の供給割合を分割すると共に、アルキレンオキシド（ＡＯ）の分割した一部を原料主供給部から反応・蒸留塔内に供給すると共に、その残りを該原料主供給部の供給位置より塔頂側に位置する副供給部から反応・蒸留塔内に供給することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法にある。 The ninth invention is the invention according to the second or fifth invention, wherein the supply ratio of the alkylene oxide (AO) is divided and a part of the divided alkylene oxide (AO) is supplied from the raw material main supply section into the reaction / distillation column. And the remainder is fed into the reaction / distillation column from the sub-feeding portion located on the top side of the column from the feed position of the raw material main feeding portion.
　第１０の発明は、モノ低級アルキルアミンとアルキレンオキシドの反応によるモノ低級アルキルモノアルカノールアミンの製造装置において、モノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを供給すると共に、塔内において気液混相状態で反応させ、該塔底部から反応生成物を液体状態で分離すると共に、未反応原料を気体状態で回収する反応・蒸留塔と、液体状態で分離した生成物を精製して目的生成物を蒸留する精製蒸留塔とを具備することを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置にある。 A tenth aspect of the invention is an apparatus for producing a mono-lower alkyl monoalkanolamine by reaction of a mono-lower alkyl amine and an alkylene oxide, and supplies the mono-lower alkyl amine (AA) and the alkylene oxide (AO), The reaction product is reacted in a liquid mixed phase and the reaction product is separated from the bottom of the column in a liquid state, and the reaction / distillation tower recovers the unreacted raw material in a gas state, and the product separated in the liquid state is purified to produce a target product. And a purification distillation column for distilling the product.
　第１１の発明は、第１０の発明において、前記反応・蒸留塔の反応温度が４０～２００℃であると共に、反応・蒸留塔の塔頂温度が４０～１００℃であり、反応・蒸留塔の塔底温度が１２０～２００℃であり、反応・蒸留塔の圧力が０．４５～１．３ＭＰａであることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置にある。 An eleventh aspect of the invention is that in the tenth aspect of the invention, the reaction temperature of the reaction / distillation column is 40 to 200 ° C., and the top temperature of the reaction / distillation column is 40 to 100 ° C. The mono-lower alkyl monoalkanolamine production apparatus is characterized in that the column bottom temperature is 120 to 200 ° C. and the pressure in the reaction / distillation column is 0.45 to 1.3 MPa.
　第１２の発明は、第１０又は１１の発明において、モノ低級アルキルアミン原料とアルキレンオキシド原料との比率（アルキレンオキシド原料／モノ低級アルキルアミン原料）が０．０５～０．５であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置にある。 The twelfth invention is characterized in that, in the tenth or eleventh invention, the ratio of the mono-lower alkylamine raw material to the alkylene oxide raw material (alkylene oxide raw material / mono-lower alkylamine raw material) is 0.05 to 0.5. In a production apparatus for mono-lower alkyl monoalkanolamine.
　第１３の発明は、第１０乃至１２のいずれか一つの発明において、前記反応・蒸留塔に供給する原料の水分量が２０％以下であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置にある。 A thirteenth aspect of the present invention is the apparatus for producing a mono-lower alkyl monoalkanolamine according to any one of the tenth to twelfth aspects of the present invention, wherein the amount of water supplied to the reaction / distillation column is 20% or less. It is in.
　第１４の発明は、第１０の発明において、前記反応・蒸留塔にゼオライト系触媒を充填してなると共に、原料を非水状態で供給してなることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置にある。 A fourteenth aspect of the invention is the mono lower alkyl monoalkanolamine according to the tenth aspect of the invention, wherein the reaction / distillation column is filled with a zeolite catalyst and the raw material is supplied in a non-aqueous state. In production equipment.
　前記構成の本発明によれば、モノ低級アルキルモノアルカノールアミンを高い収率でしかも省エネルギーで製造することができる。 According to the present invention configured as described above, a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
図１は、実施例１に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。FIG. 1 is a schematic view of an apparatus for producing a mono-lower alkyl monoalkanolamine according to Example 1. 図２は、実施例２に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。FIG. 2 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 2. 図３は、実施例３に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。FIG. 3 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 3. 図４は、実施例４に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。FIG. 4 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 4. 図５は、実施例５に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。FIG. 5 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 5. 図６は、モル分率と反応塔の段数との関係図である。FIG. 6 is a relationship diagram between the molar fraction and the number of stages of the reaction tower. 図７は、試験例に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。FIG. 7 is a schematic view of a mono-lower alkyl monoalkanolamine production apparatus according to a test example. 図８は、従来のゼオライト触媒を用いたモノ低級アルキルモノアルカノールアミンの製造装置の一例を示す図である。FIG. 8 is a view showing an example of an apparatus for producing a mono-lower alkyl monoalkanolamine using a conventional zeolite catalyst.
　以下、この発明につき図面を参照しつつ詳細に説明する。なお、この実施例によりこの発明が限定されるものではない。また、下記実施例における構成要素には、当業者が容易に想定できるもの、あるいは実質的に同一のものが含まれる。 Hereinafter, the present invention will be described in detail with reference to the drawings. Note that the present invention is not limited to the embodiments. In addition, constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art or those that are substantially the same.
　以下、本発明に係るモノ低級アルキルモノアルカノールアミンの製造方法について説明する。本発明に係るモノ低級アルキルモノアルカノールアミンの製造方法は、モノ低級アルキルアミン（原料Ｉ：ＡＡ）とアルキレンオキシド（原料ＩＩ：ＡＯ）とを反応させてモノ低級アルキルモノアルカノールアミンを製造する方法において、反応塔に原料Ｉ（ＡＡ）と原料ＩＩ（ＡＯ）とを供給すると共に、反応塔内において気液混相状態で反応させ、該反応塔内から反応生成物（アミンモノマー）を液体状態で分離するようにしている。ここで、反応塔内において気液混相状態で反応させる前記反応塔としては、反応・蒸留塔又は気液混相反応塔であることが好ましい。 Hereinafter, a method for producing a mono-lower alkylmonoalkanolamine according to the present invention will be described. The method for producing a mono-lower alkyl monoalkanolamine according to the present invention is a method for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkylamine (raw material I: AA) and an alkylene oxide (raw material II: AO). The raw material I (AA) and the raw material II (AO) are supplied to the reaction tower and reacted in a gas-liquid mixed phase in the reaction tower, and the reaction product (amine monomer) is separated from the reaction tower in a liquid state. Like to do. Here, the reaction tower that is reacted in a gas-liquid mixed phase state in the reaction tower is preferably a reaction / distillation tower or a gas-liquid mixed phase reaction tower.
　本発明では、反応塔内において気液混相状態で反応させるようにして、液体状態で目的生成物を得るようにしているので、反応収率が向上する。また、アルキレンオキシド原料とモノ低級アルキルアミン原料との比率（アルキレンオキシド原料／モノ低級アルキルアミン原料）も小さくすることがないので、未反応原料として回収するリボイラー量の低減も図ることができるものとなる。 In the present invention, the reaction product is reacted in a gas-liquid mixed phase state in the reaction tower to obtain the target product in the liquid state, so that the reaction yield is improved. In addition, since the ratio of the alkylene oxide raw material to the mono-lower alkylamine raw material (alkylene oxide raw material / mono-lower alkylamine raw material) is not reduced, the amount of reboiler recovered as an unreacted raw material can be reduced. Become.
　以下、反応塔として、反応・蒸留塔及び気液混相反応塔の具体的な実施例について詳細に説明する。 Hereinafter, specific examples of a reaction / distillation column and a gas-liquid mixed phase reaction column will be described in detail as reaction columns.
　本発明による実施例に係るモノ低級アルキルモノアルカノールアミンの製造装置について、図面を参照して説明する。
　図１は、実施例１に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。
　図１に示すように、実施例１に係るモノ低級アルキルモノアルカノールアミンの製造装置１０－１は、モノ低級アルキルアミン（ＡＡ：原料Ｉ）とアルキレンオキシド（ＡＯ：原料ＩＩ）との混合原料１１を原料主供給ラインＬ0により供給してなる反応・蒸留塔１２と、液状で分離された反応生成物１３を蒸留して目的反応生成物２０（モノマー）と、残渣（ダイマー）２１とを分離する精製蒸留塔１９とを具備するものである。なお、符号１８はリボイラーを図示する。 An apparatus for producing a mono-lower alkyl monoalkanolamine according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view of an apparatus for producing a mono-lower alkyl monoalkanolamine according to Example 1.
As shown in FIG. 1, a mono-lower alkylmonoalkanolamine production apparatus 10-1 according to Example 1 is a mixed raw material 11 of mono-lower alkylamine (AA: raw material I) and alkylene oxide (AO: raw material II). the reaction-distillation column 12 which is formed by supplying a raw material main supply line L 0, separating the desired reaction products 20 by distilling the reaction product 13 which is separated in liquid form (monomer), and a residue (dimer) 21 And a refining distillation column 19. Reference numeral 18 denotes a reboiler.
　ここで、前記反応・蒸留塔１２においては、その塔頂部１２ａからラインＬ1を介して未反応原料１６を分離すると共に、その塔底部１２ｂからラインＬ2を介して反応生成物１３を分離するものである。 Here, in the reaction-distillation column 12, as well as separating the unreacted raw materials 16 through a line L 1 from the top of the column 12a, to separate the reaction product 13 via the line L 2 from the bottom 12b Is.
　また、未反応原料１６はラインＬ1に介装された冷却器１４により冷却され、フラッシュドラム１５において液体となり、ラインＬ3を介して一時的に貯留するために貯留槽１７に送られている。そして、該貯留槽１７からラインＬ4を介して、そのほとんどが原料Ｉであるので原料Ｉの供給ライン側に戻すようにしている。 The unreacted raw material 16 is cooled by the cooler 14 interposed in the line L 1 , becomes liquid in the flash drum 15, and is sent to the storage tank 17 for temporary storage through the line L 3 . . And since most of the raw material I is from the storage tank 17 via the line L 4 , it is returned to the supply line side of the raw material I.
　本実施例では、前記フラッシュドラム１５からラインＬ5を介して反応・蒸留塔１２の内部に再投入原料１６ａを供給して、その未反応原料１６の一部を原料主供給ラインＬ0側に戻すことなく、直ちに再利用するようにしている。 In this embodiment, the supplies cycled material 16a from the flash drum 15 into the reaction-distillation column 12 via a line L 5, a part of the unreacted raw materials 16 to the material main feed line L 0 side We try to reuse it immediately without returning it.
　本実施例の反応・蒸留塔は多段式であり、蒸留量の規模によるが、例えば１０～２０段程度としている。 The reaction / distillation tower of this example is a multistage type, and it is, for example, about 10 to 20 stages depending on the scale of the distillation amount.
　ここで、本実施例においては、前記反応・蒸留塔１２の反応温度を例えば４０～２００℃とするのが好ましい。
　また、前記反応・蒸留塔１２の塔頂温度を例えば４０～１００℃、好ましくは７０～８０℃とするのが好ましい。
　また、反応・蒸留塔１２の塔底温度を例えば１２０～２００℃、好ましくは１４０～１８０℃とするのが好ましい。
　また、反応・蒸留塔１２の圧力を例えば０．４５～１．３ＭＰａ、好ましくは０．６～１．０ＭＰａとするのが好ましい。
　このように規定するのは、反応温度等及び圧力が上記範囲外であると効率的な反応が進行しないからである。 Here, in this embodiment, the reaction temperature of the reaction / distillation column 12 is preferably set to 40 to 200 ° C., for example.
Further, the top temperature of the reaction / distillation column 12 is, for example, 40 to 100 ° C., preferably 70 to 80 ° C.
The bottom temperature of the reaction / distillation column 12 is, for example, 120 to 200 ° C., preferably 140 to 180 ° C.
Further, the pressure of the reaction / distillation column 12 is, for example, preferably 0.45 to 1.3 MPa, and more preferably 0.6 to 1.0 MPa.
This is defined because the reaction does not proceed efficiently if the reaction temperature and the pressure are outside the above ranges.
　ここで、本発明で使用する原料Ｉのモノ低級アルキルアミンに特に制限はないが、例えばモノメチルアミン、モノエチルアミン、モノｎ－プロピルアミン、モノイソプロピルアミン、モノｎ－ブチルアミン、モノイソブチルアミン、モノｓｅｃ－ブチルアミン、モノｔ－ブチルアミン、モノｎ－ペンチルアミン、イソペンチルアミン、モノｎ－ヘキシルアミンなどの１～６個の炭素原子を有する直鎖状または分枝鎖状モノアルキルアミンを用いることができる。好適にはモノメチルアミン、モノエチルアミン、モノｎ－プロピルアミン、モノイソプロピルアミン、モノｎ－ブチルアミン、モノイソブチルアミン、モノｔ－ブチルアミンを用いることができ、特に好適にはモノメチルアミン、モノエチルアミン、モノｎ－プロピルアミン、モノイソプロピルアミン、モノｎ－ブチルアミンを用いることができる。 Here, the mono-lower alkylamine of the raw material I used in the present invention is not particularly limited. For example, monomethylamine, monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, monosec Linear or branched monoalkylamines having 1 to 6 carbon atoms, such as -butylamine, mono-t-butylamine, mono-n-pentylamine, isopentylamine, mono-n-hexylamine can be used . Monomethylamine, monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, mono-t-butylamine can be preferably used, and monomethylamine, monoethylamine, monon are particularly preferred. -Propylamine, monoisopropylamine, mono-n-butylamine can be used.
　本発明で使用する原料ＩＩのアルキレンオキシドに特に制限はないが、好適にはエチレンオキシド、プロピレンオキシド、ブチレンオキシドなどの２～４個の炭素原子を有するアルキレンオキシドを用いることができ、特に好適にはエチレンオキシド及びプロピレンオキシドを用いることができる。 The alkylene oxide of the raw material II used in the present invention is not particularly limited, but an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide can be preferably used, and particularly preferably. Ethylene oxide and propylene oxide can be used.
　また、本発明の水触媒法において、反応器に供給する原料中の水濃度は、水濃度が１～４０重量％の範囲で行うことが好ましい。また、好適な水濃度範囲は５～３０重量％であり、特に好適な水濃度は５～２０重量％である。 In the water catalyst method of the present invention, the water concentration in the raw material supplied to the reactor is preferably in the range of 1 to 40% by weight. A preferable water concentration range is 5 to 30% by weight, and a particularly preferable water concentration is 5 to 20% by weight.
　本発明の水触媒法によるモノ低級アルキルモノアルカノールアミンの製造においては、水の濃度によって反応速度が異なり、水の濃度が高いほど反応速度が大きくなるので好ましい。 In the production of mono-lower alkyl monoalkanolamines by the water catalyst method of the present invention, the reaction rate varies depending on the water concentration, and the higher the water concentration, the greater the reaction rate.
　また、本発明では原料の供給比率も規定している。すなわち、アルキレンオキシド原料とモノ低級アルキルアミン原料とのモル比（アルキレンオキシド（ＡＯ：原料ＩＩ）／モノ低級アルキルアミン（ＡＡ：原料Ｉ））が０．０５～０．５の範囲、より好ましくは０．１～０．３の範囲とすることが好ましい。 In the present invention, the supply ratio of raw materials is also specified. That is, the molar ratio of alkylene oxide raw material to mono-lower alkylamine raw material (alkylene oxide (AO: raw material II) / mono-lower alkylamine (AA: raw material I)) is in the range of 0.05 to 0.5, more preferably A range of 0.1 to 0.3 is preferable.
　これはモル比が０．５を超える場合では、未反応原料を回収する未反応原料回収蒸留塔のリボイラー負荷は低減されるが、反応に時間を要し、一方、０．０５未満の場合には、反応時間の短縮を図ることはできるものの大幅なリボイラー負荷となり、好ましくないからである。 When the molar ratio exceeds 0.5, the reboiler load of the unreacted raw material recovery distillation column for recovering the unreacted raw material is reduced, but the reaction takes time, whereas when the molar ratio is less than 0.05, This is because although the reaction time can be shortened, it becomes a significant reboiler load and is not preferable.
　ここで、本実施例では、精製蒸留塔１９を設けて、残渣（ダイマー）２１を除去するようにしているが、目的反応生成物２０のモノマーにおいて残渣（ダイマー）２１が混入しても良い場合には、反応・蒸留塔１２だけとしてもよい。 Here, in this embodiment, the purification distillation column 19 is provided to remove the residue (dimer) 21, but the residue (dimer) 21 may be mixed in the monomer of the target reaction product 20. Alternatively, only the reaction / distillation column 12 may be used.
　また、この反応は発熱反応であるので、反応・蒸留塔１２の内部又は外部に冷却手段を設けて所定温度に除熱するようにしてもよい。 Further, since this reaction is an exothermic reaction, a cooling means may be provided inside or outside the reaction / distillation column 12 to remove heat to a predetermined temperature.
　このように、実施例１に係るモノ低級アルカノールアミンの製造装置によれば、反応・蒸留塔１２で反応塔内において気液混相状態で原料を反応させていると共に、液体状態で反応生成物１３を回収すると共に、未反応原料を気体状態で分離することとなるので、従来のような別途の蒸留塔を設ける必要がなくなり、モノ低級アルキルモノアルカノールアミンを高い収率でしかも省エネルギーで製造することができる。 Thus, according to the mono-lower alkanolamine production apparatus according to Example 1, the reaction / distillation tower 12 reacts the raw material in the gas-liquid mixed phase state in the reaction tower, and the reaction product 13 in the liquid state. In addition, the unreacted raw material is separated in a gaseous state, so that there is no need to provide a separate distillation column as in the prior art, and mono-lower alkyl monoalkanolamine is produced with high yield and energy saving. Can do.
　また、反応・蒸留塔１２内から生成したモノマーを反応系から積極的に抜出すことにより、モノマーと未反応原料１６との反応が抑制され、残渣２１であるダイマーの生成が抑制されるので、目的反応生成物２０の収率向上にも寄与することとなる。 Moreover, since the monomer produced from the reaction / distillation tower 12 is actively extracted from the reaction system, the reaction between the monomer and the unreacted raw material 16 is suppressed, and the production of dimer as the residue 21 is suppressed. This also contributes to an improvement in the yield of the target reaction product 20.
　また、モノ低級アルキルアミン原料とアルキレンオキシド原料との比率（アルキレンオキシド原料／モノ低級アルキルアミン原料）を大きくすることができるので、設備がコンパクトになり、ユーティリティー消費量も低減することとなり、廉価にモノ低級アルキルモノアルカノールアミンを製造することができる。 In addition, since the ratio of the mono-lower alkylamine raw material to the alkylene oxide raw material (alkylene oxide raw material / mono-lower alkylamine raw material) can be increased, the equipment becomes compact and the utility consumption is reduced. Mono lower alkyl monoalkanolamines can be produced.
　本実施例について図２を参照して説明する。
　図２は、実施例２に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。
　図２に示すように、実施例２に係るモノ低級アルキルモノアルカノールアミンの製造装置１０－２は、原料Ｉと原料ＩＩとの混合原料１１を原料主供給ラインＬ0により供給してなる反応・蒸留塔１２と、分離された反応生成物１３を蒸留して目的反応生成物２０（モノマー）と、残渣（ダイマー）２１とを分離する精製蒸留塔１９とを具備すると共に、原料ＩＩ（ＡＯ）の供給割合を分割すると共に、原料ＩＩ（ＡＯ）の分割した一部を原料主供給ラインＬ0から供給すると共に、原料ＩＩ（ＡＯ）の残りを該原料主供給ラインＬ0の供給位置より塔頂側に位置する副供給ラインＬ6から内部に供給するようにしている。 This embodiment will be described with reference to FIG.
FIG. 2 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 2.
As shown in FIG. 2, the production apparatus 10-2 for mono-lower alkyl monoalkanolamine according to Example 2 is a reaction / mixture of a raw material 11 and a raw material II supplied from a raw material main supply line L 0. The distillation column 12 and the purified reaction column 19 for separating the target reaction product 20 (monomer) and the residue (dimer) 21 by distilling the separated reaction product 13 and the raw material II (AO) And a part of the raw material II (AO) is supplied from the raw material main supply line L 0, and the remainder of the raw material II (AO) is supplied to the tower from the supply position of the raw material main supply line L 0. and then supplied to the inside from the sub-supply line L 6 located at the top side.
　これは、図６に示すように、反応・蒸留塔が複数段（図６では１３段）の場合、塔頂側にいくにつれて原料Ｉ（ＡＡ）のモル分率が増加するので、原料ＩＩ（ＡＯ）を分けて供給することで反応効率を上昇させるようにしている。 As shown in FIG. 6, when the reaction / distillation column has a plurality of stages (13 stages in FIG. 6), the mole fraction of the raw material I (AA) increases toward the top of the column, so that the raw material II ( The reaction efficiency is increased by separately supplying AO).
　このように、実施例２に係るモノ低級アルキルモノアルカノールアミンの製造装置によれば、反応・蒸留塔で反応塔内において気液混相状態で原料を反応させていると共に、原料ＩＩの供給を蒸留・反応塔の塔内に分けて入れることとなるので、反応効率が向上し、モノ低級アルキルモノアルカノールアミンを高い収率でしかも省エネルギーで製造することができる。 Thus, according to the production apparatus for mono-lower alkyl monoalkanolamine according to Example 2, the reaction of the raw material in the gas-liquid mixed phase state in the reaction column in the reaction / distillation column and the distillation of the supply of the raw material II -Since the reaction is divided into the reaction towers, the reaction efficiency is improved, and the mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
　本実施例について図３を参照して説明する。
　図３は、実施例３に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。
　図３に示すように、実施例３に係るモノ低級アルキルモノアルカノールアミンの製造装置１０－３は、実施例１に係るモノ低級アルキルモノアルカノールアミンの製造装置１０－１において、反応生成物１３中に混入している水分を除去する非水蒸留塔２２を設け、水２３を除去した反応生成物１３ａを精製蒸留塔１９に送り、目的反応生成物２０を得るようにしている。
　これにより、水分を除去した目的反応生成物２０を得ることができる。 This embodiment will be described with reference to FIG.
FIG. 3 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 3.
As shown in FIG. 3, the production apparatus 10-3 for mono-lower alkylmonoalkanolamine according to Example 3 is the same as the production apparatus 10-1 for mono-lower alkylmonoalkanolamine according to Example 1 in the reaction product 13. A non-aqueous distillation column 22 for removing water mixed in is provided, and the reaction product 13a from which water 23 has been removed is sent to the purification distillation column 19 to obtain the target reaction product 20.
Thereby, the target reaction product 20 from which moisture has been removed can be obtained.
　このように、実施例３に係るモノ低級アルキルモノアルカノールアミンの製造装置によれば、非水蒸留塔２２を設けて、水分を除去することとなるので、非水状態のモノ低級アルキルモノアルカノールアミンを高い収率でしかも省エネルギーで製造することができる。 Thus, according to the production apparatus for mono-lower alkyl monoalkanolamine according to Example 3, the non-aqueous distillation tower 22 is provided to remove moisture, so that the mono-lower alkyl monoalkanol amine in the non-aqueous state is removed. Can be produced with high yield and energy saving.
　本実施例について図４を参照して説明する。
　図４は、実施例４に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。
　図４に示すように、実施例４に係るモノ低級アルキルモノアルカノールアミンの製造装置１０－４は、実施例１に係るモノ低級アルキルモノアルカノールアミンの製造装置１０－１において、反応・蒸留塔１２内に触媒充填槽３０ａ、３０ｂを充填してなり、触媒充填槽３０ａ、３０ｂに充填された触媒反応により反応生成物１３を生成するようにしている。 This embodiment will be described with reference to FIG.
FIG. 4 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 4.
As shown in FIG. 4, the mono-lower alkyl monoalkanolamine production apparatus 10-4 according to Example 4 is the same as the reaction / distillation column 12 in the mono-lower alkyl monoalkanolamine production apparatus 10-1 according to Example 1. The catalyst filling tanks 30a and 30b are filled therein, and the reaction product 13 is generated by the catalytic reaction filled in the catalyst filling tanks 30a and 30b.
　ここで、触媒充填槽に充填する触媒としては、ゼオライト触媒法で用いる公知の合成ゼオライトとして知られるＺＳＭ－５が挙げられる。なお、ＺＳＭとは、開発した会社の名に由来したＺＡＯｌＩｔＡＯｆ　Ｓｏｃｏｎｙ　ＭｏｂＩｌの略である。またＭＥＬ構造を有するものとしては、同じく合成ゼオライトとして知られるＺＳＭ－１１が挙げられる。本発明では、ゼオライトを用いることが好ましく、特に、ＺＳＭ－５を用いることが好ましい。 Here, examples of the catalyst filled in the catalyst filling tank include ZSM-5 known as a known synthetic zeolite used in the zeolite catalyst method. ZSM is an abbreviation of ZAOlItAOf Socony MobIl derived from the name of the developed company. Examples of those having a MEL structure include ZSM-11, also known as a synthetic zeolite. In the present invention, it is preferable to use zeolite, and it is particularly preferable to use ZSM-5.
　ここで、前記触媒としては、非水系での反応となるので、原料Ｉが水溶液（例えば水分４０％）の場合には、非水蒸留塔３１を設け、水分２３をあらかじめ除去しておくようにすることが必要である。 Here, since the catalyst is a non-aqueous reaction, when the raw material I is an aqueous solution (for example, 40% moisture), a non-aqueous distillation column 31 is provided to remove the moisture 23 in advance. It is necessary to.
　このように、実施例４に係るモノ低級アルキルモノアルカノールアミンの製造装置によれば、反応・蒸留塔にゼオライト系触媒を充填してゼオライト法により、反応塔内において気液混相状態で原料を反応させているので、反応効率が向上し、モノ低級アルキルモノアルカノールアミンを高い収率でしかも省エネルギーで製造することができる。 Thus, according to the production apparatus for mono-lower alkyl monoalkanolamine according to Example 4, the reaction / distillation tower is filled with the zeolite catalyst and the raw material is reacted in the gas-liquid mixed phase state in the reaction tower by the zeolite method. Therefore, the reaction efficiency is improved, and a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
　本発明による実施例に係るモノ低級アルキルモノアルカノールアミンの製造装置について、図面を参照して説明する。
　図５は、実施例５に係るモノ低級アルキルモノアルカノールアミンの製造装置の概略図である。
　図５に示すように、実施例５に係るモノ低級アルキルモノアルカノールアミンの製造装置１０－５は、原料Ｉと原料ＩＩとの混合原料１１を原料主供給ラインＬ0により供給してなる気液混相反応塔４０と、液状で分離された反応生成物１３を蒸留して目的反応生成物２０（モノマー）と、残渣（ダイマー）２１とを分離する精製蒸留塔１９とを具備するものである。 An apparatus for producing a mono-lower alkyl monoalkanolamine according to an embodiment of the present invention will be described with reference to the drawings.
FIG. 5 is a schematic view of an apparatus for producing mono-lower alkyl monoalkanolamine according to Example 5.
As shown in FIG. 5, the production apparatus 10-5 for mono-lower alkylmonoalkanolamine according to Example 5 is a gas-liquid produced by supplying a mixed raw material 11 of a raw material I and a raw material II through a raw material main supply line L 0. It comprises a mixed phase reaction column 40 and a purification distillation column 19 for separating the target reaction product 20 (monomer) and the residue (dimer) 21 by distilling the reaction product 13 separated in liquid form.
　ここで、前記気液混相反応塔４０においては、その内部では気体状態で原料Ｉと原料ＩＩとが反応し、得られた反応生成物１３が塔底部に貯まるのでそれをラインＬ2により反応生成物１３を分離するものである。 Here, in the gas-liquid mixed phase reaction tower 40, the a raw material I and the raw material II is reacted in gaseous state inside the reaction products it by the line L 2 because the reaction product 13 obtained is accumulated in the bottom portion The product 13 is separated.
　ここで、前記気液混相反応塔の反応温度としては、例えば８０～２００℃、圧力としては例えば０．２～０．８ＭＰａとするのが好ましい。 Here, it is preferable that the reaction temperature of the gas-liquid mixed phase reaction tower is, for example, 80 to 200 ° C., and the pressure is, for example, 0.2 to 0.8 MPa.
　なお、未反応原料１６はラインＬ1に介装された冷却器１４により冷却され、フラッシュドラム１５において液体とし、ラインＬ3を介して一時的に貯留するために貯留槽１７に送られている。そして、該貯留槽１７からラインＬ4を介して、そのほとんどが原料Ｉであるので原料Ｉの供給ライン側に戻すようにしている。 The unreacted raw material 16 is cooled by the cooler 14 interposed in the line L 1 , converted into liquid in the flash drum 15, and sent to the storage tank 17 for temporary storage through the line L 3 . . And since most of the raw material I is from the storage tank 17 via the line L 4 , it is returned to the supply line side of the raw material I.
　このように、実施例５に係るモノ低級アルキルモノアルカノールアミンの製造装置によれば、気液混相反応塔４０を用いて、該気液混相反応塔４０内において気液混相状態で原料Ｉと原料ＩＩとの混合原料１１を反応させているので、反応効率が向上し、モノ低級アルキルモノアルカノールアミンを高い収率でしかも省エネルギーで製造することができる。 Thus, according to the production apparatus for mono-lower alkyl monoalkanolamine according to Example 5, the raw material I and the raw material are mixed in the gas-liquid mixed phase reaction column 40 using the gas-liquid mixed phase reaction column 40. Since the mixed raw material 11 with II is reacted, the reaction efficiency is improved, and a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
［試験例］
　以下、試験例により本発明をさらに具体的に説明するが、本発明はこれにより限定されるものではない。 [Test example]
Hereinafter, the present invention will be described more specifically with test examples, but the present invention is not limited thereto.
　図７に示す実施例３と同様の構成のアミンの製造装置１０－３を用いた。反応・蒸留塔１２、非水蒸留塔２２、精製蒸留塔１９の運転条件（温度、圧力）を図７及び下記に示す。図７では、四角で囲っているのが温度（℃）であり、丸で囲っているのが圧力（ＭＰａ）である。 The amine production apparatus 10-3 having the same configuration as in Example 3 shown in FIG. 7 was used. The operating conditions (temperature, pressure) of the reaction / distillation column 12, the nonaqueous distillation column 22, and the purification distillation column 19 are shown in FIG. In FIG. 7, the temperature (° C.) is enclosed by a square, and the pressure (MPa) is enclosed by a circle.
（反応・蒸留塔１２）
　入口：温度８０℃（圧力２．６ＭＰａ）
　塔底部出口：温度１６３℃（圧力０．８２ＭＰａ）
　塔頂部出口：温度４０℃（圧力０．８０ＭＰａ）
　反応・蒸留塔１２入口における（原料ＩＩ／原料Ｉ）モル比：０．１
　反応・蒸留塔１２入口における水分濃度：８重量％ (Reaction / Distillation Tower 12)
Inlet: temperature 80 ° C. (pressure 2.6 MPa)
Tower bottom outlet: temperature 163 ° C. (pressure 0.82 MPa)
Tower top outlet: temperature 40 ° C. (pressure 0.80 MPa)
(Raw material II / Raw material I) molar ratio at the inlet of the reaction / distillation tower 12: 0.1
Water concentration at reaction / distillation tower 12 inlet: 8% by weight
　原料のモル比を０．１とすることでリボイラー量が従来に較べて、２割割程度減少し、これにより、リボイラー量の低減を図ることができた。
　なお、ゼオライト触媒法の場合には、反応・蒸留塔１２の塔底部出口の温度が１７３℃（圧力１．０２ＭＰａ）、塔頂部出口の温度が４０℃（圧力１．０ＭＰａ）とした。 By setting the molar ratio of the raw material to 0.1, the amount of reboiler was reduced by about 20% compared to the conventional case, thereby reducing the amount of reboiler.
In the case of the zeolite catalyst method, the temperature at the bottom outlet of the reaction / distillation tower 12 was 173 ° C. (pressure 1.02 MPa), and the temperature at the top outlet of the tower 40 was 40 ° C. (pressure 1.0 MPa).
　以上のように、本発明に係るモノ低級アルキルモノアルカノールアミンの製造方法及び装置によれば、モノ低級アルキルモノアルカノールアミンを高い収率でしかも省エネルギーで製造することができる。 As described above, according to the method and apparatus for producing a mono-lower alkyl monoalkanolamine according to the present invention, a mono-lower alkyl monoalkanolamine can be produced with high yield and energy saving.
　１０－１～１０－５　モノ低級アルキルモノアルカノールアミンの製造装置
　１１　混合原料
　１２　反応・蒸留塔
　１３　反応生成物
　１５　フラッシュドラム
　１６　未反応原料
　１７　貯留槽
　１８　リボイラー
　１９　精製蒸留塔
　２０　目的反応生成物 10-1 to 10-5 Mono-lower alkyl monoalkanolamine production equipment 11 Mixed raw material 12 Reaction / distillation tower 13 Reaction product 15 Flash drum 16 Unreacted raw material 17 Reservoir 18 Reboiler 19 Purification distillation tower 20 Target reaction product

Claims (14)

  1. 　モノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを反応させてモノ低級アルキルモノアルカノールアミンを製造する方法において、
    　反応塔にモノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを供給すると共に、反応塔内において気液混相状態で反応させ、前記反応塔内から反応生成物を液体状態で分離することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In a method for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine (AA) with an alkylene oxide (AO),
    Supplying mono-lower alkylamine (AA) and alkylene oxide (AO) to the reaction tower and reacting them in a gas-liquid mixed phase in the reaction tower, and separating the reaction product in the liquid state from the reaction tower. A method for producing a mono-lower alkyl monoalkanolamine, which is characterized.
  2. 　請求項１において、
    　前記反応塔が、反応・蒸留塔であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 1,
    The method for producing a mono-lower alkyl monoalkanolamine, wherein the reaction tower is a reaction / distillation tower.
  3. 　請求項２において、
    　前記反応・蒸留塔が多段式であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 2,
    The method for producing a mono-lower alkyl monoalkanolamine, wherein the reaction / distillation tower is multistage.
  4. 　請求項２において、
    　前記反応・蒸留塔の反応温度が４０～２００℃であると共に、
    　反応・蒸留塔の塔頂温度が４０～１００℃であり、
    　反応・蒸留塔の塔底温度が１２０～２００℃であり、
    　反応・蒸留塔の圧力が０．４５～１．３ＭＰａであることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 2,
    The reaction temperature of the reaction / distillation tower is 40 to 200 ° C.,
    The top temperature of the reaction / distillation tower is 40-100 ° C.,
    The bottom temperature of the reaction / distillation tower is 120 to 200 ° C.,
    A process for producing a mono-lower alkyl monoalkanolamine, wherein the pressure in the reaction / distillation tower is 0.45 to 1.3 MPa.
  5. 　請求項１において、
    　反応塔が、気液混相反応塔であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 1,
    A method for producing a mono-lower alkyl monoalkanolamine, wherein the reaction tower is a gas-liquid mixed phase reaction tower.
  6. 　請求項４において、
    　反応温度が８０～２００℃、圧力０．２～０．８ＭＰａにおいて、モノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを気体状態で反応させ、反応生成物を液体として、該反応生成物を液相から分離することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 4,
    At a reaction temperature of 80 to 200 ° C. and a pressure of 0.2 to 0.8 MPa, a mono-lower alkylamine (AA) and an alkylene oxide (AO) are reacted in a gaseous state, and the reaction product is converted into a liquid. Is separated from the liquid phase. A process for producing mono-lower alkyl monoalkanolamines.
  7. 　請求項２又は５において、
    　モノ低級アルキルアミン（ＡＡ）を反応・蒸留塔の塔頂から分離・回収し、再利用することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 2 or 5,
    A process for producing a mono-lower alkylmonoalkanolamine, comprising separating and recovering mono-lower alkylamine (AA) from the top of a reaction / distillation tower and reusing it.
  8. 　請求項２又は５において、
    　分離した未反応原料を原料主供給部に戻すか、
    　又は分離した未反応原料を反応・蒸留塔の原料主供給部の供給位置より塔頂側の箇所から内部に供給することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 2 or 5,
    Return the separated unreacted raw material to the raw material main supply section,
    Alternatively, a method for producing a mono-lower alkyl monoalkanolamine, characterized in that the separated unreacted raw material is supplied to the inside from a position at the top of the column from the supply position of the raw material main supply part of the reaction / distillation column.
  9. 　請求項２又は５において、
    　アルキレンオキシド（ＡＯ）の供給割合を分割すると共に、
    　アルキレンオキシド（ＡＯ）の分割した一部を原料主供給部から反応・蒸留塔内に供給すると共に、
    　その残りを該原料主供給部の供給位置より塔頂側に位置する副供給部から反応・蒸留塔内に供給することを特徴とするモノ低級アルキルモノアルカノールアミンの製造方法。     In claim 2 or 5,
    While dividing the supply ratio of alkylene oxide (AO),
    While supplying a part of the alkylene oxide (AO) divided from the raw material main supply section into the reaction / distillation tower,
    A process for producing a mono-lower alkylmonoalkanolamine, characterized in that the remainder is fed into a reaction / distillation column from a sub-feeding portion located on the column top side from the feed position of the raw material main feeding portion.
  10. 　モノ低級アルキルアミンとアルキレンオキシドの反応によるモノ低級アルキルモノアルカノールアミンの製造装置において、
    　モノ低級アルキルアミン（ＡＡ）とアルキレンオキシド（ＡＯ）とを供給すると共に、塔内において気液混相状態で反応させ、塔底部から反応生成物を液体状態で分離すると共に、未反応原料を気体状態で回収する反応・蒸留塔と、
    　液体状態で分離した生成物を精製して目的生成物を蒸留する精製蒸留塔とを具備することを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置。     In the production apparatus of mono-lower alkyl monoalkanolamine by reaction of mono-lower alkyl amine and alkylene oxide,
    While supplying mono-lower alkylamine (AA) and alkylene oxide (AO), the reaction is carried out in a gas-liquid mixed phase in the tower, the reaction product is separated from the tower bottom in a liquid state, and the unreacted raw material is in a gaseous state The reaction / distillation tower recovered in
    An apparatus for producing a mono-lower alkyl monoalkanolamine, comprising: a purification distillation column for purifying a product separated in a liquid state and distilling a target product.
  11. 　請求項１０において、
    　前記反応・蒸留塔の反応温度が４０～２００℃であると共に、
    　反応・蒸留塔の塔頂温度が４０～１００℃であり、
    　反応・蒸留塔の塔底温度が１２０～２００℃であり、
    　反応・蒸留塔の圧力が０．４５～１．３ＭＰａであることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置。     In claim 10,
    The reaction temperature of the reaction / distillation tower is 40 to 200 ° C.,
    The top temperature of the reaction / distillation tower is 40-100 ° C.,
    The bottom temperature of the reaction / distillation tower is 120 to 200 ° C.,
    An apparatus for producing a mono-lower alkyl monoalkanolamine, wherein the pressure in the reaction / distillation tower is 0.45 to 1.3 MPa.
  12. 　請求項１０又は１１において、
    　モノ低級アルキルアミン原料とアルキレンオキシド原料との比率（アルキレンオキシド原料／モノ低級アルキルアミン原料）が０．０５～０．５であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置。     In claim 10 or 11,
    An apparatus for producing a mono-lower alkyl monoalkanolamine, wherein the ratio of the mono-lower alkylamine raw material to the alkylene oxide raw material (alkylene oxide raw material / mono-lower alkylamine raw material) is 0.05 to 0.5.
  13. 　請求項１０乃至１２のいずれか一つにおいて、
    　前記反応・蒸留塔に供給する原料の水分量が２０％以下であることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置。     In any one of claims 10 to 12,
    An apparatus for producing a mono-lower alkyl monoalkanolamine, wherein the raw material supplied to the reaction / distillation column has a water content of 20% or less.
  14. 　請求項１０において、
    　前記反応・蒸留塔にゼオライト系触媒を充填してなると共に、原料を非水状態で供給してなることを特徴とするモノ低級アルキルモノアルカノールアミンの製造装置。     In claim 10,
    An apparatus for producing a mono-lower alkyl monoalkanolamine, wherein the reaction / distillation tower is filled with a zeolite catalyst and the raw material is supplied in a non-aqueous state.
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