JP4994692B2 - Method for producing tertiary amine - Google Patents

Description

  The present invention relates to a method for efficiently producing a corresponding tertiary amine in high yield using a film-type catalyst and using alcohol and a primary or secondary amine as raw materials.

  Many industrial reactions are carried out in mixing tank reactors using solid catalyst slurries. The reaction is performed by bringing a reactive gas such as hydrogen or ammonia into contact with the liquid in the presence of a catalyst. When the reaction is complete, the catalyst is generally removed by filtration and the reaction product is recovered.

  However, the slurryed catalyst causes problems such as safety, increased waste, operability, and productivity. For example, many catalysts are pyrophoric, and care must be taken when handling powder and slurry catalysts, and in order to recover the reaction products, the catalyst must be removed by filtration, etc. There is a problem of complexity.

  As a process that does not require a mixing operation such as stirring or gas bubbling and does not require filtration and separation of the catalyst, a fixed bed system can be mentioned. As the form of the catalyst used in the fixed bed system, conventionally formed catalysts such as pellets, noodles or tablets are well known. By forming a powdery substance having catalytic activity into the above form by a method such as compression or extrusion, it has a structure with innumerable pores in it, and both a catalyst form and a high surface area are achieved. . For example, it is disclosed in Patent Document 1.

  According to such a reaction system, problems such as catalyst handling and waste can be solved, but there are many reactions that are not applicable. For example, in reactions involving endothermic heat generation, there are problems with temperature control, and due to non-uniform distribution of liquid-gas in the reactor, the reaction rate is insufficient, or side reactions due to local concentration gradients. There were many cases.

  If a product is obtained at a high reaction rate using the shaped catalyst described in Patent Document 1 in the tertiary amination reaction, there are some undesirable by-products. As a by-product, in addition to wax or aldol condensate generated by side reaction of alcohol as a raw material, ammonia generated by disproportionation of primary or secondary amine, or tertiary produced as a by-product from primary or secondary amine Examples include amines. Various improvements have been made in the technology for carrying out highly selective operation while suppressing these by-products, but it has been difficult to carry out this reaction with high selectivity by a simple process.

  Patent Document 2 discloses a reactor in which a catalytic metal is deposited on the surface of a monolith. In this reactor, in the hydrogenation reaction between a gas and a liquid, the pressure drop of the reactor is small, An advantage has been pointed out that mass transfer is facilitated over conventional fixed bed packed reactors because the velocity of gas and liquid can be increased. However, although the reaction of a compound containing a nitrogen atom is intended, it is only shown in the case of a reaction by a simple mechanism such as hydrogenation. In addition, the examples disclosed elsewhere are mainly limited to hydrogenation reactions and the like, and the corresponding tertiary amine is produced using alcohol and primary or secondary amine as raw materials. There has never been an example of increasing the yield by applying it to a reaction having a very complicated mechanism.

Patent Document 3 discloses a gas-liquid reaction method in which a liquid and a gas are supplied from a tank as a liquid gas mixture to a monolith catalytic reactor, and a reaction product taken out from an outlet is circulated to the tank. In addition, since the temperature and cooling of the reaction raw materials and reactants can be separated from the catalyst, there are advantages such as minimization of by-product formation and catalyst deactivation. However, the reaction type is assumed to be a wide range such as hydrogenation or oxidation of organic compounds, but the examples are only measuring the mass transfer rate of oxygen using an aqueous sodium sulfite solution. It is not specifically shown. There is no description about the number of circulations per hour.
JP-A-6-21754 JP 2003-176255 A JP 2002-35569 A

  An object of the present invention is a method for efficiently producing a tertiary amine in a high yield when producing a corresponding tertiary amine using a film-type catalyst and using an alcohol and a primary or secondary amine as raw materials. Is to provide.

  The present invention is a method for producing a tertiary amine from an alcohol and a primary or secondary amine, and a reactor loaded with a film-type catalyst is installed in an external circulation line attached to a tank (hereinafter referred to as a buffer tank). And a method for producing a tertiary amine, wherein the reaction is conducted by circulating the reaction solution 3 times / Hr or more in the reactor.

  According to the production method of the present invention, a target tertiary amine can be efficiently obtained in a high yield by a simple process that does not require a catalyst separation operation.

  Examples of the starting alcohol used in the method for producing a tertiary amine of the present invention include linear or branched, saturated or unsaturated aliphatic alcohols having 8 to 36 carbon atoms. Specifically, octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, behenyl alcohol, oleyl alcohol, etc., mixed alcohols thereof, Ziegler alcohol obtained by Ziegler method, oxo alcohol and gel bean obtained by oxo method Alcohol etc. are illustrated.

  In addition, examples of the primary or secondary amine used in the method for producing the tertiary amine of the present invention include aliphatic primary or secondary amines, such as methylamine, dimethylamine, ethylamine, diethylamine, and dodecylamine. , Didodecylamine and the like.

  In the corresponding tertiary amine obtained from the alcohol as the raw material and the primary or secondary amine, the hydrogen atom bonded to the nitrogen atom of the primary or secondary amine is substituted with an alkyl and / or alkenyl group derived from the alcohol. It has been done. For example, the corresponding tertiary amine obtained from lauryl alcohol and dimethylamine is N-dodecyl-N, N-dimethylamine, which is produced as a by-product by the reaction of methylamine and ammonia produced by disproportionation of dimethylamine. Differentiated from the tertiary amines N, N-didodecyl-N-methylamine and N, N, N-tridodecylamine.

  The film-type catalyst used in the present invention refers to a catalyst in the form of a thin film having a thickness of 500 μm or less, unlike the irregular packing type having a size of about several mm of the conventional type. The process in which the reactants and products move inside the catalyst body is diffusion-dominated. By shortening the distance to 500 μm or less, the mass transfer between the outside of the catalyst body is promoted and the inside of the catalyst body is effectively achieved. In addition to being able to be utilized, it is possible to suppress overreaction of intermediate reactants inside the catalyst body. In particular, a thickness of 100 μm or less is preferable because the reaction activity per catalyst mass is remarkably increased, and a thickness of 50 μm or less is more preferable. The lower limit of the thickness is preferably 0.01 μm or more, and more preferably 1 μm or more in order to ensure the strength of the catalyst layer and obtain durability of the strength.

  The structure of the film type catalyst includes various forms depending on the reactor shape. For example, a catalyst coating layer formed on the inner wall surface of the pipe, a catalyst formed into a thin plate shape partitioning the inside of the pipe into a plurality of axial flow passages, and the like can be cited, and can be suitably used for a tubular flow reactor. Moreover, the catalyst coating layer etc. which were formed in the surface of the open type fin-shaped flat plate installed in the inside of a tank may be sufficient, and can be used suitably in the case of a tank type reactor. In any case, it is preferable to adopt a structure in which the supply of the reactant to the catalyst body and the recovery of the product from the catalyst body can easily occur. In addition, it is desirable that the surface of the catalyst body where the supply of the reactants and the recovery of the products occur as wide as possible to advance the reaction efficiently. In order to achieve the above requirements, on an inner wall surface of a bundle of tubes having an inner diameter of several mm to several tens of mm or a honeycomb structure having a cell density of several tens to several hundred cells per square inch Those provided with a film-type catalyst are preferably used.

  In order to make the film-type catalyst into the various structures described above, for example, there is a method of forming the catalyst active material itself into a honeycomb structure, but from the viewpoint of achieving both a thin catalyst layer and high mechanical strength, It is preferable to fix the film type catalyst on the surface of the support. The film type catalyst support is preferably a metal foil. For example, as described above, a method of forming a film-type catalyst by forming a coating layer containing a catalyst active material on the surface of a metal or other support having a rigid tubular shape, a flat plate shape, or a honeycomb shape can be given. As a coating method at this time, a conventionally known method can be used. For example, in addition to a physical vapor deposition method such as sputtering, a chemical vapor deposition method, an impregnation method from a solution system, a blade using a binder, a spray, a dip, Various coating methods such as spin, gravure, die coating and the like can be mentioned.

  The active material constituting the film-type catalyst is not particularly limited, and known materials can be used, but generally copper-based metals can be preferably used, and those containing copper can be used. Further preferred. For example, Cu alone or a material containing a two-component metal obtained by adding a transition metal element such as Cr, Co, Ni, Fe, or Mn to this can be used, and a material containing Cu and Ni is preferably used. Further, those containing a metal having three or more components are also preferably used. Further, those in which these are further supported on a carrier such as silica, alumina, titania, zeolite or the like can be used.

  The film type catalyst does not act as an active material by itself, but may contain a binder for immobilizing the active material to form a film type catalyst body. As the binder, in addition to the binding properties between the active materials or the support surface, a polymer or an inorganic compound having properties such as chemical resistance and heat resistance that can withstand the reaction environment and does not adversely affect the reaction system Is mentioned. For example, cellulose resins such as carboxymethyl cellulose and hydroxyethyl cellulose, fluorine resins such as polytetrafluoroethylene and polyvinylidene fluoride, urethane resins, epoxy resins, polyester resins, phenol resins, melamine resins, silicone resins, polyvinyl alcohol, polyimides Examples thereof include high molecular compounds such as resins and polyimide amide resins, and inorganic compound sols such as silica and alumina.

  The internal structure of the film-type catalyst largely depends on the type of active material constituting the catalyst body, the production method of the catalyst body, etc., but may form a dense continuous phase or may be porous. . For example, in the case of a thin film formed on the support surface by sputtering or chemical vapor deposition, it can be made into a dense continuous phase, and it can be made by a wet or dry coating method using a powdered active material. When it is formed on the surface of the support, it can be made porous.

  In the present invention, a reactor loaded with the film type catalyst as described above is used, and this reactor is installed in an external circulation line attached to the buffer tank, and the reaction solution is supplied to the reactor three times / hr. The reaction is carried out between the alcohol and the primary or secondary amine by circulating as described above.

  In the present invention, the buffer tank is a container for storing raw materials necessary for the reaction and / or products generated by the reaction, and the products coming out of the reactor and / or unreacted raw materials are stored in the buffer tank. If necessary, the gas component can be separated into a gas component and a liquid component, and the gas component can be extracted out of the system. The buffer tank is not particularly limited as long as it is a commonly used tank, but is preferably not loaded with a catalyst. The buffer tank may have a jacket and an internal coil for heating and cooling the raw materials and reactants. Moreover, in order to make a liquid uniform, you may have a stirrer and conversely, in order to improve the extrusion flow property of a reaction liquid, the structure of the non-stirring which provided the partition plate in the buffer tank may be sufficient.

  The method of the present invention does not require major modification of the reaction tank, and maintenance such as replacement of the film catalyst is easy as compared with the case where the film-type catalyst is loaded in a reaction tank not provided with a buffer tank. . Further, in the case of an existing reaction facility in which an external circulation line is already installed, the installation of a reactor loaded with a film-type catalyst in the external circulation line is further facilitated.

  Various types of reactors including those conventionally known can be adopted as the type of reactor loaded with a film-type catalyst. For example, a film-type catalyst may be rounded into a cylindrical shape or processed into a strip shape and loaded into a tubular reactor. Further, a film-type catalyst may be loaded in a shell and tube heat exchanger type tube or in a shell portion. In this case, the temperature of the reaction part can be controlled by flowing a heat medium to the tube side or the shell side not loaded with the film type catalyst. In the case of a flow-through tubular reactor, the reaction can proceed continuously by circulating supply by a method of continuously recovering the product while supplying the reactant to the film-type catalyst inside the tube.

  An example of the reaction apparatus used in the present invention is shown in FIG. In FIG. 1, 1 is a tubular reactor loaded with a film-type catalyst, 2 is a buffer tank, 3 is an external circulation pump, 4 is an external circulation conduit, 5 is a packed tower conduit, and 6 is a packed tower.

  The tubular reactor 1 is an upright circular tube type fixed bed reactor, in which a film type catalyst is loaded, and its temperature can be controlled by heating from the outside. The buffer tank 2 is a storage tank for a mixture of liquid reactants and / or products, and these are circulated with the reactor 1 by a pump 3. A mixture of reactants and / or products and gaseous primary or secondary amine and hydrogen gas are continuously fed from the lower end of the reactor 1 through the conduit 4 and unreacted and / or produced from the upper end. A mixture of substances and hydrogen gas are continuously collected and introduced into the buffer tank 2. Unreacted gaseous primary or secondary amine and water are continuously discharged through the conduit 5. In addition to the above, the component discharged from the conduit 5 may contain alcohol, and / or vapor or mist-like component of the generated tertiary amine, and the like. The remaining gas components are discharged out of the system. The reaction system is maintained at almost normal pressure.

  The method of supplying the reaction liquid to the reactor 1 may be an upflow system as shown in FIG. 1, or conversely a downflow system. As usual, the reactor is preferably temperature-controlled by a jacket or a heat exchange pipe installed inside.

  In the reaction between the alcohol and the primary or secondary amine in the present invention, the number of external circulations per hour of the reaction solution is 3 times / Hr or more, preferably 4 times / Hr or more from the viewpoint of suppressing side reactions. 5 times / hr or more is more preferable. The upper limit of the number of external circulations is preferably 200 times / Hr or less, and more preferably 100 times / Hr or less, from the viewpoint of reducing energy required for circulation.

  The number of external circulations per hour of the reaction liquid can be controlled by the amount of raw material charged and the circulation amount of the external circulation pump 3 in FIG. Further, the number of external circulations per hour may be changed depending on the reaction time, for example, increasing at the beginning of the reaction and decreasing at the end of the reaction.

  The reaction conditions between the alcohol and the primary or secondary amine in the present invention vary depending on the type of reactant, product and catalyst. The reactant may be present in the gas phase or in the liquid phase. When a gas phase is present in the reaction system, it is preferable to carry out the reaction in an atmosphere of hydrogen, nitrogen and / or a rare gas in order to maintain the activity of the catalyst. In a gas-liquid two-phase reaction system, when alcohol and primary or secondary amine are present in different phases, it is desirable to promote mass transfer between the phases by gas bubbling into the liquid. In addition, the above-described mass transfer promotion effect can be obtained by supplying the reactant in a gas-liquid mixed phase to a reaction field in which a narrow flow passage having a diameter of several mm or less is formed by a film type catalyst.

  It is desirable that the pressure in the system does not increase significantly beyond normal pressure. The reaction temperature varies depending on the type of catalyst, but it is preferable to carry out the reaction at a temperature of 150 to 300 ° C. Further, by discharging the water produced as a by-product in the course of the reaction to the outside of the reaction system, the progress of the reaction can be promoted and the activity of the catalyst can be maintained.

  According to the method of the present invention, a target tertiary amine can be efficiently produced in high yield using alcohol and a primary or secondary amine as raw materials by a simple process that does not require any special mixing operation or catalyst separation operation. Can be manufactured automatically.

  The following examples describe the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.

Production Example 1: Production of film-type catalyst A A film-type catalyst A in which a powdery catalyst was immobilized using a phenol resin as a binder was prepared as follows.

  A synthetic zeolite is charged into a 1 L flask, and then copper nitrate, nickel nitrate and ruthenium chloride are dissolved in water so that the molar ratio of each metal atom is Cu: Ni: Ru = 4: 1: 0.01. The temperature was increased while stirring. A 10% by mass aqueous sodium carbonate solution was gradually added dropwise at 90 ° C. while controlling the pH at 9-10. After aging for 1 hour, the precipitate was filtered, washed with water, dried at 80 ° C. for 10 hours, and calcined at 600 ° C. for 3 hours to obtain a powdered catalyst. The ratio of the metal oxide in the obtained powder catalyst was 50% by mass, and the ratio of the synthetic zeolite was 50% by mass.

  A phenol resin (PR-9480 manufactured by Sumitomo Bakelite, 58% non-volatile content) was added as a binder to 100 parts by mass of the powdered catalyst so that the non-volatile content of the phenol resin was 47.7 parts by mass. Further, 2-butanone was added as a solvent so that the ratio of the solid content (non-volatile content of the powdered catalyst and the phenol resin) was 55%. This was premixed for 10 minutes in a dispa, and then mixed and dispersed at 1500 rpm for 70 minutes in a basket mill (SS-3 manufactured by Asada Tekko, filled with 1.4 mm diameter titania beads 800 mL, 1900 g) to form a paint. A copper foil (thickness 40 μm, 6.5 cm × 410 cm × 1 sheet) was used as a support, and the paint was applied on both sides with a bar coater and then dried at 150 ° C. for 30 seconds. Half of the dried material is bent into a corrugated plate, wound over the remaining flat plate, wound, and then cured at 150 ° C. for 90 minutes to fix the film-type catalyst on both sides of the copper foil. Turned into. About the obtained film type catalyst, the thickness per one side except the copper foil and the total mass except the copper foil were as shown in Table 1, respectively.

Production Example 2: Production of film-type catalyst B A film-type catalyst B in which a powdery catalyst was immobilized using a phenol resin as a binder was prepared as follows.

  A phenol resin (PR-9480 manufactured by Sumitomo Bakelite, 58% nonvolatile content) is added as a binder to 100 parts by mass of the powdered catalyst produced according to Production Example 1 so that the nonvolatile content of the phenol resin is 47.7 parts by mass. I made it. Furthermore, 4-methyl-2-pentanone was added as a solvent so that the ratio of the solid content (non-volatile content of the powdered catalyst and the phenol resin) was 55%. This was premixed for 10 minutes in a dispa, and then mixed and dispersed at 1500 rpm for 70 minutes in a basket mill (SS-3 manufactured by Asada Tekko, filled with 1.4 mm diameter titania beads 800 mL, 1900 g) to form a paint. A copper foil (thickness 40 μm, 0.3 m × 36 m) was used as a support, and the paint was applied on both sides with a gravure coater and then dried at 150 ° C. for 30 seconds. The dried one is cut into 27 cm × 429 cm × 16 sheets, half of which is bent into a corrugated plate shape, and alternately stacked with the remaining flat plate shape. In the upright circular tube type fixed bed reactor 1 of FIG. After loading the cylindrical holder to be used, the film-type catalyst was fixed on both sides of the copper foil by curing at 150 ° C. for 90 minutes. About the obtained film type catalyst, the thickness per one side except the copper foil and the total mass except the copper foil were as shown in Table 1, respectively.

Production Example 3: Production of Film Type Catalyst C A film type catalyst C in which a powdered catalyst was immobilized using a phenol resin as a binder was prepared as follows.

  A phenol resin (PR-9480 manufactured by Sumitomo Bakelite, 58% nonvolatile content) is added as a binder to 100 parts by mass of the powdered catalyst produced according to Production Example 1, so that the nonvolatile content of the phenol resin is 33.3 parts by mass. I made it. Furthermore, 4-methyl-2-pentanone was added as a solvent so that the ratio of the solid content (non-volatile content of the powdered catalyst and the phenol resin) was 55%. This was premixed for 10 minutes in a dispa, and then mixed and dispersed at 1500 rpm for 70 minutes in a basket mill (SS-3 manufactured by Asada Tekko, filled with 1.4 mm diameter titania beads 800 mL, 1900 g) to form a paint. A copper foil (thickness 40 μm, 6.5 cm × 420 cm × 1 sheet) was used as a support, and the paint was applied on both sides with a bar coater and then dried at 150 ° C. for 30 seconds. Half of the dried material is bent into a corrugated plate, wound over the remaining flat plate, wound, and then cured at 150 ° C. for 90 minutes to fix the film-type catalyst on both sides of the copper foil. Turned into. About the obtained film type catalyst, the thickness per one side except the copper foil and the total mass except the copper foil were as shown in Table 1, respectively.

  In the following Examples 1 to 4, N-dodecyl-N, N-dimethylamine (hereinafter referred to as DM form) using lauryl alcohol and dimethylamine as raw materials, using the circulating fixed bed reactor shown in FIG. Manufactured. In addition, the following% shows the mass% unless there is particular notice.

Example 1
The film type catalyst A obtained in Production Example 1 was loaded into the reactor 1 having an inner diameter of 29.5 mm. The volume of the portion loaded with the film-type catalyst was 0.27 L, and a plurality of channels having a cross-sectional area of about 0.1 cm ² that were communicated in the axial direction of the reactor 1 were formed by the film-type catalyst. While charging 1.0 kg of lauryl alcohol (Calcoal 20 manufactured by Kao Corporation) into the buffer tank 2 and supplying hydrogen gas at a flow rate of 20 L / Hr in terms of standard state volume, between the buffer tank 2 and the reactor 1 Was circulated 5.1 times / hr. The number of times of liquid circulation can be obtained by the following formula (1) from the charged capacity of raw material alcohol: V (L) and the external circulation flow rate: Q (L / Hr).

Number of times of liquid circulation (times / Hr) = Q / V (1)
In Example 1, 1.0 kg of raw material alcohol was converted to a density of 0.683 (g / cm ³ ) at 220 ° C. to obtain V = 1.46 (L), and this and Q = 7.5 (L / Hr) From the above, the following formula (1) was used.

Number of times of liquid circulation = 7.5 / 1.46 = 5.1 (times / Hr)
After raising the temperature inside the reactor 1 to 220 ° C., the reaction was started at 220 ° C. by supplying dimethylamine. The amount of dimethylamine supplied was adjusted according to the progress of the reaction, and the average reaction time was 79 g / Hr. After 5.9 hours from the start of the reaction, the supply of dimethylamine was stopped, and the entire liquid in the buffer tank 2 and the reactor 1 was extracted. As a result of analysis with a gas chromatograph and quantification by an area percentage method, 1% of unreacted lauryl alcohol, 89.7% of the produced DM form, N, N-didodecyl-N which is a by-product tertiary amine -Methylamine (hereinafter referred to as M2 form) was 7.8%. N, N, N-tridodecylamine was not detected.

Example 2
After raising the temperature inside the reactor 1 to 220 ° C. by the same operation as in Example 1 except that the liquid circulation between the buffer tank 2 and the reactor 1 was performed 3.4 times / Hr, The reaction was started by feeding dimethylamine. The amount of dimethylamine supplied was adjusted according to the progress of the reaction, and the average reaction time was 86 g / Hr. After 6.2 hours from the start of the reaction, the supply of dimethylamine was stopped, and the total amount of liquid in the buffer tank 2 and the reactor 1 was extracted. As a result of gas chromatographic analysis in the same manner as in Example 1, 1% of unreacted lauryl alcohol, 87.4% of the produced DM form, and 9.5% of M2 form of by-product tertiary amine were obtained.

Example 3
The film type catalyst B obtained in Production Example 2 was loaded into the reactor 1 having an inner diameter of 101 mm. The volume of the portion loaded with the film-type catalyst was 17.4 L, and a plurality of flow paths having a cross-sectional area of about 0.1 cm ² connected in the axial direction of the reactor 1 were formed by the film-type catalyst. While charging 46.1 kg of lauryl alcohol (Calcoal 20 manufactured by Kao Corporation) into the buffer tank 2 and supplying hydrogen gas at a flow rate of 922 L / Hr in terms of standard state volume, between the buffer tank 2 and the reactor 1 Was circulated at 10.2 times / hr. After raising the temperature inside the reactor 1 to 220 ° C., the reaction was started at 220 ° C. by supplying dimethylamine. The amount of dimethylamine supplied was adjusted according to the progress of the reaction. After 3.8 hours from the start of the reaction, the supply of dimethylamine was stopped, and the entire liquid in the buffer tank 2 and the reactor 1 was extracted. As a result of analysis by gas chromatograph and quantification by area percentage method, 1% of unreacted lauryl alcohol, 90.4% of produced DM form, and 7.4% of M2 form of by-product tertiary amine. Met. N, N, N-tridodecylamine was not detected.

Example 4
After raising the temperature inside the reactor 1 to 220 ° C. by the same operation as in Example 3 except that the liquid circulation between the buffer tank 2 and the reactor 1 was performed 3.4 times / Hr, The reaction was started by feeding dimethylamine. The amount of dimethylamine supplied was adjusted according to the progress of the reaction. After 3.8 hours from the start of the reaction, the supply of dimethylamine was stopped, and the entire liquid in the buffer tank 2 and the reactor 1 was extracted. As a result of analysis by gas chromatograph in the same manner as in Example 3, the unreacted lauryl alcohol was 1%, the produced DM form was 89.9%, and the by-product tertiary amine M2 form was 8.2%.

  In Example 5 below, N, N-didecyl-N-methylamine (hereinafter referred to as M2 form) using n-decyl alcohol and monomethylamine as raw materials, using the circulating fixed bed reactor shown in FIG. Manufactured. In addition, the following% shows the mass% unless there is particular notice.

Example 5
The film type catalyst C obtained in Production Example 3 was loaded into the reactor 1 having an inner diameter of 29.5 mm. The volume of the portion loaded with the film-type catalyst was 0.27 L, and a plurality of channels having a cross-sectional area of about 0.1 cm ² that were communicated in the axial direction of the reactor 1 were formed by the film-type catalyst. While charging 0.6 kg of n-decyl alcohol (Kalco Co., Ltd. Calcoal 10) into the buffer tank 2 and supplying hydrogen gas at a flow rate of 12 L / Hr in terms of standard state volume, the buffer tank 2 and the reactor 1 The liquid circulation between them was performed at 8.8 times / Hr.

  After raising the temperature inside the reactor 1 to 180 ° C., the reaction was started at 185 ° C. by supplying monomethylamine. The supply amount of monomethylamine was adjusted according to the progress of the reaction, and the average reaction time was 18 g / Hr. After 4.5 hours from the start of the reaction, the supply of monomethylamine was stopped, and the entire liquid in the buffer tank 2 and the reactor 1 was extracted. As a result of analysis by gas chromatograph and quantification by area percentage method, 0.3% of unreacted n-decyl alcohol, 93.6% of produced M2 form, N-decyl which is a by-product tertiary amine -N, N-dimethylamine (hereinafter referred to as DM form) was 0.7%, and N, N, N-tridecylamine (hereinafter referred to as T form) was 1.2%.

1 is a schematic view showing an example of a reaction apparatus used in the present invention.

Explanation of symbols

1 Tube reactor loaded with film type catalyst 2 Buffer tank 3 External circulation pump 4 External circulation conduit 5 Packing tower conduit 6 Packing tower

Claims (5)

A method for producing a tertiary amine from an alcohol and a primary or secondary amine, wherein a reactor loaded with a film-type catalyst is installed in an external circulation line attached to a tank, and the reaction solution is placed in the reactor. A method for producing a tertiary amine, in which the reaction is carried out by circulating the liquid so that the number of times of liquid circulation obtained from the following formula (1) is 5 times / Hr or more.
Number of times of liquid circulation (times / Hr) = Q / V (1)
V (L): Raw alcohol charge capacity Q (L / Hr): Circulation flow rate in external circulation line   The method for producing a tertiary amine according to claim 1, wherein the film-type catalyst is immobilized on the surface of the support, and the thickness of the catalyst is 0.01 to 500 µm.   The method for producing a tertiary amine according to claim 1 or 2, wherein the reactor is a flow-through tubular reactor.   The method for producing a tertiary amine according to any one of claims 1 to 3, wherein the alcohol is a linear or branched, saturated or unsaturated aliphatic alcohol having 8 to 36 carbon atoms.   The manufacturing method of the tertiary amine of any one of Claims 1-4 whose primary or secondary amine is an aliphatic primary or secondary amine.

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