JP2007277160A - Method and apparatus for producing mono lower alkyl monoalkanol amine - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing a mono lower alkyl monoalkanol amine in a high yield. <P>SOLUTION: This method for producing the mono lower alkyl monoalkanol amine, comprising reacting a mono lower alkyl amine with an alkylene oxide in the presence of a catalyst comprising crystalline metallosilicate, is characterized by reducing the rise of temperature in the upstream zone to cool the reaction zone in the presence of the catalyst. The apparatus is characterized by disposing an upstream temperature-lowering mechanism for reducing the rise of the temperature in the upstream portion of the catalyst. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method and apparatus for producing a mono-lower alkyl monoalkanolamine. More specifically, the present invention relates to a production method and apparatus for obtaining mono-lower alkyl monoalkanolamine by reaction of mono-lower alkyl amine and alkylene oxide.

  Mono-lower alkyl alkanolamines are common organic synthetic intermediate materials, such as cationic flocculants, pharmaceutical and agrochemical intermediates, resin etchants, 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.

  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 a useful 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.

  On the other hand, as a method for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkylamine with an alkylene oxide, a production 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.

  Patent Document 1 discloses a method for producing monomethylaminoethanol from monomethylamine and ethylene oxide. In the method described in Patent Document 1, unreacted monomethylamine is recovered by mixing the crude liquid with alcohol in an amine recovery system distillation column or by charging the crude liquid and alcohol in a separate line. However, in this method, in order to recover monomethylamine, it is necessary to mix with alcohol, and in order to reuse monomethylamine, the process is complicated, such as the need for a further distillation column, In addition, there is a problem that the equipment cost becomes high.

  On the other hand, in the production of mono-lower alkyl monoalkanolamines from the reaction of mono-lower alkyl amines and alkylene oxides, there is no problem of heat load due to the reaction in the presence of water and mono-lower alkyl monoalkanol amines with good selectivity. There is provided a technique for obtaining (Patent Document 2).

  The feature of the technology described in Patent Document 2 is that a catalyst made of crystalline metallosilicate or a layered clay compound is used without using water as a catalyst. That is, the method for producing a mono-lower alkyl monoalkanolamine described in Patent Document 2 is a method for producing a mono-lower alkyl monoalkanol amine by reacting a mono-lower alkyl amine with an alkylene oxide, which comprises crystalline metallosilicate or The reaction is performed in the presence of a catalyst composed of a layered clay compound. The mono-lower alkyl monoalkanolamine production apparatus described in Patent Document 2 is an apparatus for producing mono-lower alkyl monoalkanol amine from mono-lower alkyl amine and alkylene oxide, and at least a catalyst is charged. And a reaction part for reacting the mono-lower alkylamine with the alkylene oxide; a recovery means for recovering the mono-lower alkylamine from the reaction product mixture discharged from the reaction part; and the recovered mono-lower It is characterized by having a circulation means for joining the alkylamine to the raw material mono-lower alkylamine.

  The technique described in Patent Document 2 is a very excellent technique capable of obtaining a mono-lower alkylmonoalkanolamine with high selectivity without a problem of heat load since water is not used for the reaction.

Ryohei Oda, Kazuhiro Teramura, “Surfactant”, Tsuji Shoten, 1965, p. 262 to 263 JP-A-8-333310 JP 2004-275933 A

  As described above, since the technique described in Patent Document 2 does not use water for the reaction, it is a very excellent technique capable of obtaining a mono-lower alkylmonoalkanolamine with good selectivity without causing a problem of heat load. However, considering the production of mono-lower alkyl monoalkanolamines in larger quantities and economically, it is desired to produce them continuously and to further improve their yield. And it is desired to provide a more efficient manufacturing method and apparatus therefor.

  This invention is made | formed in view of the said situation, The subject is providing the manufacturing method and apparatus with a higher yield of a mono-lower alkylmonoalkanolamine.

  The first invention of the present invention for solving the above-mentioned problems is a mono-lower alkyl monoalkanolamine, a mono-lower alkyl amine and an alkylene oxide in the presence of a catalyst containing a crystalline metallosilicate or / and a layered clay compound. A mono-lower alkyl, characterized in that, in the method of producing by reacting, cooling of the reaction zone in the presence of the catalyst is carried out by further reducing the temperature rise in the upstream portion of the reaction zone. It exists in the manufacturing method of monoalkanolamine.

  According to a second invention, in the first invention, the reaction zone comprises a plurality of reactors, the former reactor comprises a tubular reactor having a high cooling efficiency, and the latter reactor comprises a catalyst charge amount. In the method for producing a mono-lower alkyl monoalkanolamine, the temperature rise in the upstream portion of the reaction zone is reduced by comprising a tank type reactor having a large amount of water.

  According to a third invention, in the second invention, the diameter of the reaction tube of the preceding tubular reactor is formed such that the downstream portion is larger than the upstream portion, thereby cooling the upstream portion inside the previous reactor. It exists in the manufacturing method of the mono-lower alkylmono alkanolamine characterized by raising efficiency more.

  According to a fourth invention, in the first invention, the reaction zone is constituted by a single tubular reactor, and the diameter of the reaction tube of the tubular reactor is formed so that the downstream portion is larger than the upstream portion. Thus, the present invention provides a method for producing a mono-lower alkylmonoalkanolamine, characterized in that the temperature rise in the upstream portion of the reaction zone is reduced.

  According to a fifth invention, in the first invention, the reaction zone is composed of a plurality of tubular reactors, and the diameter of the reaction tube of the preceding tubular reactor is set to the diameter of the reaction tube of the succeeding tubular reactor. The temperature increase in the upstream portion of the reaction zone is reduced by making the number smaller than the diameter and increasing the number of reaction tubes installed in the former reactor more than the number of reaction tubes installed in the latter reactor. It exists in the manufacturing method of a lower alkyl monoalkanolamine.

  According to a sixth invention, in the first invention, the reaction zone is constituted by a single tank reactor, and a cooling pipe in which the refrigerant flows from upstream to downstream is installed in the tank reactor, whereby the reaction is performed. The present invention provides a method for producing a mono-lower alkyl monoalkanolamine characterized by reducing a temperature rise in an upstream portion of a zone.

  According to a seventh invention, in the sixth invention, the temperature of the upstream part of the reaction zone is further increased by making the density of the cooling pipe laid in the one tank reactor denser in the upstream part than in the downstream part. The present invention resides in a method for producing a mono-lower alkyl monoalkanolamine, characterized in that the rise is reduced.

  According to an eighth invention, in the first invention, the reaction zone is composed of a plurality of tank reactors, and a cooling pipe in which a refrigerant flows from upstream to downstream in the preceding tank reactor is provided, The present invention provides a method for producing a mono-lower alkyl monoalkanolamine characterized by reducing a temperature rise in an upstream portion of a reaction zone.

  According to a ninth invention, in the eighth invention, the upstream portion of the upstream portion in the reactor in the previous stage is made denser in the upstream portion than the downstream portion in the density of the cooling pipe installed in the preceding tank reactor. It exists in the manufacturing method of the mono-lower alkylmonoalkanolamine characterized by raising cooling efficiency more.

  According to a tenth aspect, in the first aspect, the reaction zone is constituted by a plurality of tank reactors in which cooling pipes in which the refrigerant flows from upstream to downstream are installed, and the reaction zone is installed in the preceding tank reactor. The mono-lower alkyl monoalkanolamine is characterized in that the temperature rise in the upstream portion of the reaction zone is reduced by making the laying density of the cooling pipe denser than the laying density of the cooling pipe laid in the downstream reactor. In the manufacturing method.

  An eleventh aspect of the invention is that in the tenth aspect of the invention, the upstream portion has a higher density of the cooling pipe installed in the preceding tank reactor than the downstream portion, so that It exists in the manufacturing method of the mono-lower alkylmonoalkanolamine characterized by raising cooling efficiency more.

  In a twelfth aspect based on the first aspect, the reaction zone is constituted by a plurality of reactors, and the particle size of the catalyst charged in the former reactor is made larger than the particle size of the catalyst charged in the latter reactor. Thus, the present invention provides a method for producing a mono-lower alkylmonoalkanolamine, characterized in that the temperature rise in the upstream portion of the reaction zone is reduced.

  In a thirteenth aspect based on the twelfth aspect, the upstream portion has a larger particle size of the catalyst packed in the upstream reactor than the downstream portion, thereby further improving the cooling efficiency of the upstream portion inside the upstream reactor. It is in the manufacturing method of the mono lower alkyl monoalkanolamine characterized by raising.

  According to a fourteenth aspect, in the first aspect, the reaction zone is constituted by a single reactor, and the particle size of the catalyst charged in the reactor is made larger in the upstream portion than in the downstream portion, whereby the reaction zone In the method for producing mono-lower alkyl monoalkanolamine, which is characterized by reducing the temperature rise in the upstream portion of the product.

  A fifteenth aspect of the invention is a process for producing a mono-lower alkylmonoalkanolamine according to any one of the first to fourteenth aspects, wherein the catalyst containing the crystalline metallosilicate further contains a layered clay compound. .

  A sixteenth aspect of the invention is the mono-lower alkyl monoalkanol according to the fifteenth aspect of the invention, wherein the mixing ratio (mass ratio) of the crystalline metallosilicate and the layered clay compound is from 5:95 to 50:50. It is in the manufacturing method of an amine.

  In a seventeenth aspect based on any one of the first to sixteenth aspects, the crystalline metallosilicate is Al, Ga, Fe, B, Zn, P, Ge, Zr, Ti, Cr, Be, V, And at least one metal element M selected from the group consisting of As and a method for producing a mono-lower alkylmonoalkanolamine.

  In an eighteenth aspect based on the seventeenth aspect, the crystalline metallosilicate is characterized in that the ratio of Si to the metal element M is Si / M = 5 to 1000 on an oxide basis. It exists in the manufacturing method of alkyl monoalkanolamine.

  A nineteenth aspect of the invention is the production of a mono-lower alkyl monoalkanolamine according to the eighteenth aspect of the invention, wherein the ratio of Si to the metal element M is Si / M = 10 to 500 on an oxide basis. Is in the way.

  A twentieth aspect of the invention is the mono lower alkyl monoalkanolamine according to any one of the first to nineteenth aspects, wherein the crystalline metallosilicate has a MOR structure, an MFI structure and / or a MEL structure. In the manufacturing method.

  A twenty-first aspect of the invention is the process for producing a mono-lower alkyl monoalkanolamine according to any one of the first to twentieth aspects, wherein the crystalline metallosilicate is a crystalline aluminosilicate.

  According to a twenty-second aspect of the invention, there is provided the method for producing a mono-lower alkylmonoalkanolamine according to the twenty-first aspect, wherein the crystalline aluminosilicate is zeolite.

  A twenty-third invention is the method for producing a mono-lower alkyl monoalkanolamine according to the first, fifteenth or sixteenth invention, wherein the layered clay compound is acid clay or activated clay.

  A twenty-fourth invention is an apparatus for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine and an alkylene oxide with a catalyst containing a crystalline metallosilicate or / and a layered clay compound. And an apparatus for producing mono-lower alkylmonoalkanolamine, which has an upstream temperature reduction mechanism for further reducing the temperature rise in the upstream portion of the catalyst.

  According to a twenty-fifth aspect, in the twenty-fourth aspect, a plurality of reactors filled with the catalyst are provided, the first-stage reactor is composed of a tubular reactor with high cooling efficiency, and the second-stage reactor is a catalyst. The apparatus for producing a mono-lower alkylmonoalkanolamine is characterized in that the upstream temperature reduction mechanism is realized by a tank reactor having a large amount of packing.

  A twenty-sixth aspect of the invention is the production of a mono-lower alkyl monoalkanolamine according to the twenty-fifth aspect of the invention, wherein the diameter of the reaction tube of the preceding tubular reactor is larger in the downstream part than in the upstream part. In the device.

  According to a twenty-seventh aspect, in the twenty-fourth aspect, the reactor filled with the catalyst comprises a single tubular reactor, and the diameter of the reaction tube of the tubular reactor is larger in the downstream portion than in the upstream portion. By forming the mono lower alkyl monoalkanolamine, the upstream temperature reduction mechanism is realized.

  In a twenty-eighth aspect, in the twenty-fourth aspect, the reactor filled with the catalyst is composed of a plurality of tubular reactors, and the diameter of the reaction tube of the preceding tubular reactor is the latter tubular reactor. It is formed smaller than the diameter of the reaction tube, and the upstream temperature reduction mechanism is realized by increasing the number of reaction tubes installed in the former reactor than the number of reaction tubes installed in the latter reactor. It is in the production apparatus of the characteristic mono-lower alkyl monoalkanolamine.

  According to a twenty-ninth aspect, in the twenty-fourth aspect, the reactor filled with the catalyst is composed of a single tank reactor, and a cooling pipe in which the refrigerant flows from upstream to downstream is laid in the tank reactor. Thus, the upstream lower temperature reduction mechanism is realized in a mono-lower alkyl monoalkanolamine production apparatus.

  A thirtieth aspect of the present invention is the mono-lower alkyl monoalkanol according to the twenty-ninth aspect of the present invention, characterized in that the installation density of the cooling pipe installed in the one tank reactor is denser in the upstream part than in the downstream part. It is in the production equipment of amine.

  According to a thirty-first aspect, in the twenty-fourth aspect, the reactor filled with the catalyst is composed of a plurality of tank reactors, and a cooling pipe in which a refrigerant flows from upstream to downstream is installed in the preceding tank reactor. Thus, the apparatus for producing mono-lower alkyl monoalkanolamine is characterized in that the upstream temperature reduction mechanism is realized.

  A thirty-second invention is the mono-lower alkyl monoalkanol according to the thirty-first invention, characterized in that the density of the cooling pipe installed in the preceding tank reactor is denser in the upstream part than in the downstream part. It is in the production equipment of amine.

  According to a thirty-third aspect, in the twenty-fourth aspect, the reactor filled with the catalyst includes a plurality of tank-type reactors in which cooling pipes in which a refrigerant flows from upstream to downstream are provided, A mono-lower alkyl, wherein the upstream temperature reduction mechanism is realized by making the installation density of the cooling pipe installed in the vessel denser than the installation density of the cooling pipe installed in the downstream reactor. It is in production equipment for monoalkanolamine.

  A thirty-fourth aspect of the invention is the mono-lower alkyl monoalkanol according to the thirty-third aspect of the invention, characterized in that the density of the cooling pipes laid in the preceding tank reactor is denser in the upstream part than in the downstream part. It is in the production equipment of amine.

  A thirty-fifth aspect of the present invention is that in the twenty-fourth aspect, the reactor filled with the catalyst is composed of a plurality of reactors, and the particle size of the catalyst charged in the former stage reactor is that of the catalyst charged in the latter stage reactor. The apparatus for producing mono-lower alkylmonoalkanolamine is characterized in that the upstream temperature reduction mechanism is realized by making it larger than the particle diameter.

  A thirty-sixth aspect of the invention is the apparatus for producing a mono-lower alkylmonoalkanolamine according to the thirty-fifth aspect of the invention, wherein the upstream portion of the catalyst packed in the preceding reactor is made larger in particle size than the downstream portion. It is in.

  In a thirty-seventh aspect based on the twenty-fourth aspect, the reactor filled with the catalyst is composed of one reactor, and the particle size of the catalyst filled in the reactor is larger in the upstream portion than in the downstream portion. Thus, the apparatus for producing mono-lower alkylmonoalkanolamine is characterized in that the upstream temperature reduction mechanism is realized.

  A thirty-eighth aspect of the invention is the apparatus for producing a mono-lower alkylmonoalkanolamine according to any one of the twenty-fourth to the thirty-seventh aspects, wherein the catalyst containing the crystalline metallosilicate further contains a layered clay compound. It is in.

  A thirty-ninth aspect of the invention is the mono-lower alkyl monoalkanol according to the thirty-eighth aspect of the invention, wherein the mixing ratio (mass ratio) of the crystalline metallosilicate and the layered clay compound is 5:95 to 50:50. It is in the production equipment of amine.

  In a 40th invention according to any one of the 24th to 39th inventions, the crystalline metallosilicate is Al, Ga, Fe, B, Zn, P, Ge, Zr, Ti, Cr, Be, V, And at least one metal element M selected from the group consisting of As and a mono-lower alkylmonoalkanolamine production apparatus.

  In a forty-first aspect according to the forty-first aspect, the crystalline metallosilicate is characterized in that the ratio of Si to the metal element M is Si / M = 5 to 1000 on an oxide basis. It is in the production apparatus of alkyl monoalkanolamine.

  A forty-second aspect of the invention is the production of a mono-lower alkylmonoalkanolamine according to the forty-first aspect, wherein the ratio of Si to the metal element M is Si / M = 10 to 500 based on the oxide. In the device.

  A forty-third aspect of the invention is the monolower alkylmonoalkanolamine of any one of the twenty-fourth to forty-second aspects, wherein the crystalline metallosilicate has an MOR structure, an MFI structure and / or an MEL structure. In production equipment.

  A forty-fourth invention is an apparatus for producing mono-lower alkylmonoalkanolamine according to any one of the twenty-fourth to forty-third inventions, wherein the crystalline metallosilicate is a crystalline aluminosilicate.

  According to a 45th aspect of the invention, in the 44th aspect of the invention, the crystalline aluminosilicate is a zeolite, which is a mono-lower alkylmonoalkanolamine.

  A forty-sixth aspect of the present invention is the apparatus for producing mono-lower alkylmonoalkanolamine according to the twenty-fourth, thirty-eighth or thirty-ninth aspect, wherein the layered clay compound is acidic clay or activated clay.

  According to the present invention having the above-described configuration, it is possible to provide a production method and apparatus of a mono-lower alkyl monoalkanolamine having a high yield.

  Hereinafter, the configuration of the present invention will be described in more detail, and representative embodiments will be described.

(Catalyst used)
In the present invention, a crystalline metallosilicate can be used as a catalyst used for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine with an alkylene oxide.

  In the present invention, as the crystalline metallosilicate, for example, at least one metal element selected from the group consisting of Al, Ga, Fe, B, Zn, P, Ge, Zr, Ti, Cr, Be, V, and As is used. Among them, those containing Al and / or Ga are preferable, and those containing Al are particularly preferable. Specifically, it is preferable to use crystalline aluminosilicate, and it is particularly preferable to use zeolite. As the crystalline metallosilicate, one prepared by a known method such as a so-called hydrothermal synthesis method or a dry gel method can be used.

  In the crystalline metallosilicate used in the present invention, the ratio of Si to the metal element M is preferably Si / M (where M represents a metal element) = 5 to 1000 on an oxide basis, More preferably, it is 10-500. If the ratio of Si to metal element M is within the above range, mono-lower alkyl monoalkanolamine (hereinafter also referred to as “di-type”) and mono-lower alkyl monoalkanolamine (hereinafter also referred to as “mono-type”). ) Can be obtained with good selectivity.

  Examples of the metallosilicate include MFI, MEL, BEA, MOR, MTW, TON, FAU and the like when expressed by a framework topology code indicating the structure of the International Zeolite Society. Among them, in the present invention, it is preferable to use those having an MOR structure, an MFI structure and / or an MEL structure from the viewpoint of selective synthesis of mono-lower alkylmonoalkanolamine. MFI and MEL are similar in structure, and intergrowth may occur and both structures may be included in one crystal, but both can be used in the present invention.

  An example of a metallosilicate having an MFI structure is ZSM-5 known as a synthetic zeolite. ZSM is an abbreviation for Zeolite of Socony Mobile, derived from the name of the company that developed it. Moreover, as what has a MEL structure, ZSM-11 similarly known as a synthetic zeolite is mentioned. In the present invention, it is preferable to use zeolite, and it is particularly preferable to use ZSM-5.

Generally, a crystalline metallosilicate contains a proton, an ammonium ion, etc. as a cation. Examples of such cations include H ⁺ , NH ₄ ⁺ , Na ⁺ , K ⁺ , Ca ²⁺ , La ^{3+, and the} like, and depending on the type of cation, proton type, ammonium ion type, etc. Called. In the present invention, any type can be used, and among them, those containing NH ₄ ⁺ , H ⁺ , and Na ⁺ are preferable, and those containing NH ₄ ⁺ and H ⁺ are particularly preferable. Is.

  In the present invention, a layered clay compound can also be mentioned as a catalyst used for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine with an alkylene oxide. Here, the “layered clay compound” refers to a clay containing a layered clay mineral, and examples of the layered clay mineral include a kaolin mineral, a mica clay mineral, and a smectite (montmorillonite) and a mixed layer mineral. Clays containing these have specific properties such as ion exchange properties, adsorptivity, catalytic ability, complex forming ability, and swelling property. These chemical activities are referred to as surface activity, and examples of the layered clay compound having this property include layered clay compounds called bentonite and acid clay containing smectite as a main component mineral. In addition, layered clay compounds are composed of hyrosite, kaolinite, smectite, vermiculite, chlorite, depending on how the silicic acid tetrahedron layers overlap in the crystalline silicate that composes them, and the type and arrangement of atoms in the layer. And so on.

  Examples of the layered clay compound suitable as a catalyst used in the present invention include acidic clay, Ca bentonite, and hyrosite, and further improving the performance such as adsorption ability, decolorization ability, and catalytic ability by acid treatment. Active clay. A particularly suitable layered clay compound in terms of selectivity is acid clay.

  The layered clay compound can be used as a catalyst as it is, but from the viewpoint of selectivity, it is preferably used after being dried. The drying treatment is preferably carried out until the weight reduction becomes constant, and can usually be carried out until the weight is reduced by about 5 to 10%, for example, at 50 to 200 ° C. for about 0.5 to 24 hours. it can.

  In the present invention, a catalyst containing the above crystalline metallosilicate and a layered clay compound can also be used in the reaction of mono-lower alkylamine and alkylene oxide. The mixing ratio (mass ratio) of the crystalline metallosilicate and the layered clay compound is preferably 5:95 to 50:50, more preferably 5:95 to 30:70. If the mixing ratio of both components is within the above range, a mono-lower alkyl monoalkanolamine can be produced with higher selectivity than when each of them is used alone. In general, the crystalline metallosilicate is more expensive than the layered clay compound, and therefore, from the viewpoint of cost, it is preferable to reduce the proportion of the crystalline metallosilicate within a range where desired selectivity can be obtained.

  In the present invention, when a catalyst containing a crystalline metallosilicate and a layered clay compound is used, there is no particular limitation on the combination of both, but preferred combinations include zeolite and acidic clay, zeolite and activated clay, zeolite and acidic clay, and activity. There is white clay. A particularly suitable combination is zeolite and acid clay.

  The catalyst can be used as it is, but may be molded to an appropriate size and hardness when used. If necessary, you may shape | mold using auxiliary agents or binders, such as various oxide sols, such as a silica sol, and clay minerals.

  The mono-lower alkylamine used in the present invention is not particularly limited, but monomethylamine, monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, mono-sec-butylamine, mono-t-butylamine A linear or branched monoalkylamine having 1 to 6 carbon atoms such as mono n-pentylamine, isopentylamine, mono n-hexylamine, etc., preferably monomethylamine, Monoethylamine, mono-n-propylamine, monoisopropylamine, mono-n-butylamine, monoisobutylamine, mono-t-butylamine can be used, and monomethylamine, monoethylamine, mono-n-propylamine, monoisopropyl are particularly preferred. Amine, mo It can be used n- butylamine.

  The alkylene oxide 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, etc. can be preferably used, and particularly preferably ethylene oxide and propylene. Oxides can be used.

  The production of the mono-lower alkyl monoalkanolamine can be carried out in the temperature range of 40 to 300 ° C., for example. A preferred temperature range is 50 to 200 ° C., and a particularly preferred temperature range is 50 to 150 ° C. The operating pressure can be, for example, 0.1 to 20 MPa, preferably 0.1 to 15 MPa, and particularly preferably 3.0 to 10 MPa. The amount of mono-lower alkylamine and alkylene oxide used and the amount of catalyst used can be appropriately set according to the reaction conditions and the like. In order to selectively obtain the mono form by the reaction of mono lower alkyl amine and alkylene oxide, it is necessary to use an excess amount of mono lower alkyl amine with respect to alkylene oxide, for example, 1.5 to 20 on a molar basis. It can be used in double amounts, and is particularly preferably used in 2 to 10 times amounts.

  The apparatus for producing mono-lower alkyl monoalkanolamines of the present invention reacts mono-lower alkyl monoalkanol amines with mono-lower alkyl amines and alkylene oxides in the presence of a catalyst containing a crystalline metallosilicate or / and a layered clay compound. Therefore, it is an apparatus to manufacture. The characteristic configuration of this manufacturing apparatus is that it has an upstream temperature reduction mechanism that further reduces the temperature rise in the upstream portion of the catalyst. Various configurations for realizing the upstream temperature reduction mechanism will be described in the following embodiments.

  As described above, the apparatus for producing a mono-lower alkyl monoalkanolamine of the present invention is a catalyst comprising a mono-lower alkyl monoalkanol amine, a mono-lower alkyl amine and an alkylene oxide, a crystalline metallosilicate or / and a layered clay compound. The apparatus to be produced by reacting in the presence is characterized by having an upstream temperature reduction mechanism that further reduces the temperature rise in the upstream portion of the catalyst.

Example 1
In the production apparatus for mono-lower alkyl monoalkanolamine of this example, the characteristic upstream temperature reduction mechanism is, as shown in FIG. 1, a plurality of reactors filled with a catalyst (two in the figure), The upstream temperature reduction mechanism 101 realized by the upstream reactor configured from the tubular reactor 1 with high cooling efficiency and the downstream reactor configured from the tank reactor 2 with a large amount of catalyst filling. It is.

  The tubular reactor 1 and the tank reactor 2 are preferably each provided with an internal cooling jacket 3 and an external jacket 4 so that the internal catalyst 5 can be cooled by a cooling medium. Although the tubular reactor 1 is illustrated as one in the figure so as not to become complicated, it is composed of a plurality of reaction tubes 6. The specific tube diameter, tube length, and number of tubes of these reaction tubes 6 are, for example, 60 inner diameters of 30 mm × length of 8000 mm. One of the tank reactors 2 has no compartments, and the entire volume is filled with the catalyst 5, and the catalyst 5 having a filling amount significantly larger than the catalyst filling amount in the tubular reactor 1 is accommodated. Yes.

  From the upper part of the tubular reactor 1, the raw material 7, that is, mono-lower alkylamine and alkylene oxide are supplied. The mono-lower alkylamine and alkylene oxide introduced into the tubular reactor 1 are reacted with each other by the catalyst 5 in each reaction tube 6 to produce a mono-lower alkylmonoalkanolamine. Since the tubular reactor 1 has a relatively small amount of catalyst filling, the reaction of the entire amount of the feedstock cannot be realized, and the unreacted raw material remains. The unreacted component is reacted in the downstream tank reactor 2. Since the amount of catalyst in the tank reactor 2 is sufficiently secured, most of the unreacted raw material is reacted.

  In the reaction product mixture 8 derived from the tank reactor 2, a mono-lower alkyl monoalkanolamine (monomer) occupying most of the reaction mixture, a small amount of unreacted raw materials, and a mono-lower alkyl which is a side reaction product. Since dialkanolamine (dimer) is contained, in the next step (not shown), unreacted raw materials are collected and circulated to the raw materials by distillation or the like, and dimers are separated and removed.

  The reaction between the mono-lower alkylamine and the alkylene oxide caused to react by the catalyst 5 is an exothermic reaction, and the calorific value is relatively large. Therefore, if the heat generated by the reaction is left uncooled, not only the reaction rate is lowered, but also the catalyst 5 is prematurely deteriorated. Since this heat generation is generated in a larger amount as the raw material concentration is higher, the heat generation in the upstream of the catalyst becomes remarkable, and the deterioration in the upstream catalyst is accelerated. However, if the temperature of the catalyst is extremely low, the reaction is less likely to occur. Therefore, it is important to control the temperature of the catalyst within a temperature range in which the deterioration of the catalyst is prevented and the reaction rate can be sufficiently increased.

  In addition, as described above, in the reaction of mono-lower alkylamine and alkylene oxide, mono-lower alkyl dialkanolamine (dimer) is generated as a by-product, and the target mono-lower alkyl depends on the amount of dimer produced. The yield of monoalkanolamine (monomer) is affected. The monomer yield increases as the temperature decreases, and the reaction rate of the raw material alkyl oxide increases as the temperature increases. From this point of view, it is necessary to control the reaction environment temperature, in other words, the catalyst temperature within the optimum range.

  In response to the above-described temperature control requirement, in the apparatus configuration shown in FIG. 1, the temperature of the catalyst 5 reduces the reaction rate because the previous reactor is composed of the tubular reactor 1 with high catalyst cooling efficiency. In addition, the temperature of the catalyst can be easily controlled within a temperature range suitable for increasing the monomer yield without shortening the life of the catalyst. The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

  Further, as described above, since the raw material concentration supplied to the preceding tubular reactor 1 is higher than the raw material concentration supplied to the subsequent tank reactor 2, when considering the monomer yield as a whole, The reaction rate in the former tubular reactor 1 is preferably 50 to 70% on the basis of one raw material alkyl oxide, and the same reaction rate in the latter tank reactor 2 is preferably 50 to 30%. Further, when the yield of the monomer is set to a sufficient value by controlling the reaction rate, the residual concentration of the raw material alkyl oxide in the reaction product mixture 7 derived from the subsequent tank reactor 2 is 500 ppm or less. To be controlled.

  In the apparatus configuration of FIG. 1, as shown in FIG. 2, the reaction tube of the preceding tubular reactor 1 may be configured of a reaction tube 6 a in which the tube diameter is formed larger in the downstream portion than in the upstream portion. By using the reaction tube 6a having such a shape, it is possible to further reduce the temperature rise in the upstream portion where the temperature rise of the catalyst 5 in the tubular reactor 1 is most likely to occur.

(Example 2)
As shown in FIG. 3, the upstream temperature reduction mechanism 102, which is a characteristic configuration of the mono-lower alkyl monoalkanolamine production apparatus according to the second embodiment, includes a single tubular reactor 9 that is filled with a catalyst. In addition, the tube diameter of the reaction tube 10 of the tubular reactor 9 is realized by forming the downstream portion larger than the upstream portion.

  The tubular reactor 9 is preferably provided with an internal cooling jacket 11 so that the internal catalyst 5 can be cooled by a cooling medium. In addition, the tubular reactor 9 is illustrated as a single unit so as not to be complicated in the drawing, but is composed of a plurality of reaction tubes 9. The specific tube diameter, tube length, and number of tubes of these reaction tubes 9 are, for example, an inner diameter of the upstream portion of 20 mm × an inner diameter of the downstream portion of 40 mm × a length of 4500 mm and 275.

  From the upper part, the tubular reactor 9 is fed with the raw material 7, that is, mono-lower alkylamine and alkylene oxide. The mono-lower alkylamine and alkylene oxide introduced into the tubular reactor 9 are reacted with each other by the catalyst 5 in each reaction tube 10 to produce mono-lower alkylmonoalkanolamine. Since the catalyst filling amount in the narrow upstream portion of each reaction tube 10 is relatively small, the reaction of the entire amount of the feedstock cannot be realized, and unreacted raw material remains. The unreacted component is reacted in the downstream portion having a large pipe diameter. Since the amount of catalyst in the downstream portion is sufficiently secured, most of the unreacted raw material is reacted.

  In the reaction product mixture 8 led out from the tubular reactor 9, a mono-lower alkyl monoalkanolamine (monomer) occupying most of it, a small amount of unreacted raw material, and a mono-lower alkyl which is a side reaction product. Since dialkanolamine (dimer) is contained, in the next step (not shown), unreacted raw materials are collected and circulated to the raw materials by distillation or the like, and dimers are separated and removed.

  In the apparatus configuration shown in FIG. 3, the upstream portion of the plurality of reaction tubes 10 installed in the tubular reactor 9 is formed thin and the cooling efficiency is increased, so that the upstream portion where the temperature is likely to rise. The catalyst temperature can be further reduced. As a result, the temperature of the catalyst 5 in the tubular reactor 9 is easily controlled to a temperature range suitable for increasing the monomer yield without reducing the reaction rate and shortening the life of the catalyst. be able to. The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

(Example 3)
In the apparatus for producing mono-lower alkyl monoalkanolamine of Example 3, the characteristic upstream temperature reduction mechanism is a plurality of reactors (two in the figure) filled with a catalyst as shown in FIG. The upstream temperature reduction mechanism realized by the fact that the former reactor is constituted by the tubular reactor 12 having a high cooling efficiency and the latter reactor is constituted by the tubular reactor 13 having the same high cooling efficiency. 103. A plurality of reaction tubes 14 and 15 are provided in the former tubular reactor 12 and the latter tubular reactor 13, respectively. The tube diameter of the reaction tube 14 in the upstream tubular reactor 12 is formed to be smaller than the tube diameter of the reaction tube 15 in the downstream tube reactor 13, and accordingly, the upstream tube reactor 12. The number of installed reaction tubes 14 is larger than the number of installed reaction tubes 15 in the subsequent tubular reactor 13.

  The specific tube diameter, tube length, and number of tubes of the reaction tube 14 in the upstream tubular reactor 12 are, for example, an inner diameter of 20 mm × length of 3600 mm and 275, and the reaction in the downstream tubular reactor 13 is performed. Specific pipe diameters, pipe lengths, and the number of installed pipes 15 are, for example, inner diameter 40 mm × length 3600 mm, 69. For this reason, the upstream tubular reactor 12 has higher cooling (heat removal) performance than the downstream reactor 13, and the downstream tubular reactor 13 has a larger amount of catalyst 15 correspondingly. It has become.

  The front-stage tubular reactor 12 and the rear-stage tubular reactor 13 are preferably provided with internal cooling jackets 16 and 17, respectively, so that the internal catalyst 5 can be cooled by a cooling medium.

  A raw material 7, that is, a mono-lower alkylamine and an alkylene oxide are supplied to the former tubular reactor 12 from the upper part thereof. The mono-lower alkylamine and alkylene oxide introduced into the tubular reactor 12 are reacted with each other by the catalyst 5 in each reaction tube 14 to produce mono-lower alkylmonoalkanolamine. Since the tubular reactor 12 has a relatively small amount of catalyst filling, the reaction of the entire amount of the feedstock cannot be realized, and the unreacted raw material remains. The unreacted component is reacted in the tubular reactor 13 at the subsequent stage. Since the amount of catalyst in this tubular reactor 13 is relatively large, most of the unreacted raw material is reacted.

  In the reaction product mixture 8 led out from the tank reactor 13, in addition to the mono-lower alkyl monoalkanolamine (monomer) occupying most of the reaction product mixture 8, a small amount of unreacted raw material and a mono-lower alkyl which is a side reaction product. Since dialkanolamine (dimer) is contained, in the next step (not shown), unreacted raw materials are collected and circulated to the raw materials by distillation or the like, and dimers are separated and removed.

  In the apparatus configuration shown in FIG. 4, a plurality of reaction tubes 14 installed in the preceding tubular reactor 12 are formed narrower than the reaction tube 15 installed in the succeeding tubular reaction tube 13. Since the cooling efficiency is enhanced, the catalyst temperature at the front end where the temperature tends to rise can be further reduced. As a result, the temperature of the catalyst 5 in the preceding tubular reactor 12 can be easily set to a temperature range suitable for increasing the yield of the monomer without reducing the reaction rate and reducing the life of the catalyst. Can be controlled. The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

Example 4
As shown in FIG. 5, the upstream temperature reduction mechanism 104, which is a characteristic configuration of the mono-lower alkyl monoalkanolamine production apparatus of the fourth embodiment, is composed of a tank reactor 18 in which a reactor is filled with a catalyst. In the tank reactor 18, a single cooling tube 19 is arranged to meander from upstream to downstream so that the internal catalyst 5 can be cooled from upstream to downstream by a cooling medium. It has become. Since the cooling medium is introduced into the cooling pipe 19 from the upstream side, the cooling (heat removal) efficiency of the catalyst becomes higher toward the upstream side.

  From the upper part of the tank reactor 18, the raw material 7, that is, mono-lower alkylamine and alkylene oxide are supplied. The mono-lower alkylamine and alkylene oxide introduced into the tank reactor 18 are reacted with each other by the catalyst 5 in the tank to produce mono-lower alkyl monoalkanolamine. Since the reactor 18 is a tank type, it is filled with a sufficient amount of the catalyst 5, and therefore most of the raw materials are reacted.

  In the reaction product mixture 8 led out from the tank reactor 18, in addition to the mono-lower alkyl monoalkanolamine (monomer) that occupies most of the reaction product mixture 8, a small amount of unreacted raw materials and mono-lower alkyl that is a side reaction product. Since dialkanolamine (dimer) is contained, in the next step (not shown), unreacted raw materials are collected and circulated to the raw materials by distillation or the like, and dimers are separated and removed.

  In the apparatus configuration shown in FIG. 5, since the cooling pipe 19 disposed in the tank reactor 18 allows the cooling medium to flow from upstream to downstream, the cooling efficiency of the upstream portion is further increased, so the temperature is It is possible to further reduce the catalyst temperature in the upstream portion that is likely to rise. As a result, the temperature of the catalyst 5 in the tank reactor 18 is easily controlled within a temperature range suitable for increasing the monomer yield without reducing the reaction rate and reducing the catalyst life. be able to. The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

  In the apparatus configuration of FIG. 5, as shown in FIG. 6, a cooling pipe disposed inside the tank reactor 18 is constituted by a reaction tube 20 having a structure that branches in parallel in the tank and flows from upstream to downstream. Also good. Even when the cooling pipe 20 having such a shape is used, the same operations and effects as those when the cooling pipe 19 shown in FIG. 5 is provided can be obtained.

  In the apparatus configuration of FIG. 5, as shown in FIG. 7, the cooling pipe of the tank reactor 18 may be constituted by a reaction tube 19 a in which the upstream portion is laid more densely than the downstream portion. By using the cooling pipe 19a having such a shape, the temperature rise in the upstream portion where the temperature rise of the catalyst 5 in the tank reactor 18 is most likely to occur can be further reduced.

  In the apparatus configuration of FIG. 6, as shown in FIG. 8, a reaction tube in which the upstream portion of the cooling pipe of the tank reactor 18 is more densely arranged than the downstream portion (in other words, a large number of branches). You may comprise from 20a. By using the cooling pipe 20a having such a shape, it is possible to further reduce the temperature rise of the upstream portion of the upstream portion where the temperature rise of the catalyst 5 in the tank reactor 18 is most likely to occur.

(Example 5)
In the apparatus for producing mono-lower alkyl monoalkanolamine of Example 5, the characteristic upstream temperature reduction mechanism has a plurality of reactors (two in the figure) filled with a catalyst as shown in FIG. Each of the first and second reactors is composed of tank reactors 21 and 22, and a single cooling tube 23 is disposed in the former tank reactor 21 so as to meander from upstream to downstream. Thus, the upstream temperature reduction mechanism 105 is realized. Since the cooling tank 23 is disposed in the preceding tank reactor 21, the heat removal effect of the catalyst in the preceding tank reactor 21 is enhanced, and further, the cooling medium from the upstream into the cooling pipe 19 is increased. Therefore, the cooling (heat removal) efficiency of the catalyst 5 in the preceding tank reactor 21 becomes higher toward the upstream in the tank.

  From the upper part, the tank reactor 21 is fed with the raw material 7, that is, mono-lower alkylamine and alkylene oxide. The mono-lower alkylamine and alkylene oxide introduced into the tank reactor 21 are reacted with each other by the catalyst 5 in the tank to produce a mono-lower alkylmonoalkanolamine. Then, the reaction product mixture is sent to the subsequent tank reactor 22, and most of the unreacted raw material in the reaction mixture is reacted by the catalyst 5 in the tank reactor 22.

  In the reaction product mixture 8 led out from the tank reactor 22 at the latter stage, a small amount of unreacted raw materials and a mono-lower, which is a side reaction product, in addition to the mono-lower alkyl monoalkanolamine (monomer) that occupies most of the reaction product mixture 8. Since alkyl dialkanolamine (dimer) is contained, in the next step (not shown), unreacted raw materials are collected and circulated for the raw materials by distillation or the like, and dimers are separated and removed.

  In the apparatus configuration shown in FIG. 9, the temperature of the catalyst in the preceding tank reactor 21 in which the amount of generated heat of reaction increases due to the cooling pipe 23 disposed in the preceding tank reactor 21. Can be suppressed. Further, since the cooling medium flows from the upstream to the downstream in the cooling pipe 23, the cooling efficiency of the upstream portion in the previous tank reactor 21 is further increased, so the catalyst temperature in the upstream portion where the temperature is likely to rise is further increased. Can be reduced. As a result, the temperature of the catalyst 5 in the tank reactor 21 is easily controlled within a temperature range suitable for increasing the monomer yield without reducing the reaction rate and shortening the life of the catalyst. be able to. The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

  In the apparatus configuration of FIG. 9, as shown in FIG. 10, the cooling pipe of the preceding tank type reactor 21 may be constituted by a reaction tube 23 a in which the upstream portion is laid more densely than the downstream portion. By using the cooling pipe 23a having such a shape, it is possible to further reduce the temperature rise in the upstream portion where the temperature rise of the catalyst 5 in the tank reactor 21 is most likely to occur.

(Example 6)
In the apparatus for producing mono-lower alkyl monoalkanolamine of Example 6, the characteristic upstream temperature reduction mechanism has a plurality of reactors (two in the figure) filled with a catalyst as shown in FIG. The first and second reactors are both composed of tank reactors 24 and 25, and each of the first and second tank reactors 24 and 25 has a single cooling structure from upstream to downstream. The upstream temperature reduction mechanism 106 is realized by arranging the pipes 26 and 27 to meander. The laying density of the cooling pipe 26 disposed in the preceding tank reactor 24 is higher than the laying density of the cooling pipe 27 disposed in the succeeding tank reactor 25, so that the preceding tank type The heat removal effect of the catalyst in the reactor 21 is further enhanced. Further, since the cooling medium is introduced into the respective cooling pipes 26 and 27 from upstream, the cooling (heat removal) efficiency of the internal catalyst 5 is higher in the respective tank reactors 24 and 27 as the upstream in each tank. Become.

  A raw material 7, that is, a mono-lower alkylamine and an alkylene oxide are supplied from the upper part of the previous tank reactor 24. The mono-lower alkylamine and alkylene oxide introduced into the tank reactor 24 are reacted with each other by the catalyst 5 in the tank to produce a mono-lower alkyl monoalkanolamine. Then, the reaction product mixture is sent to the subsequent tank reactor 27, and most of the unreacted raw material in the reaction mixture is reacted by the catalyst 5 in the tank reactor 27.

  In the reaction product mixture 8 led out from the tank reactor 27 in the subsequent stage, in addition to the mono-lower alkyl monoalkanolamine (monomer) that occupies most of the reaction product mixture 8, a small amount of unreacted raw material and a mono-lower product that is a side reaction product. Since alkyl dialkanolamine (dimer) is contained, in the next step (not shown), unreacted raw materials are collected and circulated for the raw materials by distillation or the like, and dimers are separated and removed.

  In the apparatus configuration shown in FIG. 11, the installation density of the cooling pipe 27 provided in the subsequent tank reactor 25 is set as the installation density of the cooling pipe 26 provided in the previous tank type reactor 24. By making it higher, it is possible to appropriately suppress the temperature rise of the catalyst in the preceding tank reactor 24 in which the amount of reaction heat generated increases. Further, since the cooling medium flows from the upstream to the downstream in each cooling pipe 26 and 27, the cooling efficiency of the upstream portion in each tank reactor 26 and 27 is further increased, so the temperature rises in each tank. It is possible to further reduce the temperature of the catalyst in the upstream portion, which is easy. As a result, the temperature of each catalyst 5 in the tank reactors 24 and 25 does not reduce the reaction rate, shortens the life of the catalyst, and easily falls within a temperature range suitable for increasing the monomer yield. Can be controlled. The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

  In the apparatus configuration of FIG. 11, as shown in FIG. 12, the cooling pipe of the preceding tank type reactor 24 may be constituted by a reaction tube 26 a in which the upstream portion is laid more densely than the downstream portion. By using the cooling pipe 26a having such a shape, it is possible to further reduce the temperature rise in the upstream portion where the temperature rise of the catalyst 5 in the previous tank reactor 24 is most likely to occur.

  The cooling pipe 23 shown in FIG. 9, the cooling pipe 27 shown in FIG. 11, and the cooling pipe 27 shown in FIG. 12 are composed of branch-type cooling pipes such as the cooling pipe 20 shown in FIG. 6. You may do it. Further, the cooling pipe 23a shown in FIG. 10 and the cooling pipe 26a shown in FIG. 12 may be constituted of a cooling pipe having a branched structure like the cooling pipe 20a shown in FIG.

(Example 7)
In the apparatus for producing mono-lower alkyl monoalkanolamine of Example 7, the characteristic upstream temperature reduction mechanism has a plurality of reactors (two in the figure) filled with a catalyst as shown in FIG. Both the first and second reactors are composed of tank reactors 28 and 29, and the inside of the first tank reactor 24 is filled with catalyst 5a having a fine particle size (particle size 0.8 to 1.5 mm). In addition, the upstream temperature reduction mechanism 107 is realized by filling the inside of the tank reactor 25 in the latter stage with a catalyst 5b having a medium particle size (particle size: 0.5 to 1.0 mm). Since the particle diameter of the catalyst 5b filled in the preceding tank reactor 28 is larger than the particle diameter of the catalyst 5a charged in the latter tank reactor 29, the inside of the preceding tank reactor 28 The heat removal effect of the catalyst is further enhanced.

  A raw material 7, that is, a mono-lower alkylamine and an alkylene oxide are supplied from the upper part to the preceding tank reactor 28. The mono-lower alkylamine and alkylene oxide introduced into the tank reactor 28 are reacted with each other by the catalyst 5b in the tank to produce a mono-lower alkyl monoalkanolamine. Then, the reaction product mixture is sent to the subsequent tank reactor 29, and most of the unreacted raw material in the reaction product mixture is reacted by the catalyst 5 a in the tank reactor 29.

  In the reaction product mixture 8 led out from the tank reactor 29 in the latter stage, in addition to the mono-lower alkyl monoalkanolamine (monomer) that occupies most of the reaction product mixture 8, a small amount of unreacted raw material and a mono-lower product that is a side reaction product. Since alkyl dialkanolamine (dimer) is contained, in the next step (not shown), unreacted raw materials are collected and circulated for the raw materials by distillation or the like, and dimers are separated and removed.

  In the apparatus configuration shown in FIG. 13, the particle size of the catalyst 5 b filled in the preceding tank reactor 28 is larger than the particle size of the catalyst 5 a charged in the latter tank reactor 29. Accordingly, it is possible to appropriately suppress the temperature rise of the catalyst in the preceding tank reactor 28 in which the amount of reaction heat generated increases. As a result, the temperature of the catalyst 5b of the tank reactor 28 can be easily controlled within a suitable temperature range in order not to reduce the reaction rate, shorten the catalyst life, and further increase the monomer yield. Can do. The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

  In the apparatus configuration of FIG. 13, as shown in FIG. 14, the upstream portion of the catalyst 5b charged in the preceding tank reactor 28 may be replaced with a catalyst 5c having a larger particle size. By adopting a catalyst packed arrangement with such a particle size distribution, it is possible to further reduce the temperature rise of the upstream portion (catalyst 5c) where the temperature rise of the catalyst in the preceding tank reactor 28 is most likely to occur.

(Example 8)
In the apparatus for producing mono-lower alkyl monoalkanolamine of Example 8, the characteristic upstream temperature reduction mechanism is that the reactor filled with the catalyst is composed of one tank reactor 30 as shown in FIG. The inside of the tank reactor 30 is filled with a catalyst 5a having a fine particle size (particle size 0.5 to 1.0 mm) in the downstream half, and a medium particle size (particle size 0. 1 mm in the upstream half). The upstream temperature reduction mechanism 108 is realized by being filled with the catalyst 5b or 5c having a particle size of 8 to 1.5 mm) or a large particle size (particle size of 1.5 to 2.0 mm). Since the upstream half (catalyst 5b or 5c) of the catalyst charged in the tank reactor 30 is larger than the downstream half (catalyst 5a), the upstream side of the catalyst in the tank reactor 30 is upstream. The heat removal effect is further enhanced.

  From the upper part of the tank reactor 30, the raw material 7, that is, mono-lower alkylamine and alkylene oxide are supplied. The mono-lower alkylamine and alkylene oxide introduced into the tank reactor 30 are reacted with each other by the catalysts 5c and 5b in the tank to produce a mono-lower alkylmonoalkanolamine.

  In the reaction product mixture 8 led out from the tank reactor 30, in addition to the mono-lower alkyl monoalkanolamine (monomer) that occupies most of the reaction product mixture 8, a small amount of unreacted raw material and a mono-lower alkyl dialkyl which is a side reaction product. Since alkanolamine (dimer) is contained, in the next step (not shown), the unreacted raw material is collected and circulated for the raw material by distillation or the like, and the dimer is separated and removed.

  In the apparatus configuration shown in FIG. 15, the particle diameter of the catalyst 5c filled in the upstream half of the tank reactor 30 is larger than the particle diameter of the catalyst 5b filled in the downstream half. The temperature increase in the upstream portion of the catalyst in the tank reactor 30 in which the amount of generated reaction heat is increased can be appropriately suppressed. As a result, the catalyst temperature of the tank reactor 30 can be easily controlled within a temperature range suitable for increasing the yield of the monomer without reducing the reaction rate and reducing the life of the catalyst. . The preferable temperature range is 100 ° C. to 130 ° C. when a zeolite catalyst is used as the catalyst.

  In addition, you may combine the upstream temperature reduction mechanism by the particle size control of the catalyst shown in the said Examples 7 and 8 with the apparatus structure shown in the above-mentioned FIGS. As a result, finer temperature reduction control can be realized.

  In the present invention, a raw material mono-lower alkylamine may be used as a cooling medium used for removing heat from the catalyst. By using the raw material mono-lower alkylamine as a cooling medium, energy consumption of the entire apparatus can be saved.

  As described above, the method and apparatus for producing a mono-lower alkyl monoalkanolamine according to the present invention can produce mono-lower alkyl monoalkanolamine continuously in an efficient and high yield.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram which shows Example 1 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention. It is a schematic block diagram which shows the modification of Example 1 shown in FIG. It is a schematic block diagram which shows Example 2 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention. It is a schematic block diagram which shows Example 3 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention. It is a schematic block diagram which shows Example 4 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention. It is a schematic block diagram which shows the modification of Example 4 shown in FIG. It is a schematic block diagram which shows the other modification of Example 4 shown in FIG. It is a schematic block diagram which shows the modification of the modification of Example 1 shown in FIG. It is a schematic block diagram which shows Example 5 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention. It is a schematic block diagram which shows the modification of Example 5 shown in FIG. It is a schematic block diagram which shows Example 6 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention. It is a schematic block diagram which shows the modification of Example 6 shown in FIG. It is a schematic block diagram which shows Example 7 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention. It is a schematic block diagram which shows the modification of Example 7 shown in FIG. It is a schematic block diagram which shows Example 8 of the manufacturing apparatus of the mono lower alkyl monoalkanolamine concerning this invention.

Explanation of symbols

1, 12, 13 Tube reactor 2, 9, 18, 21, 22, 24, 25, 28, 29, 30 Tank reactor 3, 4, 11, 16, 17 Cooling jacket 5, 5a, 5b, 5c Catalyst 6, 6a, 10, 14, 15 Reaction tube 7 Raw material 8 Reaction product mixture 19, 19a, 20, 20a, 23, 23a, 26, 26a, 27 Cooling tube 101, 102, 103, 104, 105, 106, 107 , 108 Upstream temperature reduction mechanism

Claims (46)

In a process for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine and an alkylene oxide in the presence of a catalyst comprising a crystalline metallosilicate or / and a layered clay compound,
A method for producing a mono-lower alkylmonoalkanolamine, characterized in that the reaction zone in the presence of the catalyst is cooled by further reducing the temperature rise in the upstream portion of the reaction zone.   The reaction zone is constituted by a plurality of reactors, the former reactor is constituted by a tubular reactor having a high cooling efficiency, and the latter reactor is constituted by a tank reactor having a large amount of catalyst, The method for producing a mono-lower alkyl monoalkanolamine according to claim 1, wherein the temperature rise in the upstream portion of the reaction zone is reduced.   3. The cooling efficiency of the upstream portion in the upstream reactor is further increased by forming the diameter of the reaction tube of the upstream tubular reactor so that the downstream portion is larger than the upstream portion. A process for producing a mono-lower alkylmonoalkanolamine as described in 1.   The reaction zone is composed of one tubular reactor, and the temperature of the upstream portion of the reaction zone is increased by forming the tube diameter of the reaction tube of the tubular reactor so that the downstream portion is larger than the upstream portion. The method for producing a mono-lower alkyl monoalkanolamine according to claim 1, wherein:   The reaction zone is composed of a plurality of tubular reactors, and the diameter of the reaction tube of the preceding tubular reactor is made smaller than the diameter of the reaction tube of the succeeding tubular reactor. 2. The mono-lower alkyl monoalkanolamine according to claim 1, wherein the temperature increase in the upstream portion of the reaction zone is reduced by increasing the number of reaction tubes installed from the number of reaction tubes installed in the subsequent reactor. Production method.   The reaction zone is composed of one tank reactor, and a cooling pipe in which the refrigerant flows from upstream to downstream is installed in the tank reactor to reduce the temperature rise in the upstream portion of the reaction zone. The method for producing a mono-lower alkyl monoalkanolamine according to claim 1,   The temperature rise in the upstream part of the reaction zone is further reduced by making the density of the cooling pipe installed in the one tank reactor denser in the upstream part than in the downstream part. A process for producing a mono-lower alkylmonoalkanolamine as described in 1.   The reaction zone is composed of a plurality of tank reactors, and a temperature rise in the upstream portion of the reaction zone is reduced by installing a cooling pipe in which the refrigerant flows from upstream to downstream in the previous tank reactor. The method for producing a mono-lower alkyl monoalkanolamine according to claim 1, wherein:   The cooling efficiency of the upstream portion in the upstream reactor is further increased by making the upstream pipe portion denser than the downstream portion in the density of the cooling pipes installed in the preceding tank reactor. A process for producing the mono-lower alkyl monoalkanolamine according to 8.   The reaction zone is composed of a plurality of tank reactors provided with cooling pipes through which the refrigerant flows from upstream to downstream, and the density of the cooling pipes installed in the preceding tank reactor is set in the subsequent reactor. The method for producing a mono-lower alkyl monoalkanolamine according to claim 1, wherein the temperature rise in the upstream portion of the reaction zone is reduced by making the density higher than the installed density of the installed cooling pipe.   The cooling efficiency of the upstream portion in the upstream reactor is further increased by making the upstream pipe portion denser than the downstream portion in the density of the cooling pipes installed in the preceding tank reactor. 10. A process for producing a mono-lower alkyl monoalkanolamine according to 10.   The reaction zone is composed of a plurality of reactors, and the temperature of the upstream portion of the reaction zone is increased by making the particle size of the catalyst charged in the preceding reactor larger than the particle size of the catalyst charged in the subsequent reactor. The method for producing a mono-lower alkyl monoalkanolamine according to claim 1, wherein:   13. The cooling efficiency of the upstream portion in the upstream reactor is further increased by making the particle size of the catalyst charged in the upstream reactor larger in the upstream portion than in the downstream portion. A process for producing mono-lower alkyl monoalkanolamines.   The reaction zone is composed of a single reactor, and the particle size of the catalyst filled in the reactor is made larger in the upstream portion than in the downstream portion, thereby reducing the temperature rise in the upstream portion of the reaction zone. The method for producing a mono-lower alkyl monoalkanolamine according to claim 1.   The method for producing a mono-lower alkyl monoalkanolamine according to any one of claims 1 to 14, wherein the catalyst containing the crystalline metallosilicate further contains a layered clay compound.   The method for producing a mono-lower alkyl monoalkanolamine according to claim 15, wherein the mixing ratio (mass ratio) of the crystalline metallosilicate and the layered clay compound is 5:95 to 50:50.   The crystalline metallosilicate includes at least one metal element M selected from the group consisting of Al, Ga, Fe, B, Zn, P, Ge, Zr, Ti, Cr, Be, V, and As. The method for producing a mono-lower alkylmonoalkanolamine according to any one of claims 1 to 16.   18. The production of mono-lower alkyl monoalkanolamine according to claim 17, wherein the crystalline metallosilicate has a Si / metal element M ratio of Si / M = 5 to 1000 based on oxides. Method.   The method for producing a mono-lower alkyl monoalkanolamine according to claim 18, wherein the ratio of Si to metal element M is Si / M = 10 to 500 on an oxide basis.   The method for producing a mono-lower alkyl monoalkanolamine according to any one of claims 1 to 19, wherein the crystalline metallosilicate has an MOR structure, an MFI structure, and / or an MEL structure. The method for producing a mono-lower alkyl monoalkanolamine according to any one of claims 1 to 20, wherein the crystalline metallosilicate is a crystalline aluminosilicate.   The method for producing a mono-lower alkyl monoalkanolamine according to claim 21, wherein the crystalline aluminosilicate is zeolite.   The method for producing a mono-lower alkyl monoalkanolamine according to claim 1, 15 or 16, wherein the layered clay compound is acidic clay or activated clay. An apparatus for producing a mono-lower alkyl monoalkanolamine by reacting a mono-lower alkyl amine and an alkylene oxide with a catalyst containing a crystalline metallosilicate or / and a layered clay compound,
An apparatus for producing a mono-lower alkyl monoalkanolamine, comprising an upstream temperature reduction mechanism for further reducing a temperature rise in an upstream portion of the catalyst.   There are a plurality of reactors filled with the catalyst, the former reactor is composed of a tubular reactor with high cooling efficiency, and the latter reactor is composed of a tank reactor with a large amount of catalyst filling. The apparatus for producing a mono-lower alkylmonoalkanolamine according to claim 24, wherein the upstream temperature reduction mechanism is realized.   26. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 25, wherein the diameter of the reaction tube of the preceding tubular reactor is formed larger in the downstream portion than in the upstream portion.   The reactor filled with the catalyst is composed of a single tubular reactor, and the diameter of the reaction tube of the tubular reactor is formed such that the downstream portion is larger than the upstream portion. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 24, which is realized.   The reactor filled with the catalyst is composed of a plurality of tubular reactors, and the diameter of the reaction tube of the preceding tubular reactor is formed smaller than the diameter of the reaction tube of the succeeding tubular reactor, 25. The mono-lower alkyl according to claim 24, wherein the upstream temperature reduction mechanism is realized by increasing the number of reaction tubes installed in the former stage reactor from the number of reaction tubes installed in the latter stage reactor. Monoalkanolamine production equipment.   The reactor filled with the catalyst is composed of one tank reactor, and the upstream temperature reduction mechanism is realized by arranging a cooling pipe in which the refrigerant flows from upstream to downstream in the tank reactor. 25. The apparatus for producing mono-lower alkyl monoalkanolamine according to claim 24, wherein:   30. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 29, wherein an upstream portion of the cooling pipe laid in the one tank reactor is denser than a downstream portion.   The reactor filled with the catalyst is composed of a plurality of tank reactors, and the upstream temperature reduction mechanism is realized by installing a cooling pipe in which the refrigerant flows from upstream to downstream in the preceding tank reactor. 25. The apparatus for producing mono-lower alkyl monoalkanolamine according to claim 24, wherein:   32. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 31, wherein the upstream pipe portion is denser than the downstream portion in the density of the cooling pipes laid in the preceding tank reactor.   The reactor filled with the catalyst is composed of a plurality of tank reactors in which cooling pipes in which refrigerant flows from upstream to downstream are installed, and the installation density of the cooling pipes installed in the preceding tank reactor is the latter stage The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 24, wherein the upstream temperature reduction mechanism is realized by being denser than a density of cooling pipes laid in the reactor. .   34. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 33, wherein the upstream pipe portion is denser than the downstream portion in the density of cooling pipes laid in the preceding tank reactor.   The reactor filled with the catalyst is composed of a plurality of reactors, and the upstream temperature is increased by making the particle size of the catalyst charged in the former reactor larger than the particle size of the catalyst charged in the latter reactor. The apparatus for producing mono-lower alkyl monoalkanolamine according to claim 24, wherein a reduction mechanism is realized.   36. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 35, wherein the upstream portion of the catalyst charged in the preceding reactor has a larger particle size than the downstream portion.   The reactor filled with the catalyst is composed of one reactor, and the upstream temperature reduction mechanism is realized by increasing the particle size of the catalyst filled in the reactor in the upstream portion from the downstream portion. 25. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 24.   The apparatus for producing a mono-lower alkyl monoalkanolamine according to any one of claims 24 to 37, wherein the catalyst containing the crystalline metallosilicate further contains a layered clay compound.   The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 38, wherein a mixing ratio (mass ratio) of the crystalline metallosilicate and the layered clay compound is 5:95 to 50:50.   The crystalline metallosilicate includes at least one metal element M selected from the group consisting of Al, Ga, Fe, B, Zn, P, Ge, Zr, Ti, Cr, Be, V, and As. The apparatus for producing a mono-lower alkyl monoalkanolamine according to any one of claims 24 to 39.   41. The production of mono-lower alkyl monoalkanolamine according to claim 40, wherein the crystalline metallosilicate has a ratio of Si to metal element M in terms of oxide of Si / M = 5 to 1000. apparatus.   42. The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 41, wherein the ratio of Si to metal element M is Si / M = 10 to 500 on an oxide basis.   43. The apparatus for producing a mono-lower alkyl monoalkanolamine according to any one of claims 24 to 42, wherein the crystalline metallosilicate has an MOR structure, an MFI structure, and / or an MEL structure. 44. The apparatus for producing mono-lower alkyl monoalkanolamine according to any one of claims 24 to 43, wherein the crystalline metallosilicate is a crystalline aluminosilicate.   The apparatus for producing a mono-lower alkyl monoalkanolamine according to claim 44, wherein the crystalline aluminosilicate is zeolite.   The apparatus for producing mono-lower alkyl monoalkanolamine according to claim 24, 38 or 39, wherein the layered clay compound is acidic clay or activated clay.

Images