WO2003091208A1 - Lactam synthesizing method - Google Patents

Abstract

A method of continuously manufacturing lactam under high temperature and high pressure fluid, characterized by comprising the step of leading ketone and a hydroxylamine compound in a reaction field under high temperature and high pressure conditions of circulating fluid to efficiently synthesize lactam in a short time, whereby lactam can be rapidly synthesized continuously from ketone under the high temperature and high pressure fluid conditions of 175°C or higher in temperature range and 7 MPa or higher in pressure range.

Description

 Description Lactam synthesis method Technical field

 The present invention relates to a method for continuously producing ratatam from ketones under high temperature and high pressure conditions, and more particularly, to a method for reacting cyclic ketones with a hydroxylamine compound under high temperature and high pressure fluid conditions. The present invention relates to a novel method for producing lactam, which produces ratatum continuously in a short time. More specifically, the present invention is to produce a cyclohexanoxoxime by reacting a conventional hexahexanone with a hydroxylamine compound, purify the cyclohexanone oxime, and then use concentrated sulfuric acid as a catalyst. A new ratatam that enables the production of ratatam from ketones by shortening the two-step manufacturing process, as seen in the manufacturing method of synthesizing ε-force prolatatam by Beckmann rearrangement using The present invention relates to a manufacturing method and provides a method suitable and useful as an industrial technology. Background art

ε-Caprolactam is produced around 390,000 tons annually worldwide in 1998. In all commercial production processes, fuming sulfuric acid or concentrated sulfuric acid is used as the reaction medium for cyclohexanoxoxime. Is produced by the Beckmann rearrangement reaction, and cyclohexanonoxime is produced by the reaction of cyclohexanenone with a hydroxylamine compound (H. I chihashiand H. sato, Applied Cata 1 sis A : General, 2 2 1 (2 0 1 1), 3 5 9—3 6 6). Its main manufacturing processes are the phenol method and the cyclohexane oxidation method. Hueno The Röhl method is a process for synthesizing cyclohexanone by hydrogenation and dehydrogenation of phenol and then oxidizing it to obtain ε-force prolatatatam by Beckmann rearrangement. On the other hand, the cyclohexane oxidation method synthesizes cyclohexanone by oxidation of cyclohexane, and produces prolatatatam by a Beckmann rearrangement reaction using cyclohexanone oxime obtained by oxidation. How to In these two production methods, the nitrogen of the amide is introduced by an oximation reaction with a hydroxylamine compound (Ken Sekoguchi, Catalyst, Vol. 33, pp. 335-340, pp. 1991) Year

) ο

 Thus, most of the ε-force prolatatam is produced from hexanoxoxime by a Beckmann rearrangement reaction using fuming sulfuric acid as a catalyst. In this rearrangement reaction, when water is present in the system, oxime is hydrolyzed, and the yield of ε-force prolatatam decreases.Therefore, a method is generally used in which fuming sulfuric acid is boiled and reacted as an acid catalyst. It has become a target. This method has been pointed out as corrosion of equipment materials or danger in the manufacturing process. Also, in order to recover ε-caprolactam, it is necessary to neutralize the used fuming sulfuric acid with ammonia, and a large amount of ammonium sulfate (ammonium sulfate) is by-produced in the Beckmann rearrangement. ε-force prolactam 1.7 kg of ammonium sulphate per kg is obtained. Since ammonium sulfate has a low commercial value, it has become difficult to use it. Therefore, its treatment is required, and the development of a new process that does not produce by-products is required.

Furthermore, in recent years, there has been an increasing concern about the deterioration of the global environment. In the chemical industry, the use of hazardous substances such as fuming sulfuric acid or no impact on the environment has been simplified, and the manufacturing process has been simplified. There is a demand for the development of an efficient chemical process that can complete the reaction in a short time. The lactam manufacturing process involves corrosion of equipment materials, operational safety and environmental concerns. There is a need for the development of new energy-saving and efficient manufacturing processes that do not use fuming sulfuric acid, which has problems in terms of use, and that can contribute to the reduction of carbon dioxide without by-products.

 As a method for solving the above problem, a method of obtaining ε-force prolactam by reacting cyclohexanonoxime under high temperature and high pressure water without using a strong acid catalyst such as fuming sulfuric acid, The batchy synthesis method (O. S at ο, Υ. I kushima, and T. Yokoyama, Journalof Organic Chemistry 1 998, 63, 9101-9102) and (B ) Flow-through synthesis method (Y.Ikushima K. Hatakeda, O. Sato, T. Yokoyamaand M. Arai, Journalof American Chemica 1 Society 200, 0, 122, 190) 8—19 18) Two methods have been proposed.

Of these, in the batch synthesis method (A), cyclohexanonoxime is sealed in a 10-ml stainless steel tube, and placed in a salt bath for about 30 seconds to produce 200- The temperature was raised to 400 ° C and the reaction was performed for 3 minutes to obtain the product. Although this method is considered to be unsuitable for mass production processes, it is attracting attention as a synthesis method that does not use an acid catalyst such as fuming sulfuric acid. In this method, the reaction is terminated each time, so the operation is intermittent, and a large amount of the hydrolysis product cyclohexanone is generated at the time of heating, and the yield of the desired _ε- caprolactam decreases. There are drawbacks.

On the other hand, the flow-type synthesis method (I) is considered to be suitable for continuous production and mass production.However, the aqueous solution of hexanone oxime is heated at room temperature to produce high-temperature and high-pressure carrier water. Therefore, it is considered that it takes time to raise to the set reaction temperature. Therefore, in experiments where the reaction was carried out at 350 ° C and 22. The results show that no ε-force prolatatam was formed at all. It was also reported that ε-force prolatatam and cyclohexanone were formed at 374.5 ° C. Therefore, similarly to the batch-type synthesis method of (Α), it takes time to raise the temperature, and the water as a solvent passes through a hydrothermal state of, for example, 100 to 300 ° C. It is considered that cyclohexanone is generated due to the progress of hydrolysis of oxime, and the yield of the desired ε-caprolactam decreases.

In almost all conventional ε-caprolactam production processes including these methods, a Beckmann rearrangement reaction step using cyclohexanone oxime as a raw material is employed. Manufactured in the previous step. In this oxime process, it is necessary to produce cyclohexanone oxime by reacting cyclohexanone and a xylaminate compound with a hydroxy compound, to separate and purify the product, and to remove water by drying. The obtained cyclohexanone oxime raw material is It is often stored in preparation for the Beckmann rearrangement reaction step. Cyclohexanone oxime is a rather unstable compound, which may be deteriorated during storage and reduce the yield of ε-caprolactam, so that it is required to shorten the storage time. In addition, in order to reduce the production cost, there is a demand for technology development that does not require a separation and purification process and a drying process for cyclohexanone oxime. In such a situation, the present inventors have considered, in view of the above-mentioned prior art, various studies on a method for producing ratatum under a high temperature and a high pressure. The reaction of oral hexanone with a hydroxylamin compound was found to produce ε_force prolatatam in a short period of time, and based on such findings, further research was conducted to complete the present invention. That is, the present invention provides a method for efficiently producing a lactam by introducing cyclohexanone and a hydroxylamine compound such as hydroxylamine sulphate into a reaction field under high-temperature and high-pressure fluid conditions such as water and reacting them. It is intended to provide

Further, the present invention is, for example, the substrate fluid obtained by dissolving cyclohexanone and sulfate inhibit Dorokishiruami down cyclohexane, continuously introduced into the reaction field of the high-temperature high-pressure water conditions which is circulated selectively the _£ per force Puroratatamu It is an object of the present invention to provide a novel method for producing a lactam, which enables efficient and rapid production. The present invention for solving the above problems is constituted by the following technical means.

 (1) A method for producing a lactam, comprising reacting a ketone and a hydroxyylamine compound in a reaction field under a predetermined high-temperature and high-pressure fluid condition.

 (2) The method for producing ratatum according to (1), wherein the ketone and the hydroxylamin compound are introduced into a continuously flowing high-temperature and high-pressure fluid and reacted.

 (3) The method for producing ratatum according to (1) or (2), wherein a ketone and a substrate solution in which the hydroxylamine compound is dissolved are introduced into a continuously flowing high-temperature and high-pressure fluid to cause a reaction.

 (4) The method for producing ratatum according to any one of (1) to (3), wherein water is used as the high-temperature high-pressure fluid.

 (5) The method for producing ratatum according to any one of (1) to (4), wherein a cyclic ketone is used as the ketone.

(6) The method for producing ratatum as described in (5) above, wherein cyclohexanone is used as the cyclic ketone. (7) At least one hydroxylamine compound selected from the group consisting of hydroxylamine sulphate, hydroxylamine hydrochloride, hydroxylamine oxalate and hydroxylamine as the hydroxylamine compound. The method for producing ratatum according to any one of (1) to (4).

 (8) The method for producing ratatum according to any one of (1) to (4), wherein the high temperature and high pressure conditions are a temperature range of 175 ° C or more and a pressure range of 7 MPa or more. Next, the present invention will be described in more detail.

 In order to facilitate the description of the present invention, a substrate fluid in which cyclohexanone and a hydroxylamine compound are dissolved is introduced into a reaction field under a high-temperature and high-pressure water condition, and then the reaction is carried out at 375 ° C and 40 MPa. The case of producing ratatum in a short time within 3 seconds under the above reaction pressure conditions will be described in detail as an example. However, the invention is not limited to the reaction of these compounds. The present inventors developed the production method of the present invention through various experiments, for example, by dissolving a substrate aqueous solution obtained by dissolving a hexahexanone and a hydroxylamine compound in a reaction field under high-temperature and high-pressure water conditions. This is a method in which ε-one-prolactam is efficiently synthesized from xanone hexone in a short time within 3 seconds by continuously introducing, for example, reaching a reaction set temperature of 375 ° C.

In the prior art, cyclohexanone oxime was produced by the reaction of cyclohexanone and a hydroxyylamine compound, and the obtained cyclohexanone oxime was purified and dried.Then, ε-proprotatatam was converted to a Beckmann rearrangement reaction using fuming sulfuric acid. It required two stages of manufacturing. The production method of the present invention provides a method that enables the f-prolactam production reaction to be carried out in a single step, comprising producing and purifying cyclohexanonoxime, drying it, and drying it to remove water. No need to remove. Also, the traditional independent Since no Beckmann rearrangement reaction step is required at all, there is no need to use fuming sulfuric acid or ammonia, which is extremely economically advantageous and is considered to be the most suitable method for ratatam production. .

 The method for producing a lactam of the present invention will be described in detail below.

 In the present invention, for example, cyclohexanone and a hydroxyylamine compound are continuously introduced into a reaction field under high-temperature and high-pressure fluid conditions and reacted, and lactams are efficiently selected from cyclohexanone with high efficiency in a short reaction time. It can be manufactured on demand. In the present invention, ketone used as a substrate material is a general term for an oxo compound in which a divalent carbonyl group is bonded to two hydrocarbon groups. Ketones with a single carbonyl group include acetone, pinacolin, mesityloxide, acetophenone, and benzophenone. Ketones with two carbonyl groups are collectively called diketones.

In the present invention, cyclic ketones can be mentioned as ketones that are particularly effectively used as a substrate material. The cyclic ketone has oxygen attached to the carbon of the ring of the cyclic compound, is represented by the following general formula (1), and has n = l to 20; and R, R ₂ , R ₃ , R _{3 4} , R ₅ and R ₆ are H or an alkyl group. As the alkyl group, any of those having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group can be used. Examples of cyclic ketones include, for example, cyclohexanone, cycloheptanone, cyclopentanone, cyclobutanone, cyclooctanone, tropone, tropolone, suberon, and the like.

However, it is not limited to these.

It is known that the hydroxylamin compound used in the present invention is used for the oximation reaction of ketones such as cyclohexanone. In the present invention, the hydroxylamine compounds include hydroxylaminate sulfate, hydroxylaminate hydrochloride, hydroxyxoleamine oxalate, hydroxyxoleamine, hydroxynoreamine nitrate, hydroxyammonium phosphate and ammonium dihydrogen phosphate. At least one hydroxylamine compound selected from the group consisting of hydroxylamine (NH ₃ OH) H ₂ PO ₄ ) and the like can be suitably used.

It has been disclosed that in the oxime process for producing f-proprotatatam in the prior art, hydroxylamine sulphate is used in the nitric oxide reduction method and rasching method, and hydroxylamine dihydrogen phosphate is used in the HPO method (Ken Sekoguchi, Catalyst, Vol. 33, pp. 335-340, 1991). In the nitric oxide reduction method, which was industrialized by BASF in 1956, ammonia was oxidized to nitrogen oxide in the presence of a platinum-based catalyst, and this was used in diluted sulfuric acid in which the platinum-based catalyst was suspended. Catalytic reduction at 60 ° C to give hydroxylamine sulfate Manufacturing. BASF then reduced nitric oxide in ammonium hydrogen sulfate ammonium sulphate buffer to produce hydroxyammonium and ammonium sulphate and reacted with cyclohexanone, an oxime process that did not produce by-product ammonium sulphate. Was developed. In the oxime process of the Rasching method, nitrite gas is absorbed into an aqueous solution of ammonium carbonate to produce ammonium nitrite, which is reduced with sulfurous acid gas and then hydrolyzed to produce hydroxylamine sulfate. In the R asching method, no new plant has been constructed since 1970, because ammonium sulfate is produced in large quantities.

 On the other hand, in the oxime process of the HPO method developed by DSM, nitrate ions are reduced in a buffer solution of phosphoric acid / monoammonium phosphate in the presence of a palladium catalyst to produce hydroxylamine dihydrogen phosphate. Hydroxylamin sulfate, hydroxyammonium / ammonium sulfate, hydroxylamine dihydrogen phosphate, etc., all of which can be used in the present invention, can be used in the present invention. By applying the reaction to the reaction conditions under the high-temperature and high-pressure fluid conditions of the present invention, ε-force prolatatam can be favorably produced from hexanone.

In the ammonium oximation process developed by Enichem, cyclohexanone reacts with ammonia and hydrogen peroxide at around 80 ° C in the presence of TS-1 catalyst. To obtain xanone oxime. In this reaction, it was reported that ammonia was oxidized with hydrogen peroxide at the Ti-1 site of the TS-1 catalyst to produce hydroxylamine, and then reacted with cyclohexanone to synthesize cyclohexanone oxime. (H. I chihashiand H. Sato, Applied Catalysis A: General, 222 (201), 359—366). The amoximation method By applying the present invention to the reaction field under high-temperature and high-pressure fluid conditions, ε-force prolactam can be favorably produced from cyclohexanone. Conventionally, there has been known a method of synthesizing cyclohexanone oxime hydrochloride by reacting cyclohexane with nitrosyl chloride in the presence of hydrogen chloride under irradiation of light of 400 to 65 nm (Sekoguchi Ken, Catalyst, Vol. 33, 335-340, 1991). By applying this method to the reaction field under the conditions of high temperature and high pressure fluid of the present invention, ε-force prolatatam can be produced favorably.

The lactam obtained by the present invention is represented by the following general formula (2), η = 20, and, RRRR _R and R _fi

, H or an alkyl group. As the alkyl group, any of those having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group can be used.

(2)

本発明で得られるラタタムは、 五員環ラタタム、 六員環ラタタム、 七 員環ラタタム等の五員環以上の多員環ラタタムである。 例えば、 ε —力 プロラクタム、 γ _ブチルラタタム、 γ —ノく レ口ラタタム、 δ —ノ レ口 ラタタム等が挙げられるが、 本発明は、 これらに限定されるものではな い。

The ratatum obtained in the present invention is a five- or more-membered multi-membered ratatam such as a five-membered ratatam, a six-membered ratatam, and a seven-membered ratatam. For example, ε-force prolactam, γ-butyl ratatam, γ-block ratatam, δ-block ratatam, etc., but the present invention is not limited to these.

 As a specific example of the production of ratatum according to the present invention, for example, for a production example of a seven-membered ring lactam, a reaction formula for producing ε-one-prolactam from cyclohexanone and hydroxylamine sulfate is represented by the following general formula (3) Shown in

 Cyclohexanone: -force prolactam

In the high-temperature high-pressure fluid reaction field of the present invention, it is considered that 1 mol of ketone and 1 mol of hydroxylamine group (NH ₃ OH group) react to produce 1 mol of ratatum. The amount of the hydroxylamine group used in the present invention varies depending on the carrier fluid temperature, reaction pressure, carrier fluid flow rate, substrate fluid introduction flow rate, ketone introduction quantity, reactor configuration, reactor capacity, and the like. Can be adjusted. In general, the amount of the hydroxylamine group can be selected in the range of 0.8 mol to 2.0 mol, preferably 1.0 mol to 1.0 mol, per 1 mol of the ketone substrate. Select a value in the range of 8 moles In addition, more preferably, a value in the range of 1.0 mol to 1.5 mol can be selected, and most preferably, a value in the range of 1.0 mol to 1.3 mol can be selected.

 The ketone as a substrate and the hydroxylamine compound containing a hydroxylamine group are introduced into a high-temperature and high-pressure fluid reaction field and reacted to produce ratatam. When introducing a ketone and a hydroxylamine compound into a high-temperature, high-pressure fluid reaction field, prepare a substrate solution by dissolving the ketone and the hydroxylamine compound together in a solution such as water in advance, and use a single pump to send the hot solution. It can be introduced into a high pressure fluid reaction field. Alternatively, the ketone and the hydroxylamine compound may be prepared in separate substrate solutions, and separately introduced into the high-temperature and high-pressure fluid reaction field by two liquid sending pumps and reacted. Further, when the ketone and the hydroxylamine compound are in a liquid state, they may be used as they are by mixing them as they are or by sending them separately to the reaction.

It is known that the production of cyclohexanone oxime by the reaction of cyclohexanone and a hydroxyylamine compound and the synthesis of lactam by Beckmann rearrangement of oxime proceed in boiling fuming sulfuric acid. It is an interesting fact that ratatam is synthesized by the reaction of a hexahexanone with a hydroxylamine compound under the high temperature and high pressure fluid conditions of the present invention. For example, in the high-temperature and high-pressure water reaction field at 350 ° C. to 400 ° C. in the present invention, the total production amount of ε-force prolactam and 6-aminohexanoic acid is large, and cyclohexanone oxime The amount is minute or not detected, and the cyclohexanone substrate is often undetected, minute or small. In the reaction at 200 ° C to 250 ° C, the overall tendency was that the amount of hexanoxoxime was increased, while the amount of ε-caprolactam produced was small. And the amount of substrate cyclohexanone has also increased slightly. From these results, in the reaction of cyclohexanone and a hydroxylamine compound in a high-temperature and high-pressure water reaction field, first, cyclohexanonoxime is formed, and then f-force prolactam is formed by the rearrangement reaction of cyclohexanone oxime. It is presumed that the possibility is high. It can be inferred that the rearrangement reaction is likely to occur at higher temperatures. On the other hand, on the low temperature side, the conversion rate is presumed to be lower because the hydrolysis of some of the generated cyclohexanone oxime generates hexoxanone. Therefore, in the present invention, it is considered advantageous to carry out the reaction in a temperature range of 330 ° C. or higher. In any case, for example, the reaction is progressing in a short time of about 1 second or less, and how ratatam is synthesized in a high-temperature, high-pressure fluid will be determined by the future physics of high-temperature, high-pressure fluid. Verification by development of chemical research is expected.

 ADVANTAGE OF THE INVENTION According to this invention, (epsilon) -force prolactam can be manufactured efficiently by introduce | transducing a xanonone and a hydroxylamine compound into a high-temperature high-pressure fluid of a predetermined condition. In this reaction, amino acids may be produced in some cases. This reaction is thought to be formed by the hydrolysis reaction of ε-force prolatatam. 6-aminohexanoic acid is also important as a raw material monomer for the production of polyproprolactam.

In the present invention, a predetermined high-temperature and high-pressure fluid can be suitably produced by using water, and water can be most preferably used as the fluid used for the high-temperature and high-pressure fluid. However, the present invention is not limited to water, and one or more of the following fluids and water groups can be used in combination as appropriate. For example, alcohols having a hydroxyl group include methanol, ethanol, ethanol, isopropyl alcohol, butanol, butanol, cyclopentanol, hexanol, cyclohexanol, heptanol, cycloheptanol, and octanol. , Cyclootatanol, nonanol, decanol, dodecanol, tridecanol, tet Ladecanol, heptadecanol, cycloheptanol, methoxyethanol, black ethanol, ethanol, ethanol, ethanol, ethanol, propanol, ethanol, benzino alcohol, ethylene glycol, ethylene glycol, triethylene glycol And the like.

 Examples of ketones or aldehydes having a carbonyl group include, for example, acetone, 2-butanone, 3-pentanone, ethynoleketone, methinoletylketone, methinolepropinoleketone, butylmethylketone, and cyclohexene. Sanone, acetophenone and the like. Examples of the nitrile having a cyano group include acetonitril and benzonitrile. ε—Lactams such as dysprolatatam and amides or urines having an amide group, for example, formamide, Ν-methylformamide, Ν, Ν'-dimethylacetamide, pyrrolidone, Ν-methylpyrolide Examples thereof include ridone, Ν, ，, monodimethylethylene urea, Ν, Ν'-dimethylpropylene urea, Ν, Ν-dimethylformamide, and tetrahydrofuran. Further, amines having an amino group may be used. For example, quinoline, triethylamine, tributylamine and the like can be mentioned.

Further, sulfides and sulfoxides include, for example, sulfolane and the like. Further, examples of the phosphoric ester include hexamethylene phosphoric acid. Further, examples of the ester or carbonic acid or carbonic acid ester which is a carboxylic acid or a carboxylic acid derivative include ethyl acetate, methyl acetate, formic acid, acetic acid, dimethyl carbonate, getyl carbonate, propylene carbonate and the like. Further, examples of the ether include diglyme, jetiethyl ether, anisol and the like. Further, as the less polar hydrocarbons, for example, methane, ethane, ethylene, acetylene, propane, propylene, nonoremanolebutane, isobutane, Vitagen, pentane, hexane, heptane, cyclohexane, decalin, benzene, Tonolen, Examples include xylene, benzene perhenoleo, benzene phnoleo, benzene hexohenole, and the like. In addition, imidazole derivative salts that are ionic fluids, and halogen-containing hydrocarbons such as methylene chloride and the like are also included.

 By selecting at least one or more types of fluids selected from these organic solvents, or by appropriately mixing these fluids, the lactam is produced as the high-temperature and high-pressure fluid of the present invention or from ketones. Can be used as a fluid having a function of accelerating the reaction. Furthermore, gases such as supercritical carbon dioxide, argon, and nitrogen can be suitably used as the high-temperature and high-pressure fluid. When the above solvents and fluids are used as high-temperature and high-pressure fluids, dissolved oxygen may oxidatively decompose organic substances or cause an oxidation reaction. It is desirable to use it afterwards. It is also preferable to remove oxygen from a raw material gas such as carbon dioxide before use.

 The temperature of the high-temperature and high-pressure fluid used in the present invention can be controlled by using a heater or a molten salt from outside the reactor. Alternatively, it is also possible to control the temperature of the internal heating method in the reactor. Alternatively, a high-temperature and high-pressure fluid may be manufactured in advance, and injected into the reactor from outside using a liquid sending pump or the like to cause a reaction. Temperature control may be performed by heating water or the like using high frequency. It is also possible to control the reaction conditions by supplying two or more types of high-temperature and high-pressure fluids with different temperature and pressure conditions to the reaction system. The pressure in the reaction vessel can be controlled by a pressure regulating valve if it is a flow type. Further, the pressure can be controlled by injecting another gas such as nitrogen gas.

The present invention is intended to produce ratatam by reacting a ketone with a hydroxylamine compound, and it is considered that oxime can be formed as an intermediate product. For example, when cyclohexanone, which is a cyclic ketone, is reacted as a substrate, cyclohexanone oxime is formed on the way, and immediately undergoes a rearrangement reaction. Ε-force prolactam is produced. In this reaction, heat is generated when the xanopenoxime and ε-force prolatatam are generated, and the generated heat is released. Therefore, the generated heat can be used for temperature control, which is favorable in terms of energy. Since the reaction often proceeds in a short time of about 1 second, it is necessary to consider the heat of production when designing and creating a manufacturing device or controlling the reaction.

 Basically, the reaction of the present invention is achieved under high-temperature and high-pressure fluid conditions of a temperature of not less than 175 ° C and a pressure of not less than 7 MPa. The reaction of the present invention can be suitably achieved under high temperature and high pressure conditions of a temperature of 250 ° C. or more and a pressure of 15 MPa or more. The reaction of the present invention is more preferably achieved by selecting high-temperature and high-pressure fluid conditions in a temperature range of 300 ° C. or more and a pressure range of 15 MPa or more. Furthermore, the reaction of the present invention is most preferably achieved by selecting high-temperature and high-pressure fluid conditions in a temperature range of 330 ° C. or more and a pressure range of 15 MPa or more. The optimal temperature condition varies depending on the processing time and pressure, but in general, a temperature range from 175 ° C to 600 ° C can be suitably selected. More preferably, a temperature range of 300 ° C. to 500 ° C. can be selected. Most preferably, a temperature range of 330 ° C. to 450 ° C. can be selected.

 The optimum pressure conditions vary depending on the processing time and reaction temperature, but usually a pressure range of 7 MPa to 80 MPa can be selected. Preferably, a pressure range of 9 MPa to 60 MPa can be selected. More preferably, a pressure range of 15 MPa and a pressure of 60 MPa can be selected, and most preferably a pressure range of 15 MPa to 50 MPa can be selected.

Further, appropriate temperature and pressure conditions can be adopted depending on the throughput and the reactor. In the present invention, it is recognized that the lactam formation reaction tends to proceed optimally in the temperature range of 330 to 450 ° C. and the pressure range of 15 MPa to 50 MPa. As the reactor, for example, a high-temperature high-pressure reactor capable of continuously flowing a high-temperature high-pressure fluid is used, but is not limited thereto, and is a device capable of setting a fluid reaction system under high-temperature high-pressure conditions. If so, the type is not restricted. Here, as a suitable reactor, for example, a flow-type high-temperature and high-pressure reactor is exemplified.

 In the present invention, for example, a room temperature substrate fluid in which cyclohexanone and a hydroxylamine compound are dissolved is introduced into the circulated high-temperature and high-pressure fluid, so that the temperature after mixing decreases. The rate of temperature decrease after mixing depends on the initial temperature of the carrier fluid, the reaction pressure, the flow rate of the carrier fluid, the flow rate of the substrate fluid, the amount of substrate such as ketones introduced, the reactor configuration, the reactor volume, etc. Therefore, it changes. In the present invention, the preset reaction temperature can be reached in a short time of 3 seconds or less by previously raising the temperature of the carrier fluid above the preset reaction temperature and mixing with a substrate solution of 10 ° C. or less. It is considered that the set temperature of the carrier fluid varies depending on the size, volume, and shape of the reaction vessel, the types of the carrier fluid and the substrate fluid, the temperature, the pressure, the value of the flow velocity ratio between the two, and the like.

 However, in general, the temperature of the carrier fluid can be set 5 to 400 ° C. higher than the set reaction temperature, preferably 5 to 300 ° C., more preferably 5 to 2 ° C. The reaction is preferably carried out at a temperature in the range of 50 ° C., and most preferably in the range of 5 to 200 ° C., with the set temperature of the carrier fluid higher than the set reaction temperature. At this time, it is preferable to control the set temperature in consideration of the influence of the reaction product heat of the intermediate product oxime—the desired product, ratatum.

In the present invention, the setting of the mixing ratio of the carrier fluid and the substrate fluid is important for determining the reaction temperature.In general, the mixing ratio is controlled by controlling the feed rates of the carrier fluid and the substrate fluid. Can be. Assuming that the flow rate of the carrier fluid is 1, the flow rate of the substrate fluid is usually 0.0 A value in the range of 0 1 to 100 can be selected as appropriate, but is preferably 0.01 to 10, more preferably 0.05 to 10 and most preferably 0.1 to 10. It is better to select a value in the range.

Even if the same flow rate is used, the flow rate used varies depending on the size, cross-sectional area, length, etc. of the reaction vessel, so that a linear velocity can be used instead of the flow rate. In the present invention, the flow rate of Kiyariya fluids and substrates fluid can be usually employed a flow rate of the linear velocity of ^{1 0- 4 ~ 1 0 4 m} / sec. Suitably ^{1 CD- 3 ~: L 0 3} mZ the flow rate of the linear velocity of sec, 1 0 the more the flow rate of the linear speed of preferably ^{1 0- 3 ~ 1 0 2 m} / sec, and most preferably - ² to 1 0 use a flow linear velocity of ² m / sec is desirable. The mixing ratio of the carrier fluid and the substrate fluid can also be expressed by the linear velocity ratio. Assuming that the linear velocity of the carrier fluid is 1, the linear velocity of the substrate fluid can usually be appropriately selected from the range of 0.001 to 10000, but is preferably 0.01 to 1 It is preferable to select a value in the range of 0.000, more preferably 0.005 to 500, and most preferably 0.01 to 100.

In the present invention, as a substrate fluid used for dissolving a ketone such as cyclohexanone and a hydroxyylamine compound, for example, water can be suitably used, but these fluids can be used in the present invention. However, the present invention is not limited to this, and one or more of the following fluids can be used in appropriate combination. For example, alcohols having a hydroxyl group include methanol, ethanol, propylene, isopro / ethanol, butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, heptanol, cycloheptanol. Mono-ole, otano-mono, cyclo-otanol, ethylene glycol, triethylene glycol and the like. Furthermore, ketones or aldehydes having a carbonyl group include, for example, acetone, 2-butanone, 3-pentanone, ethynoleketone, methinolethynole Examples include ketone, methinolepropynoleketone, ptinolemethinoleketone, cyclohexanone, and acetophenone.

 Examples of nitrile having a cyano group include acetonitril and benzonitrile. Examples of the amide or urea having an amide group include formamide, N-methylformamide, N, N'-dimethylacetamide, pyrrolidone, N-methylpyrrolidone, N, N-dimethylform. Amides and the like. Further, pentane, hexane, heptane, cyclohexane, decalin, benzene, toluene, xylene and the like can be used as the less polar hydrocarbon. It can be used as a substrate fluid for dissolving ketones by selecting at least one or more fluids selected from these organic solvent groups, or by appropriately mixing these fluids.

 The most characteristic feature of the present invention is that, as described above, a substrate fluid or ketone or hydroxyammonium obtained by dissolving a ketone in a high-temperature and high-pressure fluid at a temperature about 5 to 300 ° C. higher than the set temperature. This is to shorten the heating time of the reaction substrate to 3 seconds or less by directly introducing the system. Thereby, the selectivity and the yield of ratatum can be improved. Preferably, the heating time of the reaction substrate is 1 second or less, more preferably, the heating time of the reaction substrate is 0.5 second or less, and It is preferable that the heating time of the substrate is 0.3 seconds or less.

In particular, it is considered that the mixing speed is sharply increased when the carrier water in the supercritical state is used, because the viscosity of the fluid decreases and the diffusion coefficient increases as compared to the liquid carrier water. . In addition, it is known that in high-temperature and high-pressure water at sub-critical water conditions close to the supercritical point, the dielectric constant decreases and the solubility of organic substances rapidly increases. It is thought that the degree of resolution also increases, and provides favorable conditions for the transfer reaction. The reaction conditions vary depending on the type and concentration of the ketone used, the volume of the reaction tube, the high-temperature and high-pressure fluid conditions, the reaction time, and the like. In the present invention, the ketone or the hydroxylamine compound used by dissolving in the basic fluid used in the reaction is not limited to one type, and the reaction suitably proceeds even when a mixture of two or more types is used. The concentration of ketone introduced into the reactor can be controlled by controlling the flow rate of high-temperature and high-pressure water used as the carrier fluid of the flow system and the introduction flow rate of the ketone-containing substrate fluid as the reaction substrate.

 Usually, the concentration of the ketone introduced into the reactor can be selected within a concentration range of ImM or more. Preferably, an appropriate concentration value between 2 mM and 20 M can be selected, and most preferably, an appropriate concentration value between 2 mM and 10 M is selected. Is not limited to these concentration values. Also, the ketone as a substrate can be used directly in the reaction. For example, siphon hexanone is a liquid at room temperature, and can be introduced into a high-temperature, high-pressure fluid reaction field by a direct liquid sending pump. In the present invention, the reaction system temperature, pressure, reactor inner diameter, reactor volume, flow velocity, linear velocity, organic solvent type, reaction substrate concentration, reaction time, etc. are adjusted according to the type of ketone. Thus, the reaction yield of lactam can be controlled.

The reaction system of the present invention may be a substrate fluid in which the ketone and the hydroxylamine compound are dissolved in a high-temperature, high-pressure fluid having a temperature of not less than 175 ° C and an operating pressure of not less than 7 MPa, At that time, for example, the reaction proceeds without adding a water-soluble catalyst such as a metal ion, an acid or a base, a metal-supported catalyst, a solid catalyst such as a solid acid or a solid base, or an enzyme. The most characteristic of the present invention is that a ketone and a hydroxylamine compound are present in a high-temperature and high-pressure fluid to synthesize a lactam from the ketone. Water-soluble catalysts such as acids, bases, etc., metal-supported catalysts, solid catalysts such as solid acids and solid bases or enzymes Even if it reacts, it can not be done at all.

 In the present invention, a lactam is synthesized from ketones by the above-mentioned reaction system in a short reaction time of usually 0.0001 to 60 seconds. When a flow reactor is used, the reaction time depends on the reaction temperature, reaction pressure, flow rate and linear velocity of the high-temperature and high-pressure fluid, flow rate and linear velocity of the reaction substrate and substrate fluid, reactor shape, reactor inner diameter, reactor The reaction time can be controlled by controlling the length of the flow channel of the reaction. More preferably, the reaction time can be selected from a value in the range of 0.01 to 30 seconds, more preferably a value in the range of 0.001 to 20 seconds can be selected, Further, more preferably, a value in the range of 0.01 to 10 seconds can be selected, and most preferably, a value in the range of 0.01 to 5 seconds can be selected. However, it is not limited to these values.

As shown in the examples described below, the present inventors have shown that gas chromatography can perform a conversion reaction from ketone to ratatum in a short time (for example, a reaction time of about 1 second) under high temperature and high pressure fluid conditions. Tomography analyzer, high-performance liquid chromatography mass spectrometer (LC-MS), nuclear magnetic resonance spectrometer (NMR) ゃ Flier-infrared spectrophotometer (FTIR) I have confirmed. Furthermore, by using an LC-MS device, the types of ketones, ratatams, and by-product amino acids can be identified, and their contents can be accurately quantified. In addition, the lactam obtained continuously is separated and purified by an ion-exchange resin column, the infrared absorption spectrum is measured by an FTIR measuring device, and compared with that of a high-grade reagent product, the ratatam species is obtained. Can be accurately identified. Similarly, the type and purity of the lactam can be confirmed by NMR spectrum measurement. Their structures can be confirmed by gas chromatography mass spectrometry (GC-MS), LC-MS, NMR measurement, and FTIR. The reaction yield of the lactam produced in the present invention is determined by the reaction conditions such as temperature and pressure, the type of ketone, the concentration of ketone, the type of substrate fluid, the type of reactor, the size of the reactor, the type of carrier fluid, It fluctuates depending on the flow rate and linear velocity of the carrier fluid, ketone introduction rate and linear velocity, reaction time, and the like. For example, the resulting lactam may be recovered in a mixture with oxime. Similarly, according to the present invention, various rattam amino acids can be recovered together with the raw material substrate from various oximes or a mixture thereof, for example, by using a solvent extraction method, or by using a cation exchange resin or an anion exchange resin. Or lactams or amino acids can be separated from oxime ketone by their combination.

Furthermore, since ratatam and amino acids or ratatam can be separated, ratatam and amino acids can be purified and concentrated for each type. The ketone recovered at the same time can be reused as a raw material. Therefore, for example, under the conditions of high-temperature and high-pressure fluid, hexanone hexanone and hydroxylamine sulfate are reacted to synthesize ε-force prolatatam, and a solvent extraction method is applied to the obtained reaction fluid, or an ion exchange resin is used. By separating and purifying ラ -caprolactam and 6-aminohexanoic acid using, high-purity ε-caprolactam and 6-aminohexanoic acid can be suitably produced. In the present invention, a substrate fluid in which ketones such as cyclohexanone and a hydroxylamine compound are dissolved at a predetermined concentration as a reaction substrate is introduced into a reaction field under a high-temperature and high-pressure fluid condition that is circulated. By elevating the temperature of the substrate in a short time and reacting it under predetermined high-temperature and high-pressure conditions, for example, ε-caprolactam is synthesized from cyclohexanone. In addition, by continuously introducing a substrate fluid in which these ketones and a hydroxyylamine compound are dissolved into a reaction field of a flowing high-temperature and high-pressure fluid, each ketone is continuously obtained. Various ratatams corresponding to tons can be synthesized. As is evident from the above, the present invention is directed to controlling the type of carrier fluid, the reaction conditions, the type of ketone of the reaction substrate, the concentration of ketone, the type of substrate fluid, and the like in the above reaction system. This is a new continuous ratatam production method that enables continuous production of lactam in a shorter time, and is useful as a method for producing ratatam. BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is an explanatory view of a flow-type high-temperature and high-pressure reactor attached to two water pumps used in the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

 Next, the present invention will be specifically described based on examples, but the present invention is not limited at all by the following examples.

Example 1

 Using a continuous high-temperature and high-pressure reactor as shown in Fig. 1, under a high-temperature and high-pressure water condition at a temperature of 375 ° C and a pressure of 40 MPa, cyclohexanone (Aldrich Chemica IC Ompany, Inc. special grade) Reactor) and hydroxylamine sulfate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) were reacted to attempt continuous production of ε-force prolactam.

The material of the reactor is Hastelloy alloy C-276, the inner diameter of the reactor: 0.5 mm and the length of the reactor: 50 cm, so that the reactor volume is 0.0981 cm ³ was calculated. Each introduced preparation was injected with a high-pressure pump. Dissolved oxygen was expelled by publishing distilled water with nitrogen gas, and then heated to produce a carrier fluid at 495 ° C and 4 OMPa, which was flowed at a flow rate of 5.0 m1 / min. The linear velocity was 0.42 τα / sec. same Similarly, using deoxygenated distilled water, cyclohexanone and hydroxylamine sulfate were added to prepare a substrate solution.

The hexanone concentration of the substrate solution was 0.1 M, and the concentration of hydroxyxylamine sulfate was 0.060 M. The substrate solution at room temperature and 4 OMPa was introduced into the carrier fluid at the inlet of the reactor at a flow rate of 2.O ml / min (linear velocity 0.17 m / sec) and mixed. The reaction temperature of the mixed high-temperature and high-pressure water measured with a thermocouple (1) placed 1 cm from the inlet of the reactor was 375 ° C, which coincided with the temperature measured with the thermocouple (2) at the reactor outlet. However, the temperature inside the reactor is constant, and it is considered that the carrier fluid and the substrate solution are homogeneously mixed. The flow rate of the mixed high-temperature and high-pressure water was 7.00 ml / min (linear velocity 0.59 m / sec). Temperature 3 7 5 ° C, the density of the high-temperature high-pressure water at a pressure 4 0 MP a was 0. 6 0 9 6 g Bruno cm ^3.

The substrate concentration after mixing in high-temperature, high-pressure water was calculated to be 28.6 mM, and the hydroxysulfamine concentration was 17.1 mM. The reaction time was 0.513 seconds. Therefore, it is considered that the mixing was completed completely within a short time within 0.011 seconds. For the reaction solution recovered after the reaction, the composition obtained from gas chromatography and high performance liquid chromatograph-peak area of the mass spectrometer was calculated as follows: Protolactam: 87.0% and 6-amino Xanic acid: 13.0%, no cyclohexanone was detected, and the conversion was 100%. 6-aminohexanoic acid is considered to have been obtained by hydrolysis of ε-force prolactam, and is important as a monomer for the production of poly-force prolactam. The total selectivity of ε-caprolactam and 6-aminohexanoic acid was 100%. Almost no xanone oxime was detected. Example 2 Using high-temperature and high-pressure water as a carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of _ε -force prolactam. However, the reaction was performed under the following reaction conditions. (Reaction conditions)

Temperature and pressure of carrier fluid: 510 ° C and 40MPa

Carrier fluid flow velocity and linear velocity: 2.0 m1 Zmin and 0.17 m

/ s e c

 Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

Temperature and pressure of 0.1 M substrate solution: room temperature and 40 M Pa

 Flow rate and linear velocity of 0.1 M substrate solution: 1.0 m 1 Zmin and 0.08 m / sec

Temperature of reaction high-pressure and high-pressure water mixed fluid: 375 ° C

Pressure of reaction high-temperature high-pressure water mixed fluid: 4 O M P a

Density of reaction high-temperature and high-pressure water mixture: 0.6096 _g Z cm ³

The flow rate and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 3. O ml / min and 0.2 oxn./sec The substrate concentration after mixing in the high-temperature and high-pressure water mixed fluid is 33.3 mM and sulfuric acid. The concentration of droxylamin was calculated to be 18.3 mM. The reaction time was 1.196 seconds. Therefore, it is considered that the mixing was completed completely in a short time within 0.024 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction by gas chromatography and high-performance liquid chromatograph-mass spectrometry was ε-force prolatatam: 82.3%, 6-amino Xanic acid: 17.0%, cyclohexanone: 0.7%, and the conversion was 99.3%. ε—Proprolactam and 6-aminohexa The total selectivity of the acid was 100%. Cyclohexanone oxime was hardly detected. Example 3

Using high-temperature and high-pressure water as a carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of _ε -force prolactam. However, the reaction was performed under the following reaction conditions. (Reaction conditions)

Temperature and pressure of carrier fluid: 470 ° C and 40MPa

Flow velocity and linear velocity of the carrier fluid: 10 Oml / min and 0.85 rs / sec

 Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

 Temperature and pressure of 0.1 M substrate solution: room temperature and 40 MPa

 Flow rate and linear velocity of 0.1 M substrate solution: 2. Oml / min and 0.17 mZ sec

Temperature of reaction high-pressure and high-pressure water mixed fluid: 375 ° C

Pressure of reaction high-temperature and high-pressure water mixed fluid: 40 MPa

Density of reaction high-temperature and high-pressure water mixture: 0.6096 g Z cm ³

Flow velocity and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 1 2. ^! Eno! ! ! ! ! as well as

The substrate concentration after mixing in the mixed fluid of 1.0 m / sec high-temperature and high-pressure water was calculated to be 16.7 mM and the concentration of hydroxylamine sulfate to be 9.2 mM. The reaction time was 0.299 seconds. Therefore, it is considered that the mixing was completed completely in a short time within 0.006 seconds. The mixed high-temperature and high-pressure aqueous solution collected after the reaction is Chromatography and high-performance liquid chromatography-mass spectrometry revealed that the composition was as follows: ε-force prolactam: 73.0%, 6-aminohexanoic acid: 20.8%, cyclohexane Xanone oxime: 0.3%, and cyclohexanone: 5.9%, and the conversion was 94.1%. The total selectivity for ε-proratetam and 6-aminohexanoic acid was 99.7%. Example 4

Using a high-temperature high-pressure water as a wire carrier rear fluid, the same operation in _Ε by reacting cyclohexanone and sulfate inhibit Dorokishiruamin cyclohexane Example 1 - attempting continuous production of forces Purora Kutamu. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)

Carrier fluid temperature and pressure: 277 ° C and 15 MPa

Velocity and linear velocity of carrier fluid: 5. Oml / min and 0.42 msec

 Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

 0.1 M substrate solution temperature and pressure: room temperature and 15 MPa

 Flow rate and linear velocity of 0.1 M substrate solution: 1. S ml Zmin and 0.10 m / sec

Temperature of reaction high-pressure and high-pressure water mixed fluid: 200 ° C

Pressure of reaction high-temperature and high-pressure water mixed fluid: 15MPa

Density of reaction high pressure water mixture: 0.8 7 4 6 g Z c ni ³

Flow rate and linear velocity of reaction high-temperature and high-pressure water mixed fluid: 6.2 ml / min and 0.53 mZ sec The substrate concentration after mixing in the mixed fluid of high-temperature and high-pressure water was calculated to be 19.4 mM and the concentration of hydroxylamine sulfate to be 10.6 mM. The reaction time was 0.830 seconds. Therefore, it is considered that the mixing was completed completely within a short time within 0.017 seconds. The mixed high-temperature and high-pressure aqueous solution recovered after the reaction was measured by gas chromatography and high-performance liquid chromatograph-mass spectrometry, and the composition obtained was ε-force prolatatam: 5.7%, cyclohexanone oxime: 7 1.2% and cyclohexanone: 23.1%, and the conversion was 76.9%. The selectivity of ε-caprolactam was 7.4%. 6-Aminohexanoic acid was hardly detected. Comparative Example 1

Using high-temperature and high-pressure water as a carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of _ε -force prolactam. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)

Temperature and pressure of carrier fluid: 23.3 ° C and 5 MPa

Velocity and linear velocity of carrier fluid: 5.0 mln and 0.42 m

/ s e c

Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

Temperature and pressure of 0.1 M substrate solution: room temperature and 5 MPa

Flow rate and linear velocity of 0.1 M substrate solution: 1.211 1 111 1 11 and 0.10 m / sec

Temperature of reaction high-pressure and high-pressure water mixed fluid: 150 ° C

Reaction high pressure and high pressure water mixed fluid pressure: 5MPa

高温高圧水混合流体中での混合後の基質濃度は 1 9. 4 mM及び硫酸 ヒ ドロキシルァミン濃度は 1 0. 6 mMと計算された。 反応時間は 1. 0 3 2秒であった。 従って、 0. 0 2 1秒以内の短時間で混合は完全に 行われていると考えられる。 反応後に回収した混合高温高圧水溶液をガ スクロマ トグラフィ一及び高速液体ク口マ トグラフィ一質量分析装置で 測定して得られた組成は、 シクロへキサノ ンォキシム ： 6 8. 8 %、 及 ぴシクロへキサノン ： 3 1. 2 %であり、 転化率は 6 8. 8 %であった 。 ε —力プロラクタムと 6—アミノへキサン酸は全く検出されなかった Density of reaction high-temperature high-pressure water mixed fluid: 1.0 8 7 4 _gcm ³ Flow velocity and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 6.2 1 111 1 111 1 11 and 0

The substrate concentration after mixing in the mixed fluid of high-temperature and high-pressure water was calculated to be 19.4 mM and the concentration of hydroxylamine sulfate to be 10.6 mM. The reaction time was 1.032 seconds. Therefore, it is considered that the mixing was completed completely within a short time within 0.021 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction by gas chromatography and high-performance liquid chromatograph-mass spectrometry is cyclohexanonoxime: 68.8%, and cyclohexanone. : 31.2%, and the conversion was 68.8%. ε-caprolactam and 6-aminohexanoic acid were not detected at all

Example 5

 Using high-temperature and high-pressure water as the carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of ε-force prolactam. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)

Temperature and pressure of the carrier fluid: 37 4 ° C and 9 MPa

Velocity and linear velocity of carrier fluid: 5. Oml / min and 0.42 m / sec

 Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

0.1 M substrate solution temperature and pressure: room temperature and 9 M Pa

Flow rate and linear velocity of 0.1 M substrate solution: 1.2 ml Zmin and 0.10 m / sec Temperature of reaction high-pressure high-pressure water mixed fluid: 298 ° C

Pressure of reaction high-temperature and high-pressure water mixed fluid: 9 MPa

Density of reaction high pressure water mixture: 0.7 1 3 4 g Z cm ³

Flow rate and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 6.2 ml / min and 0.53 m./sec The substrate concentration after mixing in the high-temperature and high-pressure water mixed fluid is 19.4 mM and hydrosulfate. The xylamine concentration was calculated to be 10.6 mM. The reaction time is 0.

6 7 7 seconds. Therefore, it is considered that the mixing was completed completely within a short time of less than 0.014 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction with a gas chromatograph and a high performance liquid chromatograph mass spectrometer was ε-force prolactam: 49.6%, cyclohexanone oxime: 0. 7%, 6-aminohexanoic acid: 4.5%, and cyclohexanone: 45.2%, and the conversion was 54.8%. The total selectivity of ε-caprolactam and 6-aminohexanoic acid is 98.

7%. Example 6

 Using high-temperature and high-pressure water as the carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of ε-force prolactam. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)

Carrier fluid temperature and pressure: 3335 ° C and 15MPa

Flow rate and linear velocity of Kiyariya fluid: 5.0 ₁ 11 _1/1] 1 1 11及Pi 0. 4 2 m / sec Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

 0.1 M substrate solution temperature and pressure: room temperature and 15 MPa

 Flow rate and linear velocity of 0.1 M substrate solution: 1.2 m 1 in and 0.10 m / sec

Temperature of reaction high pressure water mixed fluid: 250 ° C

Pressure of reaction high-temperature and high-pressure water mixed fluid: 15MPa

Density of reaction high pressure water mixture: 0. S ll S gZ cm ³

Flow rate and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 6.2 ml / min and 0.53 m / sec The substrate concentration after mixing in the high-temperature and high-pressure water mixed fluid is 19.4 mM and the concentration of hydroxylamine sulfate Was calculated to be 10.6 mM. The reaction time was 0.770 seconds. Therefore, it is considered that the mixing was completely performed within a short time within 0.016 seconds. The mixed high-temperature and high-pressure aqueous solution recovered after the reaction was measured by gas chromatography and high-performance liquid chromatograph-mass spectrometry, and the composition obtained was as follows: £ —force prolatatam: 34.3%, cyclohexanone oxime: 28.1%, 6-aminohexanoic acid: 1.3%, and cyclohexanone: 36.3%, and the conversion was 63.7%. _The total selectivity of _ε- caprolactam and 6-aminohexanoic acid was 55.9%. Example 7

Using high-temperature and high-pressure water as the carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of ε-force prolactam. However, the reaction was performed under the following reaction conditions. (Reaction conditions)

Temperature and pressure of carrier fluid: 380 ° C and 15MPa

Carrier fluid flow velocity and linear velocity: 5. Oml Zmin and 0.42 m

/ s e c

 Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

0.1 M substrate solution temperature and pressure: room temperature and 15 M Pa

 Flow rate and linear velocity of 0.1 M substrate solution: 1.? ! ! ! Yeah! ! ! ! ! as well as. . 10 m / sec

Temperature of reaction high-pressure and high-pressure water mixed fluid: 300 ° C

Pressure of reaction high-temperature and high-pressure water mixed fluid: 15 MPa

Density of reaction high-temperature high-pressure water mixed fluid: 0.72 600 g Z cm ³

Flow velocity and linear velocity of the reaction high-temperature high-pressure water mixed fluid: 6.2 ml Zmin and 0

The substrate concentration after mixing in a mixed fluid of 53 m / sec high-temperature and high-pressure water was calculated to be 19.4 mM and the concentration of hydroxylamine sulfate to be 10.6 mM. The reaction time was 0.689 seconds. Therefore, it is considered that the mixing was completed completely within a short time of less than 0.014 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction with a gas chromatograph and a high performance liquid chromatograph mass spectrometer was ε-force prolatatam: 70.6%, 6-aminohexanoic acid : 2.0%, cyclohexanone oxime: 5.0%, and cyclohexanone: 22.4%, and the conversion was 77.6%. The total selectivity of ε-prolactam and 6-aminohexanoic acid was 93.6%. Example 8 Using high-temperature, high-pressure water as the carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of E-force prolactam. However, the reaction was performed under the following reaction conditions. (Reaction conditions)

Temperature and pressure of carrier fluid: 4 65 ° 5 and 3 01 ^? 3

Velocity and linear velocity of carrier fluid: 5.0 m1 Zmin and 0.42 m

/ s c

 Hydroxylaminate sulfate concentration of 0.1 M substrate solution: 0.055 M

0.1 M substrate solution temperature and pressure: room temperature and 30 M Pa

Flow rate and linear velocity of 0. 1 M substrate solution: 1. 2 ml ^/ / min and 0. 1 0 m / sec

Temperature of reaction high pressure water mixed fluid: 350 ° C

Pressure of reaction high-temperature high-pressure water mixed fluid: 3 OMP a

Density of reaction high pressure water mixed fluid: 0. e AS gZ cm ³

Flow velocity and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 6.2 ml / min and 0.53 m / sec The substrate concentration after mixing in the high-temperature and high-pressure water mixed fluid is 19.4 mM and hydroxyamine sulfate. The concentration was calculated to be 10.6 mM. The reaction time was 0.615 seconds. Therefore, it is considered that the mixing was completed completely within a short time within 0.013 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction with gas chromatography and high-performance liquid chromatograph-mass spectrometry was ε-force prolatatam: 73.0%, 6-amino Xanic acid: 20.4%, cyclohexanone oxime: 0.1%, and cyclohexanone: 6.5%, and the conversion was 93.5%. The total selectivity of ε-caprolactam and 6-aminohexanoic acid was 99.9%. Example 9

 Using high-temperature and high-pressure water as the carrier fluid, cyclohexanone and hydroxylamine sulfate were reacted in the same manner as in Example 1 to attempt continuous production of ε-force prolactam. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)

Carrier fluid temperature and pressure: 510 ° C and 40MPa

Velocity and linear velocity of carrier fluid: 5.0 m1 / min and 0.42 m / sec

 Hydroxylyamine sulfate concentration of 0.1 M substrate solution: 0.055 M

Temperature and pressure of 0.1 M substrate solution: room temperature and 4 O M Pa

Flow rate and linear velocity of 0.1 M substrate solution: 1.2 ml / min and 0.10 m / sec

Temperature of reaction high-pressure high-pressure water mixed fluid: 400 ° C

Pressure of reaction high-temperature high-pressure water mixed fluid: 4 O M P a

Density of reaction high pressure water mixed fluid: 0.5 2 3 7 _g cm ³

Flow velocity and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 6.? ! ! ! Yeah! ! ! ! ! as well as.

The substrate concentration after mixing in the mixed fluid of 5.3 m / sec high-temperature and high-pressure water was calculated to be 19.4 mM and the concentration of hydroxylamine sulfate to be 10.6 mM. The reaction time was 0.497 seconds. Therefore, it is considered that the mixing was completely performed within a short time within 0.010 seconds. The mixed high-temperature and high-pressure aqueous solution collected after the reaction is The composition obtained by mass spectrometry using high-performance liquid chromatography and high performance liquid chromatography was as follows: ε-force prolactam: 80.4%, 6-aminohexanoic acid: 9.9%, cyclohexane Hexanone oxime: 0.2%, cyclohexanone: 8.9%, and the conversion was 91.1%. _The total selectivity of _f- caprolactam and 6-aminohexanoic acid was 99.8%. Example 10

 Using distilled water as the carrier fluid, the same procedure as in Example 1 was used to react hexagonal hexanone with hydroxyamine hydrochloride (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) to give E-force prolatatatam. Tried continuous production. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)

Temperature and pressure of carrier fluid: 485 ° C and 40MPa

Carrier fluid flow velocity and linear velocity: 2.5 m1 / min and 0.21 m / sec

 Hydroxylamine hydrochloride concentration of 0.1 M substrate solution: 0.1 M

0.1 M substrate solution temperature and pressure: room temperature and 40 MPa

Flow rate and linear velocity of 0.1 M substrate solution: 1.0 111 1 111 ₁ 1 and 0.08 m / sec

Temperature of reaction high-pressure and high-pressure water mixed fluid: 370 ° C

Pressure of reaction high-temperature and high-pressure water mixed fluid: 40 MPa

Density of reaction high-temperature and high-pressure water mixed fluid: 0.6 2 3 g Z cm ³

Flow velocity and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 3.5111 1 / ^/ 1 ₁ 1 1 1 and 0.30 m / sec The substrate concentration after mixing in the mixed fluid of high-temperature and high-pressure water was calculated to be 28.6 mM and the concentration of hydroxylamine hydrochloride to be 31.4 mM. The reaction time was 1.048 seconds. Therefore, it is considered that the mixing was completed completely within a short time within 0.021 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction by gas chromatography and high-performance liquid chromatograph-mass spectrometry is f-force prolatatam: 2.9%, 6-aminohexanoic acid : 92.8%, and cyclohexanone: 4.3%, and the conversion ratio was 95.7%. The total selectivity of ε-caprolactam and 6-aminohexanoic acid was 100%. Cyclohexanonoxime was hardly detected. Example 1 1

 Using high-temperature and high-pressure water as the carrier fluid, cyclohexanone and hydroxyamine oxalate (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) were reacted in the same manner as in Example 1 to obtain ε-force prolatatatam. Continuous production was attempted. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)

Temperature and pressure of carrier fluid: 457 ° C and 40MPa

Carrier fluid flow velocity and linear velocity: 5.0 m 1 Zm i η and 0.42 m / sec

 Hydroxylamine oxalate concentration in 0.1 M substrate solution: 0.1 M

Temperature and pressure of 0.1 M substrate solution: room temperature and 4 O M Pa

Flow rate and linear velocity of 0.1 M substrate solution: 1. ! ! ! ! ! ! ! Influence. . 0 8 vs \ / sec Temperature of reaction high pressure water mixed fluid: 37 1 ° C

Reaction high pressure water mixed fluid pressure: 4 OMP a

Density of reaction high pressure water mixed fluid: 0.620 gZ cm ³

Flow velocity and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 6. O ml Zmin and 0.51 m / sec The substrate concentration after mixing in the high-temperature and high-pressure water mixed fluid is 16.7 mM and the concentration of hydroxylamine oxalate Was calculated to be 18.3 mM. The reaction time was 0.608 seconds. Therefore, it is considered that the mixing was completed completely within a short time within 0.013 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction with a gas chromatograph and a high performance liquid chromatography mass spectrometer was ε-force prolatatam: 40.6%, 6-aminohexanoic acid: 3.0%, cyclohexanonoxime: 6.9%, and cyclohexanone: 49.5%, and the conversion was 93.1%. The total selectivity of Ε-caprolactam and 6-aminohexanoic acid was 46.8%. Example 1 2

 Using high-temperature and high-pressure water as the carrier fluid, the same operation as in Example 1 was carried out to react the hexahexanone with a 50% aqueous solution of hydroxyamine (a special-grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) to obtain ε— Attempted continuous production of force prolatatam. However, the reaction was performed under the following reaction conditions.

(Reaction conditions)-Temperature and pressure of the carrier fluid: 410 ° C and 40 MPa

Velocity and linear velocity of carrier fluid: 2.9 m 1 in and 0.25 m / s

 Hydroxylamin concentration of 0.1 M substrate solution: 0.1 M

 Temperature and pressure of 0.1 M substrate solution: room temperature and 4 OMPa

Flow rate and linear velocity of 0.1 M substrate solution: 1. 0111 1 / ^/ 111 1 11 and 0.08 mZ sec

Temperature of reaction high-pressure and high-pressure water mixed fluid: 380 ° C

Pressure of reaction high-temperature and high-pressure water mixed fluid: 40 MPa

Density of reaction high-temperature high-pressure water mixed fluid: 0.5 9 4 8 g Z cm ³

The flow rate and linear velocity of the reaction high-temperature and high-pressure water mixed fluid: 3.9 ml Zmin and 0.33 m / sec The substrate concentration after mixing in the high-temperature and high-pressure water mixed fluid is 25.6 mM and hydroxylamine The concentration was calculated to be 28.2 mM. The reaction time was 0.760 seconds. Therefore, it is considered that the mixing was completed completely within a short time of less than 0.016 seconds. The composition obtained by measuring the mixed high-temperature and high-pressure aqueous solution recovered after the reaction with a gas chromatograph and a high-performance liquid chromatograph-mass spectrometer was ε-force prolactam: 48.4%, cyclohexane Nonoxime: 0.8%, cyclohexanone: 50.9%, and the conversion was 49. 1%. The selectivity for ε-caprolactam was 98.6%. 6-Aminohexanoic acid was hardly detected. Industrial applicability

As described in detail above, the present invention efficiently synthesizes ratatum in a short time by introducing a ketone and a hydroxylamine compound dissolved in a substrate fluid into a flowing reaction field under high-temperature and high-pressure fluid conditions. A continuous production method of ratatum, characterized in that The present invention relates to a continuous ratatum production method characterized by selectively producing a tom.

According to the present invention, there is provided a high-yield lactam production method characterized by 1) efficient production of ratatam from ketone dissolved in a substrate fluid, and 2) use of a ketone and a hydroxylamine compound. 3) The ratatom can be produced in a short time by reacting the ketone with the hydroxylamine compound under high temperature and high pressure.4) The heating time of the reaction substrate is shortened to 3 seconds or less. By doing so, the selectivity and yield of ratatam can be significantly improved.5) It is said that ratatam can be synthesized in a short period of time, usually from 0.0001 seconds to 60 seconds. A special effect is achieved.

Claims

The scope of the claims 1. A method for producing a lactam, which comprises reacting a ketone with a hydroxylamine compound in a reaction field under predetermined high-temperature and high-pressure fluid conditions. 2. The method for producing ratatum according to claim 1, wherein the ketone and the hydroxylamine compound are introduced into a continuously flowing high-temperature and high-pressure fluid and reacted. 3. The method for producing a lactam according to claim 1, wherein a ketone and a substrate solution in which a hydroxylamine compound is dissolved are introduced into a continuously flowing high-temperature and high-pressure fluid to cause a reaction. 4. The method for producing a lactam according to claim 1, wherein water is used as the high-temperature high-pressure fluid. 5. The method for producing ratatum according to any one of claims 1 to 4, wherein a cyclic ketone is used as the ketone. 6. The method for producing ratatum according to claim 5, wherein cyclohexanone is used as the cyclic ketone. 7. The method according to any one of claims 1 to 4, wherein the hydroxylamine compound is at least one selected from the group consisting of hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine oxalate, and hydroxylamine. The method for producing ratatum according to any one of the above. 8. The method for producing a lactam according to any one of claims 1 to 4, wherein the high-temperature and high-pressure conditions are a temperature range of 175 ° C or more and a pressure range of 7 MPa or more.