JP4811764B2 - Nitro compound production method and production apparatus thereof - Google Patents

Description

  The present invention relates to a method for producing an organic nitro compound characterized by synthesizing an organic nitro compound by a reaction between an organic substrate and a nitrating agent using a reaction system using high-temperature and high-pressure water as a reaction medium, and a production apparatus therefor. More specifically, in a reaction system using high-temperature high-pressure water having a temperature of 300 ° C. or higher and a pressure of 20 MPa or higher, for example, subcritical water or supercritical water as a reaction medium, the organic nitro compound is safely and continuously added. The present invention relates to a new production technology for nitro compounds that enables efficient production.

  Organic nitro compounds are important compounds that are used as starting materials or intermediates for organic industrial products in a wide range of fields, taking advantage of their diverse reactivity. However, the industrial manufacturing method has conventionally had problems such as operational danger, control of exothermic reaction, and environmental pollution. The present invention makes it possible to fundamentally solve these problems of the prior art, and a method for producing an organic nitro compound that can be mass-produced in a short time by a simple method and apparatus, and the production thereof. It provides new technology for equipment.

  Nitro compounds are extremely important as starting materials or intermediates for industrial products because of their abundant reactivity. In particular, aromatic nitro compounds are important as starting materials or intermediates in the manufacture of a wide range of organic industrial products such as pharmaceuticals, agricultural chemicals, dyes, fibers, plastics, etc. Every year, millions of tons of nitro compounds worldwide Is consumed. For example, taking the simplest compound, nitrobenzene, as an example, according to UN statistics (1997), its consumption in 1995 was 561,240 tons in North America, 241,470 tons in Japan, and 172, EC in EC. Considering the demand for nitro compounds as strategic explosives that have not been statistically released, it is 280 tons (Non-patent Document 1). is expected. These nitro compound groups form distinctive product form groups from the intensity of reaction in the manufacturing process and the danger of products.

  Nitro compounds are basic industrial products with such a great demand, but their industrial synthesis involves the nitration of nitric acid alone or in combination with sulfuric acid, a technique developed in the first half of the last century. Even now, it is adopted worldwide as a practical method. Since this method uses a large amount of strong acid, it has technical problems that cannot be avoided, such as operational danger, acid resistance equipment, and control of exothermic reaction. Treatment of waste acid and wastewater generated during the nitration reaction is indispensable due to environmental problems, and is a major factor that presses down on manufacturing costs. In addition, in nitration reaction with nitric acid, it is difficult to produce the corresponding nitro compound from saturated hydrocarbons with high yield.

  Therefore, by producing aromatic nitro compounds without using inorganic acids that are difficult to handle such as nitric acid, sulfuric acid, and phosphoric acid, aromatic nitro compounds can be produced in an environmentally friendly manner with less pollution. There has been proposed a method for producing an aromatic nitro compound by dissolving or suspending a group compound in a halogenated organic solvent and allowing oxygen or air containing nitrogen oxide and ozone to act (see Patent Document 1). However, this method requires a catalyst in order to increase the reaction rate, and it is necessary to provide ancillary equipment such as an ozone generator for generating ozone.

In addition, as another method, for example, using N ₂ O ₃ produced by the reaction of one of N ₂ O and NO with oxygen and oxygen, in the absence of a catalyst, under relatively mild conditions Nitration of an organic substrate to produce a nitro compound with high conversion and selectivity (see Patent Document 2), and further, nitration without using nitric acid, a catalyst having a rare earth element and a perfluoroalkyl group, Group III A reaction method for nitrating aromatic compounds in the presence of elemental nitrates and carboxylic acid anhydrides (see Patent Document 3) has been proposed. However, this type of method has various problems. However, it is difficult to say that it is suitable for industrial production.

  The nitro compound produced by the above method is, for example, hydrogenated and converted to an aromatic amine or the like that is an intermediate material for industrial products. As a hydrogenation reaction of an aromatic nitro compound, for example, when an aromatic amine is produced by hydrogenation of an aromatic nitro compound in a gas phase on a fixed catalyst, the inlet is adiabatically under a specific pressure. A method of performing by specifying a temperature and a pore catalyst temperature (see Patent Document 4), and catalyzing a granular composite inorganic ion exchanger obtained by supporting a heteropolyacid compound in the pores of a porous inorganic support A hydrogenation reaction of an aromatic nitro compound (see Patent Document 5) and the like have been proposed.

  The produced amines, for example, tolylenediamine, are produced in large quantities as intermediates of tolylene diisocyanate (TDI), which is a raw material for polyurethane resins. In the production process of toluidine isocyanate, toluene is converted into dinitrotoluene by nitration, converted to tolylenediamine by catalytic hydrogenation, and further converted into diisocyanate by phosgene. The routed process is suitable as a continuous process for mass production of diisocyanate.

JP-A-4-217645 JP-A-10-236987 JP 2003-81920 A JP-A-8-59569 JP 2001-269582 A Chemical Economy, March Special Issue, “Polyisocyanate” (2002)

  In such a situation, in view of the above prior art, the present inventors operate without using a large amount of inorganic acids such as nitric acid and sulfuric acid, and environmentally difficult harmful substances such as heavy metal catalysts. As a result of intensive research aimed at developing new nitro compound synthesis technology that does not cause problems such as high risk, acid resistance equipment, and exothermic reaction control, a reaction system using high-temperature and high-pressure water as a reaction medium was used. Thus, it has been found that by synthesizing an organic nitro compound by reaction of an organic substrate and a nitrating agent, the organic nitro compound can be produced safely, simply and efficiently, and the present invention has been completed.

  That is, the present invention provides a method and apparatus for producing a nitro compound that can efficiently produce an organic nitro compound with a simple apparatus by using high-temperature and high-pressure water under high-temperature and high-pressure conditions as a reaction medium. It is intended to provide. Another object of the present invention is to provide an organic nitro compound production method and production apparatus that do not cause problems in operational danger, acid resistance equipment, exothermic reaction control, and the like. Another object of the present invention is to provide a reaction process for producing an organic nitro compound in one step, continuously in a very short reaction time, and maintaining a high degree of selectivity. Furthermore, an object of the present invention is to provide a method for producing an environmentally friendly organic nitro compound which does not require treatment of a large amount of waste acid and waste water.

The present invention for solving the above-described problems comprises the following technical means.
(1) using a reaction system as a reaction medium high-temperature and high-pressure water, a process for the preparation of organic nitro compounds you synthesize organic nitro compound by reaction of an organic substrate and a nitrating agent,
The reaction medium is high-temperature high-pressure water of 300 ° C. or higher and 20 MPa or higher, or subcritical water or supercritical water, and the organic substrate is an aliphatic hydrocarbon, aliphatic alcohol, aromatic hydrocarbon, polycyclic A method for producing an organic nitro compound, which is an aromatic compound or a nitrogen-containing aromatic.
( 2 ) The method for producing an organic nitro compound according to (1) above, wherein the organic nitro compound is synthesized from the organic substrate by a one-step reaction process.
( 3 ) The method for producing an organic nitro compound according to (1), wherein the organic nitro compound is synthesized from the organic substrate by a continuous process.
( 4 ) The method for producing an organic nitro compound according to (1), wherein the nitrating agent is nitric acid, ammonium nitrate, lithium nitrate, sodium nitrate, potassium nitrate, or calcium nitrate.
( 5 ) The production of the organic nitro compound according to (1), wherein the selectivity, conversion rate, and / or yield of the target compound is controlled by adjusting the composition, temperature, pressure, and / or time of the reaction system. Method.
( 6 ) An apparatus for synthesizing an organic nitro compound using a reaction system using high-temperature high-pressure water as a reaction medium, which is used in the method for producing an organic nitro compound according to any one of (1) to (5). And
Reactors (including piping) resistant to the high-temperature and high-pressure water and nitrating agent , high-temperature and high-pressure water supply means, organic substrate supply means, and nitrating agent supply means. A high-temperature high-pressure channel for supplying the substrate and the nitrating agent to the reactor, and the organic substrate and the nitrating agent are mixed with the high-temperature high-pressure water in the channel before flowing into the reactor. Then, each of the above means is arranged to be supplied to the reactor, and the reaction medium is high-temperature high-pressure water having a temperature of 300 ° C. or higher and a pressure of 20 MPa or higher, or subcritical water or supercritical water, In the reactor, an organic nitro compound is synthesized in a short reaction time of 0.001 seconds to 30 seconds using a reaction system in which high temperature and high pressure water is used as a reaction medium from an organic substrate and a nitrating agent. Organic nitro compounds Manufacturing equipment.
( 7 ) The apparatus for producing an organic nitro compound according to ( 6 ), which is a continuous production apparatus provided with continuous operation means.

Next, the present invention will be described in more detail.
The present invention is characterized by a method for producing an organic nitro compound, which synthesizes an organic nitro compound by a reaction between an organic substrate and a nitrating agent using a reaction system using high-temperature and high-pressure water as a reaction medium, and a production apparatus thereof. Is. The present invention is a raw material or intermediate in the synthesis of organic nitro compounds by a one-step reaction, continuously without risk of operation, and in the manufacture of organic industrial products such as pharmaceuticals, agricultural chemicals, dyes, fibers and plastics. The present invention provides a novel reaction process capable of safely producing an organic nitro compound useful as

  In the present invention, high-temperature and high-pressure water is used as the reaction medium. Specifically, high-temperature and high-pressure water having a temperature of 300 ° C. or higher and a pressure of 20 MPa or higher is preferably used, preferably subcritical water or supercritical water. Water is used as the reaction medium. Here, supercritical water refers to the state of water at a temperature of 375 ° C. or higher and a pressure of 22.1 MPa or higher. Subcritical water is water in a high-temperature and high-pressure state close to supercritical water, and usually means water whose temperature is close to the critical temperature of water and / or whose pressure is close to the critical pressure of water. Water in the vicinity of 300 to 370 ° C. and a pressure of 20 to 22 MPa is included.

  There are three types of water: gas (water vapor), liquid (water), and solid (ice). When the temperature exceeds the critical temperature and exceeds the critical pressure, it does not condense even when pressure is applied. The liquid boundary disappears and a single fluid phase appears. This state is defined as a supercritical state, and high-temperature and high-pressure water such as water in a supercritical state or a subcritical state close to the supercritical state exhibits properties different from the normal properties of liquids and gases. That is, the density of water in the supercritical or subcritical state is close to that of a liquid, the viscosity is close to that of a gas, and the thermal conductivity and diffusion coefficient show intermediate properties between the gas and the liquid and have a specific effect on the progress of chemical reactions. give.

  The high-temperature and high-pressure water such as supercritical water used in the present invention is produced by a method known per se. It is controlled by the internal heat system in the vessel. Alternatively, high-temperature and high-pressure water may be produced in advance and injected from the outside into the reactor using a water pump or the like to adjust the temperature and pressure in the reactor. It is also possible to control the reaction conditions by supplying two or more types of high-temperature and high-pressure water having different temperatures to the reaction system. Moreover, if the pressure in a reaction container is a continuous type, it can be controlled with a pressure control valve. Furthermore, the pressure can be controlled by injecting another gas such as nitrogen gas.

  The water used for producing the high-temperature and high-pressure water of the reaction medium is not particularly limited, and for example, distilled water, ion exchange water, tap water, ground water, etc. may be used, but dissolved oxygen adversely affects the reaction. Therefore, it is desirable to remove them by bubbling with nitrogen gas, helium or the like in advance. Unlike the conventional synthesis method, the method of the present invention can synthesize an organic nitro compound without using a metal catalyst or an organic solvent, and therefore does not require a catalyst or an organic solvent. It does not necessarily prevent. In the present invention, for example, in the case of using a catalyst, a catalyst addition and removal step can be added as appropriate. In general, any catalyst can be used as long as it is a catalyst used in this type of reaction. For example, any catalyst that promotes the nitration reaction can be used.

  In the present invention, an organic substrate, a nitrating agent, and a reaction medium are introduced into a reactor and held for a predetermined time, whereby the organic substrate is converted into a nitro compound. The organic substrate is not particularly limited, and examples thereof include aliphatic compounds, aromatic compounds, and heterocyclic compounds, but preferably aliphatic hydrocarbons, aliphatic alcohols, aromatic hydrocarbons. , Polycyclic aromatic compounds, nitrogen-containing aromatic compounds and the like are used. Specifically, examples of the aliphatic hydrocarbon include propane, butane, pentane, and hexane. Examples of the aliphatic alcohol include ethylene glycol, glycerin, cellulose, and pentaerythritol.

  Examples of the aromatic hydrocarbon include toluene, phenol, anisole, and chlorobenzene. Examples of the polycyclic aromatic compound include naphthalene and anthracene. Moreover, a pyridine is mentioned as a nitrogen-containing aromatic compound. These organic substrates can have a substituent as long as they do not inhibit the nitration reaction of the present invention. Examples of such a substituent include an aromatic alkyl group, an aromatic alkylene group, a phenolic hydroxyl group, a halogen group, a carboxyl group, and an alkoxy group.

  However, the present invention is not limited to these compounds. In the present invention, any compound that is equivalent or similar to the above-described compound and that causes a nitration reaction using a nitrating agent is used in the same manner. be able to. As the nitrating agent, a nitrating agent used in a normal nitration reaction can be used. For example, nitric acid, ammonium nitrate, lithium nitrate, sodium nitrate, potassium nitrate, calcium nitrate and the like can also be used. . Nitric acid is preferably used.

  In the present invention, in order to synthesize a nitro compound, the concentration of the organic substrate and the concentration of the nitrating agent in the reactor can be arbitrarily adjusted according to the target compound. Since the nitrating agent in the reactor is diluted with a large amount of medium to a low concentration, it is easy to control the reaction temperature. In addition, the nitration reaction proceeds efficiently at a low concentration, so the use of an excessive amount of nitrating agent can be avoided, and the target compound can be easily separated from the reaction mixture. Generation of acid and treatment of waste liquid can be avoided.

  In the present invention, it is preferable to reach a predetermined set temperature within a time of at least 1 second or less using a high-temperature and high-pressure water supply device capable of supplying high-temperature and high-pressure water at 350 to 700 ° C. and 20 to 50 MPa, for example. Although a continuous high-temperature and high-pressure reactor having a mechanism capable of being used is used, a batch reactor can also be used. In this invention, the manufacturing method of the organic nitro compound of this invention and its manufacturing apparatus can be arbitrarily designed using the appropriate reaction apparatus containing these.

  In the present invention, suitable reaction conditions are a reaction temperature of 350 to 400 ° C., a reaction pressure of 20 to 50 MPa, a reaction time of 1 second or less (instantaneous), and an organic substrate, a nitrating agent, and It is preferable to introduce reaction media and allow them to reach a predetermined set reaction temperature in at least 0.02 to 0.05 seconds. Thereby, for example, the elapsed time to the set reaction temperature is extremely shortened as compared with a batch reactor (1 to 5 hours) and a conventional continuous reactor (10 to 120 seconds). By doing so, the reaction yield and the selectivity of the product can be increased.

  In the present invention, by adopting the above-described reaction mode, for example, an aromatic nitro compound is synthesized from an aromatic compound in a short time of a reaction time of 0.001 seconds to 60 seconds. When using a continuous reactor, the reaction time controls the reaction temperature, reaction pressure, high-temperature and high-pressure water flow rate, reaction substrate introduction flow rate, reactor shape, reactor inner diameter, reactor flow path length, etc. To control the reaction time. More preferably, the reaction time can be selected in the range of 0.001 seconds to 30 seconds, and most preferably in the range of 0.05 seconds to 10 seconds.

  However, the present invention is not limited to these values. As a result, a complex reaction is less likely to occur within the elapsed time up to the set reaction temperature, and a sharp reaction is possible. That is, when the elapsed time to the set temperature is long, a complicated reaction occurs, and it becomes difficult to synthesize the target compound with high selectivity. In the present invention, since the reaction time is short, it is possible to obtain a large amount of product in a short time with a small apparatus, and to construct a method for producing an organic nitro compound with high production efficiency and its apparatus. it can.

  In the case of the continuous method, for example, a method of adding aromatic compounds and nitric acid separately or mixed to supercritical water continuously supplied, and then adding them continuously, or a predetermined amount of nitric acid is added. Dissolved water is fed by a liquid feed pump, passed through a preheater and heated to the reaction temperature, and the aromatic compound as a raw material is fed by the liquid feed pump and passed through the preheater. The method of making it merge can be adopted. Thereby, in the present invention, an aromatic compound and nitric acid are passed at high speed through a reactor through which supercritical water at a predetermined temperature flows, and reacted at a predetermined time, set temperature, and pressure to obtain a target product. Can do.

  In both continuous and batch reaction systems, the reaction mixture after completion of the reaction contains impurities such as unreacted raw materials or by-products in addition to the target organic nitro compound. By separating and purifying them, a desired compound can be obtained. The separation / purification method is not particularly limited, and a separation method using distillation, extraction, silica gel, an ion exchange resin column or the like, which is usually used industrially, can be applied. In the case of the batch method, for example, an organic substrate and a nitrating agent as raw materials are placed in a pressure vessel (autoclave), and the temperature and pressure are controlled so that water becomes a supercritical state or a subcritical state. The method of making it react under predetermined time, predetermined preset temperature, and pressure is illustrated.

  The apparatus for producing an organic nitro compound of the present invention includes, for example, a constant temperature device for maintaining the reactor at a predetermined temperature, a nitration reactor, a high-temperature high-pressure water supply device, an organic substrate supply device, a nitrating agent supply device, and It has a reaction product take-out device, and the reactor and each supply device are connected by a high-temperature high-pressure channel. An example is shown in FIG. A high-temperature and high-pressure channel leading to a high-temperature and high-pressure water supply device, an organic substrate supply device and a nitrating agent supply device is connected to the upstream side of one end of the reactor, and a reaction product take-out device is connected to the downstream side of the other end A high-temperature and high-pressure channel leading to is connected.

  High-temperature and high-pressure water, an organic substrate, and a nitrating agent are supplied to the reactor from each supply device provided in connection with this flow path. By controlling the temperature, pressure, flow rate, flow rate, etc., the inside of the reactor is adjusted to predetermined reaction conditions, and the organic substrate and nitrating agent react under the predetermined temperature and pressure in the reactor. Converted to organic nitro compounds. The reaction mixture is recovered by being reduced in pressure and cooled by a reaction product take-out device. The nitro compound production apparatus of the present invention can be appropriately provided with incidental facilities such as an emergency cooling pump that can cool the apparatus in an emergency and a cleaning pump that cleans the inside of the apparatus.

  The organic nitro compound synthesized by the present invention is an important compound as a raw material or intermediate for the production of a wide range of organic industrial products. For example, as an example, the production of a synthetic raw material for diisocyanates used in the production of polyurethane. Useful for. Conventionally, organic synthesis methods such as acrylic acid, amines, and aromatic carboxylic acids have been known as a synthesis method using high-temperature and high-pressure water as a reaction medium. However, the present invention is intense in reaction and difficult to control. The present invention is to provide a new reaction system that overcomes the problems of the conventional organic nitro compound synthesis process that may be accompanied by a risk of product explosion. In addition, the present invention continuously improves the efficiency of organic nitro compounds with a simple production apparatus by a reaction system using high-temperature and high-pressure water (350 ° C., 20 MPa or more), for example, subcritical water or supercritical water as a reaction medium. It is possible to synthesize well, safely, synthesize organic nitro compounds in large quantities in a short time, and synthesize with high selectivity.

The present invention has the following effects.
(1) An organic nitro compound can be produced in a short time and in one step by press-fitting an organic substrate and a nitrating agent into a reaction field of high-temperature and high-pressure water at high speed.
(2) It is possible to provide a method for producing a nitro compound and an apparatus for producing the same, which do not cause problems in operational risk in the production process, acid resistance equipment, exothermic reaction control, and the like.
(3) Since reaction inclusions such as an organic solvent and a reaction catalyst are not necessary, there is little risk of impurities being mixed into the product.
(4) Since the reaction time is short, it is suitable for synthesizing a large amount of organic nitro compounds in a short time.
(5) The reaction is selective and the target compound can be obtained with high purity.
(6) Since the reaction medium is water, handling of the reaction product is easy, and the product can be easily separated from the reaction medium.
(7) Since water is used as the reaction medium and organic solvents, catalysts, etc. need not be used, waste such as waste acid and waste liquid are less discharged from the manufacturing process, and there is no need for such treatment. It is possible to provide a method for producing an organic nitro compound and a production apparatus therefor that can be well harmonized and can reduce production costs.
(8) According to the method for synthesizing an organic nitro compound of the present invention, a new production technique for a nitro compound that can be substituted for the conventional method can be provided.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention is not limited at all by the following Examples.

(1) Production of picric acid by continuous process In this example, picric acid was produced by these reactions using toluene as the organic substrate and nitric acid as the nitrating agent. The reaction formula is shown in Chemical Formula 1.

(2) Manufacturing apparatus The manufacturing apparatus of the continuous organic nitro compound shown by FIG. 1 was used as a manufacturing apparatus. The reaction conditions with high-temperature and high-pressure water were a supercritical state with a reaction temperature of 375 ° C. and a reaction pressure of 40 MPa. The reaction tube was constituted by a tube having a total volume of 0.105 cm ³ , an inner diameter of 0.5 mm, and a length of 50 cm. As the raw material toluene and nitric acid, commercially available special grade reagents were used, and deionized and deoxygenated pure water was used as the high-temperature and high-pressure water.

A tube made of Hastelloy C-276 was used for the high-temperature and high-pressure channel connecting the reactor and each supply device such as high-temperature and high-pressure water. The reactor was connected to the high-temperature and high-pressure water supply device, the toluene supply device, the nitric acid supply device, and the product take-out device through the flow path. Toluene and nitric acid were mixed with high-temperature and high-pressure water in the flow path before flowing into the reactor, and then each apparatus was arranged to be supplied to the reactor. The reactor consisted of a tube of Inconel 625 with an inner diameter of 0.5 mm, a length of 50 cm and a total volume of 0.105 cm ³ . In addition, thermocouples and pressure gauges were provided at necessary locations, temperature and pressure were monitored, and the apparatus was controlled so that the inside of the reactor was in a predetermined reaction condition.

(3) Experimental operation While supplying supercritical water at 5 ml / min with the high-pressure pump A, the pressure is a discharge valve and the temperature is the supercritical water supply device and the thermostat so that the target condition is 375 ° C./40 MPa. Controlled with. The high-pressure pump B supplied toluene as a substrate at 1 ml / min, and the dilute nitric acid (3N) was introduced from the high-pressure pump C at 2 ml / min. High-pressure pumps D and E were provided, and each was used as a cold water supply pump for cleaning and emergency cooling.

  Under these conditions, nitration reaction was performed by supplying toluene and nitric acid to the reactor using supercritical water as a reaction medium. The reaction time under these reaction conditions was 0.482 seconds. In this case, 3 to 6% of picric acid in which a nitro group was introduced into the aromatic ring of toluene was formed in the reaction completion liquid. Furthermore, the experiment was conducted by changing the reaction conditions to 370 ° C./40 MPa, 373 ° C./40 MPa, and 376 ° C./40 MPa. All of the recovered reaction solutions were yellow solutions, indicating the production of picric acid.

(4) Confirmation of reaction product The organic solvent part of the reaction eluate obtained in this example was analyzed by GC-MS to confirm the reaction product. As the analyzer, HP5973MS & 6890GC System was used. HP19091B-112 Ultra 25% Phenyl Methyl Siloxane 25m 320nm 0.52nm was used as a separation column, and analysis was performed under conditions of a flow rate of 0.8 ml / min and a temperature of 100 to 280 ° C (4 ° C / min). The chromatogram of the analysis result is shown in FIG. From this, it was found that a large amount of picric acid was produced as the main component, and a slight amount of dinitrophenol was produced.

  Further, FIG. 3 shows a mass spectrum obtained by analyzing a component having a retention time of 14.2 minutes with a mass spectrometer. Since the mass spectrum (FIG. 3) obtained by mass spectrometry of the compound synthesized in this example is consistent with the mass spectrum of picric acid, which is a known substance (standard substance) shown in FIG. It was confirmed that the acid was synthesized as the main component. Further, FIG. 5 shows an infrared absorption spectrum of the compound synthesized in this example, and FIG. 6 shows an infrared absorption spectrum of picric acid, which is a known substance (standard substance). By comparing both infrared absorption spectra, it was confirmed that the compound synthesized in this example was picric acid.

  In this example, toluene was tried to be nitrated using toluene as an organic substrate and nitric acid as a nitrating reagent (Chemical Formula 2). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Toluene nitration reagent: Nitric acid Reaction temperature: 376 ° C
Reaction pressure (density): 40 MPa (606.4 kg / m ³ )
Reaction time: 0.446 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 reaction tube having an outer diameter of 1/16 inch, an inner diameter of 0.5 mm, a length of 500 mm, and a volume of 0.098 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), toluene 1 ml / min.

  Product confirmation: GC-MS analysis conditions; HP5973MS & 6890GC System, Column: HP19091B-112 Ultra2 5% Phenyl Methyl Siloxane 25m * 320nm * 0.52nm Flow rate: 3.6 ml / min, 70 ml / min, 70 ml / min, 70 ml / min. (2min)-(25C / min) -130- (20C / min) -310C (5min).

(2) Synthesis result 1: A peak of nitrobenzene (1) was observed at a retention time of 2.46 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 7 shows standard substance data and data with a concordance rate of 97% by library search.

2: A peak of 2,4,6-trinitrophenol (13) was observed at a retention time of 7.27 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 8 shows standard substance data and data with a match rate of 93% by library search. Since (13) is also an explosive called picric acid, it was separated and compared with an infrared absorption spectrum to confirm that it coincided (FIG. 9).

3: A peak of 2,4,6-trinitrobenzene (5) was observed at a retention time of 6.3 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 10 shows standard substance data and data with a matching rate of 73% by library search. This low coincidence rate is due to the fact that the peak below m / z 167 of the mass fragment of # 98403: 1,3,5-trinitrobenzene of Data Base Wiley 275 integration is not taken in. Therefore, for reference, FIG. 11 shows a mass spectrum of 1,3,5-trinitrobenzene (5) in the spectrum database SDBS of organic compounds for reference. In this case, the coincidence rate is 98%.

  In this example, the nitration of toluene was attempted by changing the synthesis conditions (Chemical Formula 3). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Toluene nitration reagent: Nitric acid Reaction temperature: 300 ° C
Reaction pressure (density): 40 MPa (764.4 kg / m ³ )
Reaction time: 1.12 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube with an outer diameter of 1/16 inch and titanium-lined reaction tube, inner diameter 0.5 mm, length 1000 mm, and volume 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), toluene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Results of synthesis Nitrobenzene (1), ortho (o) -nitrotoluene (6), meta (m) -nitrotoluene (7), para (p) -nitrotoluene (8) were produced. The ratio of ortho: meta: para was about 3: 1: 5.

1: A peak of nitrobenzene (1) was observed at a retention time of 2.46 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data example 2).

2: A peak of ortho (o) -nitrotoluene (6) was observed at a retention time of 3.15 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 12 shows the standard substance data and 95% matching rate by library search.

3: A peak of meta (m) -nitrotoluene (7) was observed at a retention time of 3.45 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 13 shows the reference substance data and the matching rate of 95% by library search.

4: A peak of para (p) -nitrotoluene (8) was observed at a retention time of 3.58 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 14 shows the reference material data and the matching rate of 95% by library search.

  In this example, the nitration of toluene was attempted by changing the synthesis conditions (Chemical Formula 4). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Toluene nitration reagent: Nitric acid Reaction temperature: 350 ° C
Reaction pressure (density): 40 MPa (671.9 kg / m ³ )
Reaction time: 0.99 seconds (from calculation)
Flow-type high-temperature high-pressure water nitration reactor: Same as the apparatus used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), toluene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Results of synthesis Nitrobenzene (1), ortho (o) -nitrotoluene (6), meta (m) -nitrotoluene (7), para (p) -nitrotoluene (8) were produced. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data examples 2 and 3). The ratio of ortho: meta: para was about 2: 1: 6.

  In this example, the nitration of toluene was attempted by changing the synthesis conditions (Chemical Formula 5). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Toluene nitration reagent: Nitric acid Reaction temperature: 375 ° C
Reaction pressure (density): 40 MPa (609.3 kg / m ³ )
Reaction time: 0.90 seconds (from calculation)
Flow-type high-temperature high-pressure water nitration reactor: Same as the apparatus used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), toluene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Results of synthesis Nitrobenzene (1), ortho (o) -nitrotoluene (6), meta (m) -nitrotoluene (7), para (p) -nitrotoluene (8) were produced. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data examples 2 and 3). The ratio of ortho: meta: para was almost the same as at 350 ° C.

  In this example, nitration of benzene was attempted (Chemical Formula 6). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Benzene nitration reagent: Nitric acid Reaction temperature: 300 ° C
Reaction pressure (density): 40 MPa (764.4 kg / m ³ )
Reaction time: 1.12 seconds (from calculation)
Flow-type high-temperature high-pressure water nitration reactor: Same as the apparatus used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), benzene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: A peak of nitrobenzene (1) was observed at a retention time of 2.46 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data example 2).

2: A peak of p-dinitrobenzene (4) was observed at a retention time of 4.86 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 15 shows the data.

3: A peak of m-dinitrobenzene (3) was observed at a retention time of 5.0 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 16 shows the data.

4: A peak of o-dinitrobenzene (2) was observed at a retention time of 5.12 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 17 shows the data.

5: A peak of 1,3,5-trinitrobenzene (5) was observed at a retention time of 6.30 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data example 2).

6: A peak of 2,4,6-trinitrophenol (13) was observed at a retention time of 7.27 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data example 2). The matching rate by search was 90 or more.
7: About 1/2 of the produced nitro compound was nitrobenzene.

  In this example, nitration of benzene was attempted by changing the synthesis conditions (Chemical Formula 7). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Benzene nitration reagent: Nitric acid Reaction temperature: 350 ° C
Reaction pressure (density): 40 MPa (671.9 kg / m ³ )
Reaction time: 0.99 seconds (from calculation)
Flow-type high-temperature high-pressure water nitration reactor: Same as the apparatus used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), benzene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Results of synthesis Nitrobenzene (1), ortho (o) -dinitrobenzene (2), meta (m) -dinitrobenzene (3), and para (p) -dinitrobenzene (4) were produced. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data examples 2 and 6). The ratio of ortho: meta: para was almost the same as at 350 ° C. 1,3,5-trinitrobenzene (5) and 2,4,6-trinitrophenol (picric acid) (13) were produced in the same manner, but were analyzed more than Example 6. Under these conditions, the amount of nitro compound in the product was about 83%, and nitrobenzene reached about 70% of the product.

  In this example, nitration of benzene was attempted by changing the synthesis conditions (Chemical Formula 8). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Benzene nitration reagent: Nitric acid Reaction temperature: 375 ° C
Reaction pressure (density): 40 MPa (609.3 kg / m ³ )
Reaction time: 0.90 seconds (from calculation)
Flow-type high-temperature high-pressure water nitration reactor: Same as the apparatus used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), benzene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Results of synthesis Nitrobenzene (1), ortho (o) -dinitrobenzene (2), meta (m) -dinitrobenzene (3), and para (p) -dinitrobenzene (4) were produced. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. (See Spectral Data Examples 2 and 6). The ratio of ortho: meta: para was almost the same as at 350 ° C. 1,3,5-trinitrobenzene (5) and 2,4,6-trinitrophenol (picric acid) (13) were produced in the same manner, but were analyzed more than Example 7. Under these conditions, the amount of nitro compound in the product is about 91.4%, nitrobenzene is about 61%, but 2,4,6-trinitrophenol (picric acid) is increased to about 15.5%. did.

  In this example, pyridine was tried to be nitrated using pyridine as a substrate and nitric acid as a nitrating reagent (Chemical Formula 9). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Pyridine nitration reagent: Nitric acid Reaction temperature: 300 ° C
Reaction pressure (density): 40 MPa (764.4 kg / m ³ )
Reaction time: 1.12 seconds (from calculation)
Flow-type high-temperature high-pressure water nitration reactor: Same as the apparatus used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), pyridine 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: A peak of 3-nitropyridine (15) (CAS Registry No .: 002530-26-9) was observed at a retention time of 2.54 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (FIG. 18).

2: A peak of 2-nitropyridine (14) was observed at a retention time of 3.44 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances (FIG. 19).

3: The ratio of the nitro compound to the product under these conditions was about 48.5%, 2-nitropyridine (14) was about 22%, but 3-nitropyridine (15) was about 19%. It was.

  In this example, nitration of pyridine was attempted by changing the synthesis conditions (Chemical Formula 10). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Pyridine nitration reagent: Nitric acid Reaction temperature: 350 ° C
Reaction pressure (density): 40 MPa (671.9 kg / m ³ )
Reaction time: 0.99 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), pyridine 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Results of synthesis As main nitro compounds, 2-nitropyridine (14) and 3-nitropyridine (15) were similarly produced. Under these conditions, the amount of the nitro compound in the product was about 33.1%, 2-nitropyridine (14) was about 18.7%, and 3-nitropyridine (15) was about 11%. It was.

  In this example, nitration of pyridine was attempted by changing the synthesis conditions (Chemical Formula 11). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Pyridine nitration reagent: Nitric acid Reaction temperature: 375 ° C
Reaction pressure (density): 40 MPa (609.3 kg / m ³ )
Reaction time: 0.90 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), pyridine 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Results of synthesis The main nitro compounds were 2-nitropyridine (14) and 3-nitropyridine (15). Under these conditions, the amount of the nitro compound in the product is about 73.9%, 2-nitropyridine (14) is about 45.7%, but 3-nitropyridine (15) is about 26.4%. Met.

  In this example, n-hexane was nitrated using n-hexane as a substrate and nitric acid as a nitrating reagent (Chemical Formula 12). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: n-hexane nitrating reagent: nitric acid Reaction temperature: 300 ° C
Reaction pressure (density): 40 MPa (764.4 kg / m ³ )
Reaction time: 1.12 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), n-hexane 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: A peak of 1-nitrohexane (16) (CAS Registry No .: 646-14-0) was observed at a retention time of 2.11 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances (FIG. 20).

In this example, nitration of n-hexane was attempted by changing the synthesis conditions. The synthesis conditions and synthesis results are shown below.
(1) Synthesis conditions Substrate: n-hexane nitrating reagent: Nitric acid Reaction temperature: 350 ° C.
Reaction pressure (density): 40 MPa (671.9 kg / m ³ )
Reaction time: 0.99 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), n-hexane 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: Similarly, a peak of 1-nitrohexane (16) (CAS Registry No .: 646-14-0) was observed at a retention time of 2.11 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data example 12).

In this example, nitration of n-hexane was attempted by changing the synthesis conditions. The synthesis conditions and synthesis results are shown below.
(1) Synthesis conditions Substrate: n-hexane nitrating reagent: Nitric acid Reaction temperature: 375 ° C.
Reaction pressure (density): 40 MPa (609.3 kg / m ³ )
Reaction time: 0.90 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, nitric acid 2 ml / min (3N), n-hexane 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: Similarly, a peak of 1-nitrohexane (16) (CAS Registry No .: 646-14-0) was observed at a retention time of 2.11 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data example 12).

  In this example, nitration of benzene was attempted by changing the synthesis conditions (Chemical Formula 13). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Benzene nitration reagent: Ammonium nitrate Reaction temperature: 375 ° C
Reaction pressure (density): 40 MPa (609.3 kg / m ³ )
Reaction time: 0.90 seconds (from calculation)
Flow-type high-temperature high-pressure water nitration reactor: Same as the apparatus used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, ammonium nitrate 2 ml / min (20% by weight aqueous solution), benzene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: Similarly, a peak of nitrobenzene (1) was observed at a retention time of 2.46 minutes. The peak was identified from the library search of Data Base Wiley 275 and the analysis results of known substances (see spectral data example 2).

2: Similarly, o-nitrophenol (9) and p-nitrophenol (11) peaks were observed at retention times of 2.89 and 5.76 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. 21 and 22 show the data. The concordance rate was 96%.

3: Similarly, a peak of 2,4-dinitrophenol (12) was observed at a retention time of 5.41 minutes. The peak was identified from the library search of Data Base Wiley275 and the analysis results of known substances. FIG. 23 shows the data. The concordance rate was 97%.

(See Spectral Data Example 2).
3: Nitrate in the total product under these conditions is about 4%, indicating that it can be a nitrogen source.

  In this example, nitration of benzene was attempted using sodium nitrate as the nitration reagent (Chemical Formula 14). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Benzene nitration reagent: Sodium nitrate Reaction temperature: 375 ° C
Reaction pressure (density): 40 MPa (609.3 kg / m ³ )
Reaction time: 0.90 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, sodium nitrate 2 ml / min (20% by weight aqueous solution), benzene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: A peak of 2-nitrobiphenyl (17) was observed at a retention time of 6.59 minutes. The peak was identified by library search of Data Base Wiley275. FIG. 24 shows data with a concordance rate of 97%.

2: Similarly, a peak of 3-nitrobiphenyl (18) was observed at a retention time of 7.33 minutes. The peak was identified by library search of Data Base Wiley275. FIG. 25 shows data with a concordance rate of 97%.

3: Similarly, a peak of 4-nitrobiphenyl (19) was observed at a retention time of 7.45 minutes. The peak was identified by library search of Data Base Wiley275. FIG. 26 shows data with a concordance rate of 97%.

4: Nitrate in the total product under these conditions is about 2%, indicating that it can be a nitrogen source.

  In this example, nitration of benzene was attempted using sodium nitrite as a nitration reagent (Chemical Formula 15). The synthesis conditions and synthesis results are shown below.

(1) Synthesis conditions Substrate: Benzene nitration reagent: Sodium nitrite Reaction temperature: 375 ° C
Reaction pressure (density): 40 MPa (609.3 kg / m ³ )
Reaction time: 0.90 seconds (from calculation)
Flow-type high-temperature and high-pressure water nitration reactor: Same as that used in Example 1.
Reactor: Inconel 625 tube having an outer diameter of 1/16 inch and a titanium-lined reaction tube, an inner diameter of 0.5 mm, a length of 1000 mm, and a volume of 0.196 cm ³ .
Injection conditions: water 5 ml / min, sodium nitrite 2 ml / min (20% by weight aqueous solution), benzene 1 ml / min.
Product confirmation: GC-MS analysis conditions are the same as in Example 2.

(2) Synthesis result 1: of 2-nitrobiphenyl (17), 3-nitrobiphenyl (18), and 4-nitrobiphenyl (19) at retention times of 6.59, 7.33, and 7.45 minutes, respectively. A peak was observed. The peak was identified by library search of Data Base Wiley 275 (see spectral data example 16).

2: A peak of p-phenylazophenol (20) was observed at a retention time of 8.22 minutes. The peak was identified by library search of Data Base Wiley275. FIG. 27 shows data with a matching rate of 94%.

2: As for the nitro compound, biphenyl nitro compounds (17), (18) and (19) were also analyzed. Under these conditions, 4-phenylazophenol (20) was synthesized as a main product. This is a nitrogen source that enables azo compound synthesis.

  As described in detail above, the present invention provides an organic nitro compound characterized in that an organic nitro compound is synthesized by a reaction between an organic substrate and a nitrating agent using a reaction system using high-temperature and high-pressure water as a reaction medium. The present invention relates to a method and an apparatus for producing the same, and according to the present invention, an unavoidable problem in a method of nitration of an organic substrate using a large amount of nitric acid, which is conventionally carried out in the industrial production of nitro compounds. It is possible to provide a new method for producing a nitro compound and an apparatus for producing the same, which can reliably eliminate the problem.

  For example, aromatic nitro compounds are important compounds as starting materials or intermediates for a wide range of organic industrial products such as pharmaceuticals, agricultural chemicals, dyes, and plastics. Acids are required, and there are various technical problems such as operational danger, acid resistance equipment, control of exothermic reaction, waste acid, purification treatment of waste water, and the solution of these problems has been strongly demanded. The present invention synthesizes an organic nitro compound by reacting an organic substrate with a nitrating agent using high-temperature and high-pressure water as a reaction medium, so that it is safer and more efficient without using a large amount of a high-concentration nitrating agent. It is possible to synthesize organic nitro compounds, enable mass production with a simple apparatus, and achieve highly selective synthesis of nitro compounds. In addition, according to the present invention, it is possible to provide an environmentally friendly organic nitro compound production technique that hardly emits waste acid, waste liquid, and the like. Furthermore, the organic nitro compound produced by the present invention is important as a raw material for producing polyisocyanate, which is one of the main raw materials of polyurethane, for example, and the present invention is a new production technology for these chemical industrial products. It is useful as a thing to provide.

An example of the manufacturing apparatus of the organic nitro compound of this invention is shown. The chromatogram by GC of the reaction product obtained in Example 1 is shown. The mass spectrum of the main reaction product obtained by separation by GC in Example 1 is shown. The mass spectrum of picric acid which is a known substance (standard substance) is shown. The infrared absorption spectrum of the main reaction product obtained in Example 1 is shown. The infrared absorption spectrum of picric acid which is a known substance (standard substance) is shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. The comparison (KBr) of the infrared absorption spectrum of synthetic picric acid is shown. The mass spectrum library search result is shown. Reference data are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown. Reference data are shown. Reference material data and mass spectrum library search results are shown. Reference material data and mass spectrum library search results are shown.

Explanation of symbols

(Reference in FIG. 1)
1: High pressure pump 2: Back pressure valve 3: Balance 4: Supercritical water supply device 5: Constant temperature device 6: Thermocouple 7: Reaction tube 8: Pressure gauge and safety valve 9: Connection unit 10: Cooling device A: Critical water supply pump B: Toluene supply pump C: Nitric acid supply pump D: Cleaning water supply pump E: Cold water supply pump for emergency cooling

Claims (7)

The high-temperature high-pressure water using a reaction system as a reaction medium, a process for the preparation of organic nitro compounds you synthesize organic nitro compound by reaction of an organic substrate and a nitrating agent,
The reaction medium is high-temperature high-pressure water of 300 ° C. or higher and 20 MPa or higher, or subcritical water or supercritical water, and the organic substrate is an aliphatic hydrocarbon, aliphatic alcohol, aromatic hydrocarbon, polycyclic A method for producing an organic nitro compound, which is an aromatic compound or a nitrogen-containing aromatic.   The method for producing an organic nitro compound according to claim 1, wherein the organic nitro compound is synthesized from the organic substrate by a one-step reaction process.   The method for producing an organic nitro compound according to claim 1, wherein the organic nitro compound is synthesized from the organic substrate by a continuous process.   The method for producing an organic nitro compound according to claim 1, wherein the nitrating agent is nitric acid, ammonium nitrate, lithium nitrate, sodium nitrate, potassium nitrate, or calcium nitrate.   The method for producing an organic nitro compound according to claim 1, wherein the selectivity, conversion rate, and / or yield of the target compound is controlled by adjusting the composition, temperature, pressure, and / or time of the reaction system. An apparatus for synthesizing an organic nitro compound using a reaction system using high-temperature high-pressure water as a reaction medium, which is used in the method for producing an organic nitro compound according to claim 1 ,
Reactors (including piping) resistant to the high-temperature and high-pressure water and nitrating agent , high-temperature and high-pressure water supply means, organic substrate supply means, and nitrating agent supply means. A high-temperature high-pressure channel for supplying the substrate and the nitrating agent to the reactor, and the organic substrate and the nitrating agent are mixed with the high-temperature high-pressure water in the channel before flowing into the reactor. Then, each of the above means is arranged to be supplied to the reactor, and the reaction medium is high-temperature high-pressure water having a temperature of 300 ° C. or higher and a pressure of 20 MPa or higher, or subcritical water or supercritical water, In the reactor, an organic nitro compound is synthesized in a short reaction time of 0.001 seconds to 30 seconds using a reaction system in which high temperature and high pressure water is used as a reaction medium from an organic substrate and a nitrating agent. Organic nitro compounds Manufacturing equipment. The apparatus for producing an organic nitro compound according to claim 6 , which is a continuous production apparatus provided with a continuous operation means.