JP2011144068A - Non-clogging nozzle, and manufacturing method for solid production utilizing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a means to easily supply a raw material chemical agent to a raw material chemical liquid in a reaction system in which a solid reaction product is produced and clogs a supply nozzle as seen in manufacture of a metal amide or an imide compound by a reaction of a metal halide and liquid ammonia. <P>SOLUTION: The non-clogging nozzle for obtaining a solid reaction product by injecting a raw material chemical agent in a raw material chemical liquid by using the nozzle includes a hollow cylindrical unit inside which the raw material chemical agent flows, and a drive shaft installed in the hollow cylinder unit so as to share the center axis with the hollow cylinder unit. The hollow cylinder unit has a chemical agent supply port to introduce the raw material chemical agent in the hollow cylinder unit, and a chemical agent discharge port to discharge the raw material chemical agent to the raw material chemical liquid, wherein at least a part of the front part of the drive shaft in the chemical agent discharge port extends outside the surface or the vicinity thereof formed by the front end of the hollow cylinder unit with respect to the positional relationship in the longitudinal axis direction of the drive shaft. The method for manufacturing a solid reaction product by using the non-clogging nozzle is provided. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention is stable without obstructing the discharge port when carrying out a very fast reaction in which the product precipitates as a solid under conditions that require no leakage from the reaction device such as use of a high-pressure atmosphere or toxic substances. The present invention relates to a nozzle for supplying a raw material and a method for producing a solid product by using a non-blocking nozzle to react one raw chemical with a different raw chemical to obtain a solid product. Relates to a method for producing a metal amide or imide compound powder useful as a precursor for producing metal nitride powder.

  A method of synthesizing a metal amide or imide compound powder by a reaction between a metal halide and liquid ammonia and thermally decomposing the powder is known as a method for producing a high-purity metal nitride powder suitable for mass production.

  In Patent Document 1, a liquid halogen and an organic solvent having a specific gravity greater than that of liquid ammonia dissolved in liquid ammonia are separated into two layers due to a difference in specific gravity. By supplying a hydride, liquid ammonia and a metal halide are reacted to synthesize a precursor metal amide or imide compound powder, which is thermally decomposed in a nitrogen or ammonia atmosphere to produce a corresponding metal nitride powder. A method of manufacturing is disclosed.

  In the reaction between a metal halide and liquid ammonia, ammonium halide is by-produced in addition to the target metal amide or imide compound. Ammonium halide is easily dissolved in liquid ammonia, but is hardly soluble in a low-polar organic solvent that does not dissolve in liquid ammonia. Therefore, the filtrate obtained by filtering and separating the metal amide or imide compound from the reaction mixture according to the method described in Patent Document 1 is recovered as a mixture of liquid ammonia in which by-product ammonium halide is dissolved and an organic solvent. Reuse of liquid ammonia and organic solvent as a reaction raw material is indispensable in industrial implementation. However, in order to separate and purify liquid ammonia and organic solvent from the mixture as described above, it is complicated and multistage. There is a problem that this process is required and the equipment cost becomes expensive.

  For example, Patent Document 2 discloses a recovery technique when a halogenated silane is used as the metal halide. This is shown in the lower organic solvent layer of the reaction system in which liquid ammonia and an organic solvent having a specific gravity greater than that of liquid ammonia are separated into two layers due to the difference in specific gravity. When the nitrogen-containing silane compound is produced by reacting the halogenated silane with liquid ammonia by supplying a mixed solution of the halogenated silane and the organic solvent, the nitrogen-containing silane compound is separated from the reaction solution, A method of adding 2.3 to 20.0% by volume of water to a mixed solution in a step of supplying a mixed solution of a solvent, liquid ammonia and by-product ammonium halide to a thin film evaporator and separating and recovering each of them. It is. According to this method, ammonia is taken out from the top of the evaporator, and a mixture in which a small amount of ammonia is mixed into the organic solvent, ammonium halide and water can be recovered from the can. Next, it is necessary to separate the organic solvent from the mixture, which has been suggested to be possible by methods such as static separation. However, when the solvent is actually reused as a solvent to be mixed with the halogenated silane, a further purification process for removing moisture mixed in a trace amount is essential. As illustrated in this way, a complicated and multi-stage separation / purification process is required to recover and reuse ammonia and organic solvent from a mixed solution of organic solvent, liquid ammonia, and by-product ammonium halide, respectively. .

  In order to avoid the above problem, it is desired to directly react a metal halide and liquid ammonia without using an organic solvent. Also, reducing the amount of the organic solvent used per weight of the target metal amide or imide compound is beneficial in reducing the size of the organic solvent recovery and purification equipment.

  Patent Document 3 discloses a method for producing silicon diimide, which includes a reaction method in which silicon halide is dropped from a space in a reaction site with respect to liquid ammonia at a temperature of −69 to −33.3 ° C. This is certainly an example of a reaction method between a metal halide and liquid ammonia without using an organic solvent, but requires an extremely low temperature of -69 to -33.3 ° C, preferably -65 ° C. . For this reason, a cryogenic refrigerant facility is required, and it must be said that it is remarkably uneconomical as an industrial manufacturing method.

  On the other hand, the reaction between the metal halide and liquid ammonia near room temperature is a very intense exothermic reaction, as described in Patent Document 1, for example, and the by-product ammonium halide blocks the reaction apparatus. It is only pointed out that there is a cause of trouble, such as being possible, and a specific method of directly mixing and reacting a metal halide and liquid ammonia without using an organic solvent has been disclosed or suggested. There is no situation.

Actually, SiCl ₄ is used as a metal halide, a SUS pipe is installed in liquid ammonia as a supply nozzle, and SiCl ₄ is supplied without solvent, so that pressurization is performed at a corresponding ammonia vapor pressure at room temperature. Under the conditions, when SiCl ₄ is reacted with liquid ammonia, the reaction heat can be removed by refluxing the liquid ammonia. However, the reaction is very fast, and the nitrogen-containing silane compound mainly composed of silicon diimide is discharged from the supply nozzle. For reasons such as immediate precipitation in the vicinity, it has been found that unless a supply pump having a high discharge pressure is used, the supply nozzle is blocked and the reaction cannot be carried out.

Japanese Examined Patent Publication No. 56-44006 Japanese Patent Laid-Open No. 7-223811 JP 62-223008 A

  The present invention has been made in view of the above problems of the prior art. That is, when a metal amide or an imide compound is produced by supplying a metal halide in liquid ammonia as a solution of an inert organic solvent containing no metal halide or containing a high concentration in liquid ammonia and reacting the metal halide with liquid ammonia. In this way, in a reaction system in which a solid product is generated and the reactor is blocked, means for easily supplying one raw material drug to another raw material chemical solution, and one raw material drug and a different raw material using the means It is an object of the present invention to provide a method for producing a solid product obtained by reacting a chemical solution to obtain a solid product, particularly a method for producing a metal amide or imide compound from a metal halide and liquid ammonia.

  The present invention for solving the above problems relates to the following matters.

1. A non-blocking nozzle for injecting one raw chemical into a different raw chemical using a nozzle to obtain a solid reaction product,
A hollow cylindrical portion through which the raw material drug flows, and a drive shaft installed in the hollow cylindrical portion so as to rotate while sharing a central axis with the hollow cylindrical portion;
The hollow cylindrical portion has a drug supply port for introducing the raw material drug into the hollow cylindrical portion, and a drug discharge port for discharging the raw material drug into the raw drug solution,
At least a part of the tip of the drive shaft in the medicine discharge port extends to the surface formed by the tip of the hollow cylindrical portion or to the outside in the positional relationship in the major axis direction of the drive shaft. Non-blocking nozzle characterized by

  2. Item 2. The non-occluding nozzle according to item 1, wherein a gap between the hollow cylindrical portion and the drive shaft is 30 μm to 1 mm in the medicine discharge port.

  3. A motor for driving the drive shaft, and a flange with a medicine supply path is interposed between a portion of the drive shaft that receives the driving force from the motor and the hollow cylindrical portion; The apparatus has a supply path for supplying the raw material medicine from the outside into the hollow cylindrical part, and the drive shaft extends through the flange with the chemical supply path into the hollow cylindrical part. The non-blocking nozzle according to 1 or 2.

  4). Item 4. The non-blocking nozzle according to item 3, wherein one end of the hollow cylindrical portion forms a flange, and the flange is liquid-tightly coupled to the flange with the drug supply path.

  5. Item 4. The non-blocking nozzle according to item 3, wherein the flange with the drug supply path can be directly connected to the reactor.

  6). Item 4. The non-blocking nozzle according to item 3, wherein power transmission from the motor to the drive shaft is a magnetic induction type.

  7). Item 7. The item according to any one of Items 1 to 6, wherein a tip portion of the drive shaft is removably connected as a frame, and an annular gap is formed between the frame and the hollow cylindrical portion. Non-blocking nozzle.

  8). The hollow cylindrical portion has a widened tip, the tip of the drive shaft also has a widened shape, and the raw drug discharged from the gap between the two tips is contained in the raw drug solution. Item 8. The non-blocking nozzle according to any one of Items 1 to 7, wherein the nozzle is widely dispersed.

9. A method for producing a solid product, wherein the non-blocking nozzle according to any one of Items 1 to 8 is used to react one raw material drug with a different raw material chemical solution to obtain a solid product,
The raw material chemical is supplied into the raw chemical from an annular gap formed from the inner wall of the cylindrical portion and the outer peripheral surface of the drive shaft while the chemical discharge port is installed in the raw chemical and the drive shaft is rotated. A method for producing a solid product.

10. The raw chemical is a metal halide or a solution of an inert organic solvent having a metal halide concentration of 60 wt% or more, the raw chemical is liquid ammonia, and the solid product is a metal amide or imide compound. Item 10. The method for producing a solid product according to Item 9, wherein
11. Item 11. The method for producing a solid product according to Item 10, wherein the metal halide is a halogenated silane.

  When using the non-blocking nozzle of the present invention, under the conditions where no leakage from the reaction apparatus such as high-pressure atmosphere and use of toxic substances is required, the reaction is very fast and the product is precipitated as a solid. The raw material can be stably supplied without blocking the nozzle. Specifically, the product is very fast under conditions of high pressure and using toxic substances, such as the reaction of metal halide (first raw chemical) and liquid ammonia (second raw chemical) at room temperature. In carrying out the reaction that precipitates as a solid, the liquid is stable and easily liquid as an inert organic solvent solution containing no metal halide (first raw material drug) or containing it in a high concentration. It can supply in ammonia (2nd raw material chemical | medical solution). As a result, a supply pump having a high discharge pressure is not required, and the reaction between the metal halide and liquid ammonia can be carried out industrially stably, and the equipment cost and maintenance labor can be reduced. Also, unlike conventional methods, a large amount of inert organic solvent is not required, and metal amides or imide compounds can be produced using no solvent or a small amount of inert organic solvent, eliminating the need for organic solvent recovery equipment. Or it can be miniaturized.

It is a schematic diagram which shows an example of the non-blocking nozzle of this invention. 1A is a longitudinal sectional view, and FIG. 1B is an end view of the nozzle tip. It is a schematic diagram which shows one Embodiment of the reaction apparatus in the manufacturing method using the non-blocking nozzle of this invention. Using non-blocking nozzle of the present invention, it is a graph showing changes in the pressure of the SiCl ₄ supply pipe when supplying the SiCl ₄ without a solvent in liquid ammonia. Using a SUS pipe nozzle is a graph showing changes in the pressure of the SiCl ₄ supply pipe when supplying the SiCl ₄ without a solvent in liquid ammonia.

  Hereinafter, the present invention will be described in detail.

  FIG. 1 is an example of the non-blocking nozzle of the present invention.

  The non-blocking nozzle of the present invention is arranged by combining a cylinder and a columnar drive shaft having an outer diameter smaller than the inner diameter of the cylinder, and constantly rotating the drive shaft from the inner wall of the cylinder and the outer peripheral surface of the drive shaft. The chemical | medical agent used as the raw material of reaction is supplied by making the cyclic | annular clearance gap formed into a discharge outlet. In the present invention, the raw chemical (first raw chemical) supplied from the non-blocking nozzle into the raw chemical is mainly liquid, but can also be gas. In the following, for the sake of simplicity, it is described that the first raw material drug is a liquid (raw material chemical solution), but the present invention is not limited to the case where the first raw material drug is a liquid but a gas. The present invention can be applied in the same manner, and the same effects can be achieved.

  When a normal nozzle such as a SUS pipe is used in a reaction in which the product precipitates as a solid very quickly, the product is deposited across the discharge port while adhering to the nozzle wall surface. In this case, a product bridge is formed. As a result, the nozzle discharge port area is reduced, and the pump pressure required for supplying the raw chemical is increased. If the supply pump has a sufficient discharge pressure, it is not impossible to carry out the reaction while recovering the discharge port area by destroying the bridge of the product by discharging the raw chemical solution at a high pressure. However, the smaller the discharge port area, the higher the pump discharge pressure required for supply, while it becomes possible to cover the discharge port with a smaller amount of product bridge, so the discharge pressure of the supply pump is sufficient. If it is not too high, the supply nozzle will eventually be blocked and the reaction cannot be carried out.

  On the other hand, in the non-blocking nozzle of the present invention, the drive shaft that forms one wall surface of the annular gap that is the discharge port is always rotating, so that the product solid precipitates across the annular gap and forms a bridge. Can not do it. For this reason, since the discharge port area is maintained in a substantially constant state, the discharge pressure necessary for supply does not increase, and the raw material chemical solution can be supplied stably.

The non-blocking nozzle of the present invention can be manufactured using a commercially available magnetic induction stirrer manufactured by, for example, Nitto High Pressure Co., Ltd. or pressure-resistant glass industry. That is, the stirring shaft of the magnetic induction stirrer is used as the drive shaft in the non-blocking nozzle of the present invention, and the flange 4 provided with the supply path for the raw material chemical solution and the cylinder 7A as the other member constituting the discharge unit are provided. It can be configured by combining the flanges 7.
In the non-blocking nozzle of the present invention, the material of the hollow cylindrical part constituting the discharge part is sufficient if the raw material chemical solution is resistant to corrosion, but the material of the raw material chemical solution or product hardly adheres is preferable. Generally, it is a nickel alloy such as stainless steel or Hastelloy.
In the non-blocking nozzle of the present invention, means for rotating the drive shaft is not limited, but power transmission by magnetic force induction is simple.

  The outer magnet 1, the inner magnet storage inner cylinder 2, the inner magnet 3 and the drive shaft 11 shown in FIG. 1 are ordinary parts constituting a commercially available magnetic induction stirrer. The inner cylinder 2 for storing the inner magnet is connected by screwing it into the reactor flange with the sealing material 6 sandwiched between them in a normal stirrer application. The non-blocking nozzle of the present invention can be configured by connecting the inner magnet storage inner tube 2 and the chemical solution supply path-equipped flange 4 in the same manner. FIG. 1 schematically shows a configuration example of the non-blocking nozzle of the present invention using a commercially available magnetic induction stirrer, and details of each member such as a bearing seal portion in the internal magnet 3 are omitted. .

  The flange 4 with the chemical solution supply path to which the inner cylinder 2 for storing the internal magnet is connected is connected to the reaction tank side mounting flange 8 with the gasket 9 interposed between them and sandwiching the flange 7 with the nozzle cylindrical portion 7A. Fixed with bolts.

  A drive shaft tip piece 12 is connected to the tip of the nozzle drive shaft 11, and is formed between the outer periphery portion of the drive shaft tip piece 12 and the inner periphery portion of the nozzle cylinder portion 7A provided in the flange 7 with the nozzle cylinder portion. The annular gap 13 forms the chemical solution discharge port 13. FIG. 1B shows an end view of the nozzle tip, and a gap 13 having a circular cross section (doughnut shape) is formed between the nozzle cylindrical portion 7A and the drive shaft tip piece 12. This ring gap 13 Forms a chemical discharge port. Although it is possible to form the chemical solution discharge port 13 by extending the drive shaft 11 without using the drive shaft tip piece 12, the width of the annular gap can be easily changed. Installation is useful.

  The nozzle drive shaft 11, the drive shaft tip piece 12, and the nozzle cylindrical portion are installed in common with the structural central axis, and the central axis when the drive shaft rotates is the same as the structural central axis. In addition, there is always a certain gap between the outer wall surface of the nozzle drive shaft 11 and the drive shaft tip piece 12 and the inner wall surface of the nozzle cylindrical portion 7A, and the drive shaft portion and the nozzle cylindrical portion are not in the rotation. Kept in contact. The axial length of the drive shaft tip piece 12 is not limited, but is usually 10 mm to 300 mm.

  The outer magnet 1 is connected to the inner magnet storage inner cylinder. When the external magnet is rotated, the internal magnet 3, the moving shaft 11 and the drive shaft tip piece 12 that are guided by the magnetic force and connected thereto rotate. When the raw material chemical solution is fed into the chemical solution supply port 5 using a pump or the like while rotating the drive shaft in this manner, the chemical solution can be supplied from the discharge port 13 to the reaction tank without being blocked.

  The magnetic induction stirrer can be suitably used for the non-blocking nozzle of the present invention because it is used for leak-free stirring in pressurizing conditions and reactions using harmful substances. Note that the non-blocking nozzle of the present invention may be configured using a non-leakage stirrer other than the magnetic induction stirrer as long as it is possible to avoid the formation of a precipitate bridge due to the rotation of the top piece at the discharge port. Specific leak-free stirrers other than the magnetic induction type include mechanical seal type and gland packing type stirrers.

  There is no restriction | limiting in the material of the structural material and sealing material which comprise the non-blocking nozzle of this invention, According to the raw material chemical | medical solution to be used and the property of reaction, it can select and manufacture suitably. In the case of producing a metal amide or imide compound from a metal halide and liquid ammonia, although not limited, as a structural material, for example, stainless steel such as SUS304 or 316, and as a sealing material, for example, Teflon (registered trademark), carbon Teflon (registered trademark), and the like are preferably used.

  In the positional relationship between the nozzle cylindrical portion 7A provided on the flange 7 with the nozzle cylindrical portion and the drive shaft front end piece 12 in the vicinity of the discharge port 13 of the non-blocking nozzle of the present invention, as viewed in the nozzle long axis direction, It is preferable to dispose the tip of the outer peripheral portion so that it is always located outside the surface formed by the tip of the nozzle cylindrical portion or the cylindrical portion. Accordingly, it is possible to reliably prevent the precipitate bridge from being formed at the nozzle tip by the rotation of the drive shaft tip piece 12. However, in the positional relationship described above, the tip of the outer peripheral portion of the drive shaft tip piece 12 slightly enters the inside of the nozzle cylindrical portion even if it is not on or outside the surface formed by the tip of the nozzle cylindrical portion. Since the function of the non-blocking nozzle is not lost as long as it is approximately, such a configuration can also be adopted in the present invention. However, when the tip of the outer peripheral portion of the drive shaft tip piece 12 is positioned more inside than the tip of the nozzle cylindrical portion, it is impossible to avoid the precipitation bridge due to the rotation of the drive shaft tip piece 12. The degree to which the tip of the outer peripheral portion of the drive shaft tip piece 12 may enter the inside of the nozzle cylindrical portion depends on the reaction speed, the diameter of the nozzle and the piece (gap), the flow rate of the raw material chemical solution, etc. Furthermore, 5 mm or less is good.

  The tip of the nozzle cylindrical portion 7A attached to the flange 7 with the nozzle cylindrical portion in the non-blocking nozzle of the present invention does not need to have a shape cut by a plane perpendicular to the major axis direction of the nozzle. As long as the positional relationship in the nozzle major axis direction with the tip of the outer peripheral portion of the nozzle is satisfied, it may be processed into an arbitrary shape. For example, the drive shaft tip piece may have a conical shape whose radius is gradually reduced or enlarged outside the tip of the nozzle cylindrical portion. If the conical shape has an increased radius, there is an effect that the first raw material chemical liquid discharged from the nozzle is widely dispersed in the second raw material chemical liquid.

  In the vicinity of the discharge port 13 of the non-blocking nozzle of the present invention, the width of the annular gap obtained from the difference between the inner diameter of the nozzle cylindrical portion and the outer diameter (both radii) of the drive shaft tip piece 12 is the type of reaction, the flow rate of the raw chemical solution Depending on the above, when producing a metal amide or imide compound by reaction of a metal halide with liquid ammonia, it is usually 30 μm to 1 mm, preferably 30 μm to 500 μm.

  The drive shaft tip piece 12 in the non-blocking nozzle of the present invention does not need to have a columnar shape, and satisfies the positional relationship in the nozzle major axis direction with respect to the nozzle cylindrical portion tip and the width of the annular gap near the discharge port 13. If so, it may be processed into an arbitrary shape.

  Ideally, the top end of the drive shaft in the non-blocking nozzle of the present invention rotates while maintaining a non-contact state with the nozzle cylindrical portion. May come into contact with the nozzle cylinder and cause troubles such as poor rotation. For this reason, it is preferable to manufacture the top end piece of the drive shaft from a material different from that of the inner cylinder portion of the nozzle, or to coat the outer peripheral portion thereof with a high hardness alloy such as stellite, ceramics such as alumina or chromium oxide.

  The rotational speed of the drive shaft when using the non-blocking nozzle of the present invention depends on the type of reaction, the flow rate of the raw material chemical solution, etc., but basically, if the formation of a precipitate bridge at the discharge port can be avoided by the rotation. good. The rotation speed is usually 0.02 m / sec or more, preferably 0.2 m / sec or more, as the peripheral speed of the outer peripheral surface of the drive shaft tip piece 12 near the discharge port.

  The rotational torque of the drive shaft when using the non-blocking nozzle of the present invention is usually 0.5 N · m or more, preferably 1.0 N · m or more. If the torque is large, even if a precipitate bridge is formed across the discharge port by a very high-speed reaction, it can be peeled off or broken.

  The non-blocking nozzle of the present invention is capable of performing a very fast reaction in which the product precipitates as a solid under high pressure atmosphere or use of toxic substances, such as the use of toxic substances, a large amount of organic solvent or high discharge pressure. This is useful because it can be carried out without using a feed pump having Specifically, in the production of metal amide or imide compound powder, which is useful as a precursor for the production of metal nitride powder, the metal halide is preferably used in a process of supplying and reacting with liquid ammonia. it can.

  The synthesis of metal amide or imide compound powder using the non-blocking nozzle of the present invention will be described in detail below.

  This embodiment of the present invention uses a non-blocking nozzle in reacting a metal halide with liquid ammonia as a solution of an inert organic solvent having a metal halide concentration of 60 wt% or more. In addition, the present invention relates to the production of a metal amide or imide compound, which is supplied into liquid ammonia.

  Examples of the method for producing a metal amide or imide compound in the case of using a halogenated silane as the metal halide include the methods described in Japanese Patent Application Nos. 2009-082730 and 2009-082747. These are methods capable of producing a nitrogen-containing silane compound powder more efficiently than before, but can be more suitably carried out industrially by applying the non-blocking nozzle of the present invention.

Metal halides used in this embodiment of the invention include SiCl ₄ , BCl ₃ , TiCl ₄ , VCl ₄ , SiBr ₄ , TiBr ₄ , GeCl ₄ , HSiCl _3, etc. III, IV, Group V metal halides Can be mentioned. The reaction between these compounds and liquid ammonia proceeds very rapidly with a large exotherm, and the product metal amide or imide compound is precipitated.

  In the practice of this embodiment of the reaction, the metal halide is supplied as a solution without solvent or diluted with a small amount of organic solvent. When the metal halide is supplied without a solvent, the filtrate obtained by filtering the produced metal amide or imide compound from the reaction slurry is composed of only two components of liquid ammonia and ammonium halide dissolved therein. . For this reason, compared with the case where it supplies by diluting with an organic solvent, the advantage that collection | recovery / reuse of liquid ammonia can be implemented by a simpler process is added.

The organic solvent used for diluting the metal halide can be appropriately selected from those which dissolve the metal halide and do not react with the metal halide or liquid ammonia. For example, C5-C12 chain aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, cyclic aliphatic hydrocarbons such as cyclohexane and cyclooctane, toluene And aromatic hydrocarbons such as xylene.
A preferable metal halide concentration in the mixed solution of the organic solvent and the metal halide is usually 60 wt% or more, more preferably 70 wt% or more.

  In the practice of this embodiment of the present invention, the outlet for supplying the metal halide as a solution without solvent or diluted with a small amount of organic solvent is installed in liquid ammonia in the reactor.

  In the practice of this embodiment of the invention, the mixing ratio of metal halide and liquid ammonia in the reactor is metal halide weight / liquid ammonia weight = 0.02 to 0.25. There is no restriction | limiting in particular in the format which implements reaction, A batch type or a continuous type may be sufficient. The above mixing ratio refers to the ratio of the total amount of metal halide and liquid ammonia supplied to the reactor per batch when the reaction is carried out in batch mode, and in the case of continuous mode, it is in steady operation state. The ratio of the weight flow rate of metal halide and liquid ammonia in When the mixing ratio is greater than 0.25, the viscosity of the reaction slurry becomes too high, and stirring and mixing in the reactor becomes difficult. When the mixing ratio is too small, productivity per reactor is lowered, which is not preferable.

  In the implementation of this embodiment of the present invention, the reaction temperature is not particularly limited, and can be selected in the range from low temperature to room temperature according to the equipment specifications. However, when the reaction temperature is increased, the vapor pressure of liquid ammonia increases. It may be necessary to increase the pressure specification of the vessel. On the other hand, if the reaction temperature is too low, an excessive load may be applied to the cooling facility. A suitable reaction temperature range is from about 10 ° C to about 40 ° C, more preferably from about 0 ° C to about 30 ° C.

  The pressure in carrying out this embodiment of the invention may be defined according to the vapor pressure of liquid ammonia occupying the majority of the reaction slurry, or by introducing an inert gas into the reactor as necessary. Alternatively, it may be kept higher than the vapor pressure of liquid ammonia in the reactor. The introduction of the inert gas may show an effect of reducing halogen impurities remaining in the product metal amide or imide compound. The vapor pressure of liquid ammonia in the reaction slurry depends on the reaction temperature, and is usually about 0.3 to 1.6 MPa, preferably about 0.4 to 1.6 MPa (absolute pressure). When introducing an inert gas, assuming that the pressure applied to the reactor by the introduction is ΔP, the normal range of ΔP is about 0.5 MPa or more, preferably about 0.7 MPa or more.

  The carbon content of the metal amide or imide compound produced in this embodiment of the invention is about 0.03 wt% or less. In the reaction with liquid ammonia, the metal halide is supplied as a solution without a solvent or diluted with a small amount of an organic solvent, but when supplied without a solvent, the product is substantially free of carbon. In addition, even when diluted with an organic solvent and supplied, the amount of carbon used in the product can be extremely reduced because the amount used is small. For this reason, the carbon content of the produced metal amide or imide compound is about 0.03 wt% or less.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.

  FIG. 2 is a schematic view showing one embodiment of the reaction apparatus in the production method using the non-blocking nozzle of the present invention. In FIG. 2, reference numeral 20 is a reactor, 21 is a conduit for supplying a metal halide or a mixed solution of a metal halide and an organic solvent, 22 is an adapter for connecting a non-blocking nozzle, 23 is a nozzle cylindrical portion, and 24 is a supply of liquid ammonia. 25, a nitrogen gas supply conduit, 26 a stirrer, 27 a thermometer sheath tube, 28 a cooling tube, 29 a back pressure valve, 30 a reaction mixture extraction conduit, 31 a jacket refrigerant supply conduit, 32 is a jacket refrigerant discharge conduit, and 40 is a non-blocking nozzle.

<Example 1>
For the reaction, as shown in FIG. 2, a jacketed SUS pressure-resistant reactor 20 having an internal volume of about 2 L equipped with a stirrer 26 and a condenser was used, and a cylindrical part having an inner diameter of 8 mm as shown in FIG. And a non-blocking nozzle 40 in which a front shaft top piece having an outer diameter of 7.9 mm is combined. Accordingly, the width of the annular gap obtained from the difference between the two is 50 μm. The material of the cylindrical part was SUS304, and the top end piece of the drive shaft was manufactured with stellite on the outer peripheral surface. The length of the drive shaft tip piece in the major axis direction is 40 mm and is projected from the cylindrical portion, and the tip position is 10 mm outside the tip of the cylindrical portion. After the inside of the reactor 20 was replaced with nitrogen gas, 1 L of liquid ammonia was charged, and then 50 mL of SiCl ₄ was supplied without dilution with an organic solvent while rotating the stirring blade of the reactor at 400 rpm. The reaction was performed. The SiCl ₄ is sent to the metal halide supply conduit 21 of the non-blocking nozzle by a plunger pump, and is supplied from the discharge port of the non-blocking nozzle 40 installed in the liquid ammonia. In supplying SiCl ₄ , the drive shaft of the non-blocking nozzle 40 was always rotated at 400 rpm, and 50 mL of the total amount of SiCl ₄ was supplied at a flow rate of 2.5 mL / min. The temperature of the reaction mixture during the supply of SiCl ₄ was 18 to 20 ° C., and the pressure in the reactor 20 was 0.7 to 0.8 MPa (gauge pressure). At this time, the pressure of the supply piping during supply of SiCl ₄ was very stable, and the maximum value was about 1.0 MPa (gauge pressure). The pressure in the reactor 20 was almost the same.

  After completion of the reaction, the produced slurry was transferred to a SUS pressure-resistant vessel (Nutsche type) with a jacket having an internal volume of about 2 L equipped with a stirrer and a sintered metal filter, and filtered. The resulting wet cake was further batch washed with about 1 L of liquid ammonia and then filtered. This washing / filtration operation was repeated a total of 7 times.

  The wet cake thus obtained was dried to obtain a nitrogen-containing silane compound powder mainly composed of silicon diimide. In the drying operation, hot water of 90 ° C. is circulated through the jacket of the filtration tank and heated, the pressure in the tank is kept at 0.6 MPa (gauge pressure) while appropriately releasing the internal pressure, and the temperature in the tank is 60 ° C. The end point was reached.

  Next, the filtration tank was carried into a large glove box, and nitrogen gas was circulated overnight to sufficiently expel the internal oxygen and moisture. Thereafter, the filtration tank was opened in the glove box, and the produced nitrogen-containing silane compound powder was taken out. The reaction proceeded quantitatively, and the amount obtained was 25.6 g.

<Example 2>
Using the same reactor as in Example 1, after charging liquid ammonia into the reactor, nitrogen gas was introduced so that the nitrogen partial pressure in the reactor was 1.2 MPa, and the flow rate of the SiCl ₄ supply was The reaction, filtration, washing, and drying operations were performed in the same manner as in Example 1 except that the flow rate was 5 mL / min. The temperature of the reaction mixture during supply of SiCl 4 is 17 to 21 ° C., the pressure in the reactor is 2.0 to 2.1 MPa (gauge pressure), the pressure of the supply pipe is very stable, and the maximum value is It was about 2.2 MPa (gauge pressure). The obtained amount of the nitrogen-containing silane compound powder mainly composed of silicon diimide was 27.1 g.

<Comparative Example 1>
In the supply of SiCl _4, the reaction, filtration, washing and drying operations were performed in the same manner as in Example 1 except that a SUS nozzle having an inner diameter of 0.8 mm installed in liquid ammonia was used instead of the non-blocking nozzle 40. Went. The temperature of the reaction mixture during the supply of SiCl ₄ was 18 to 21 ° C., and the pressure in the reactor 20 was 0.7 to 0.8 MPa (gauge pressure). On the other hand, the pressure in the supply pipe 21 during the supply of SiCl ₄ was unstable and changed while moving up and down violently, and the maximum value reached 5.3 MPa (gauge pressure). The weight of the obtained nitrogen-containing silane compound powder mainly composed of silicon diimide was 25.2 g.

FIGS. 3 and 4 show charts showing changes in pressure of the SiCl ₄ supply pipe 21 during the reactions of Example 1 and Comparative Example 1, respectively. Table 1 summarizes the reaction conditions and the analysis results of the obtained nitrogen-containing silane compound. The differential pressure in the term of SiCl ₄ supply pressure in Table 1 is calculated according to the following formula 1, and is a guideline for the discharge pressure to be secured in the pump used for supplying SiCl ₄ when implementing the present invention. It will be.
Differential pressure (Pa) = SiCl ₄ Maximum supply pressure (gauge pressure) −Minimum reactor pressure (gauge pressure) (Equation 1)

  The analysis results shown in Table 1 were measured as follows. The apparent density was measured according to JIS K5101. The specific surface area was determined by the BET single point method using Shimadzu Flowsorb II type 2300. The Cl content was obtained by hydrolyzing the product powder and eluting the Cl component into the liquid phase, followed by quantitative analysis by ion chromatography. The carbon content was measured by a combustion-thermal conductivity method using a WR-12 type carbon analyzer manufactured by LECO.

Figure 3 is a graph using a non-blocking nozzle 40, the SiCl ₄ when supplying the SiCl ₄ without a solvent in liquid ammonia shows the change of pressure in the supply pipe 21 of the present invention.

FIG. 4 is a graph showing the transition of the pressure of the supply pipe of SiCl ₄ when supplying SiCl _{4 in} liquid ammonia without solvent using a SUS pipe nozzle.

<Example 3>
With TiCl ₄ in 25mL instead of 50 mL SiCl ₄ of, except that the supply flow rate of TiCl ₄ was 10 mL / min, reaction and filtration in the same manner as in Example 1, washed, the operation of drying. The temperature of the reaction mixture during the supply of TiCl ₄ is 16 to 21 ° C., the pressure in the reactor is 0.7 to 0.8 MPa (gauge pressure), and the pressure of the supply pipe is very stable, its maximum value. Was about 0.9 MPa (gauge pressure). Moreover, the weight of the obtained tan solid was 34.8g.

  This product powder was filled in a siliconite atmosphere furnace (maximum use temperature 1600 ° C., furnace core tube: high alumina, heating element: SiC) and fired at 1500 ° C. for 1 hour while flowing nitrogen gas at 500 mL / min ( (Raising time 6 hours).

  During firing, the generation of decomposition gas was remarkable, and after firing, golden powder adhered to the core tube, but the solid in the crucible was black-brown powder. When this powder was pulverized in a mortar and subjected to X-ray diffraction analysis, the formation of TiN was confirmed.

<Example 4>
The reaction, filtration, washing, and drying operations were performed in the same manner as in Example 1 except that 50 mL of VCl ₄ was used instead of 50 mL of SiCl ₄ and the supply flow rate of VCl ₄ was 15 mL / min. The temperature of the reaction mixture during the supply of VCl ₄ is 18 to 20 ° C., the pressure in the reactor is 0.7 to 0.8 MPa (gauge pressure), and the pressure of the supply pipe is very stable, its maximum value. Was about 1.0 MPa (gauge pressure). Moreover, the obtained amount of the black solid was 78.9 g.

  When this product powder was baked in the same apparatus and conditions as in Example 3, a blackish brown powder was obtained. When this was ground in a mortar and subjected to X-ray diffraction analysis, VN was confirmed as the main product.

  As can be seen from FIGS. 3 and 4, when the non-blocking nozzle of the present invention is used, the product precipitates as a solid very quickly under conditions requiring no leakage from the reaction apparatus such as a high-pressure atmosphere or use of toxic substances. When carrying out the reaction, the raw material can be stably supplied without blocking the discharge port. Specifically, in carrying out a reaction such as a reaction between a metal halide and liquid ammonia at room temperature, the metal halide can be used as a solvent-free or inert organic solvent solution containing the metal halide in a high concentration. And it can supply to liquid ammonia easily. As a result, the production of metal amide or imide compound, which is a precursor of industrially useful high-purity metal nitride powder, does not require a supply pump having a high discharge pressure, and can stably produce metal halide and liquid ammonia. The equipment cost and maintenance labor can be reduced. In addition, since a metal amide or imide compound can be produced without using a large amount of an inert organic solvent and using no solvent or a small amount of an inert organic solvent, an organic solvent recovery facility becomes unnecessary or It can be downsized.

DESCRIPTION OF SYMBOLS 1 External magnet 2 Inner cylinder for storing internal magnet 3 Internal magnet 4 Flange 6 Sealing material 7, 8 Flange 9 Gasket 11 Drive shaft 12 Top 13 Chemical solution discharge port 20 Reactor 21 Metal halide conduit 22 Adapter 23 Nozzle cylindrical portion 24 Liquid ammonia Supply conduit 25 Nitrogen gas supply conduit 26 Stirrer 27 Thermometer sheath tube 30 Reaction mixture extraction conduit 40 Non-blocking nozzle

Claims (11)

An unoccluded nozzle for injecting one raw chemical into a different raw chemical using a nozzle to obtain a solid reaction product,
A hollow cylindrical portion through which the raw material drug flows, and a drive shaft installed in the hollow cylindrical portion so as to rotate while sharing a central axis with the hollow cylindrical portion;
The hollow cylindrical portion has a drug supply port for introducing the raw material drug into the hollow cylindrical portion, and a drug discharge port for discharging the raw material drug into the raw drug solution,
At least a part of the tip of the drive shaft in the medicine discharge port extends from the vicinity of the surface formed by the tip of the hollow cylindrical portion to the outside in the positional relationship in the longitudinal direction of the drive shaft. A non-blocking nozzle characterized by   2. The non-occluding nozzle according to claim 1, wherein a gap between the hollow cylindrical portion and the drive shaft is 30 μm to 1 mm in the medicine discharge port.   A motor for driving the drive shaft, and a flange with a medicine supply path is interposed between a portion of the drive shaft that receives the driving force from the motor and the hollow cylindrical portion; It has a supply path which supplies the raw material medicine from the outside into the hollow cylindrical part, and the drive shaft extends into the hollow cylindrical part through the flange with the chemical supply path. Item 3. The non-blocking nozzle according to item 1 or 2.   The non-blocking nozzle according to claim 3, wherein one end portion of the hollow cylindrical portion forms a flange, and the flange is liquid-tightly coupled to the flange with the medicine supply path.   The non-blocking nozzle according to claim 3, wherein the flange with the drug supply path can be directly connected to the reactor.   The non-blocking nozzle according to claim 3, wherein power transmission from the motor to the drive shaft is a magnetic induction type.   The tip end portion of the drive shaft is removably connected as a top, and an annular gap is formed between the top and the hollow cylindrical portion. Non-blocking nozzle as described.   The hollow cylindrical portion has a widened tip, the tip of the drive shaft also has a widened shape, and the raw drug discharged from the gap between the two tips is contained in the raw drug solution. The non-blocking nozzle according to any one of claims 1 to 7, wherein the non-blocking nozzle has a structure that is widely dispersed. A method for producing a solid product using the non-blocking nozzle according to any one of claims 1 to 8, wherein the raw material drug and the raw material chemical solution are reacted to obtain a solid product,
The raw material chemical is supplied into the raw chemical from an annular gap formed by the inner wall of the cylindrical portion and the outer peripheral surface of the drive shaft while the chemical discharge port is installed in the raw chemical and the drive shaft is rotated. A process for producing a solid product, characterized in that   The raw chemical is a metal halide or a solution of an inert organic solvent having a metal halide concentration of 60 wt% or more, the raw chemical is liquid ammonia, and the solid product is a metal amide or imide compound. 10. The method for producing a solid product according to claim 9, wherein   11. The method for producing a solid product according to claim 10, wherein the metal halide is a halogenated silane.