CN113024263B - Silicon nitride composite formula powder, preparation method and preparation device thereof - Google Patents
Silicon nitride composite formula powder, preparation method and preparation device thereof Download PDFInfo
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Abstract
The invention provides a preparation method of silicon nitride composite formula powder, the silicon nitride composite formula powder prepared by the preparation method and a preparation device thereof. The preparation method comprises the following steps: step 1, adding silicon tetrachloride, a diluent and a sintering aid into a reaction kettle, and mixing to form uniform mixed slurry; step 2, slowly introducing ammonia gas into the reaction kettle for reaction until the concentration of the solid phase in the slurry reaches a first concentration; step 3, conveying the slurry obtained by the reaction to a solid-liquid separation device for solid-liquid separation; and step 4, transferring the separated solid phase into a sintering furnace for decomposition and calcination to obtain the silicon nitride composite formula powder. The preparation method of the invention does not need thinning and grinding, and reduces the introduction of impurities.
Description
Technical Field
The invention relates to silicon nitride composite formula powder, a preparation method and a preparation device thereof.
Background
Silicon nitride is widely applied to the industrial fields of photovoltaics, machinery, chemical engineering, semiconductors, ceramics and the like because of good mechanical strength, chemical properties, thermal shock resistance, electrical insulation and the like. In the known silicon nitride production technology, the direct nitridation method has long nitridation time and high power consumption, and the production of high-quality products requires not only fine control of the process but also strict requirements on equipment. In addition, the production efficiency of the direct nitriding method is low, and the produced silicon nitride powder is low-quality silicon nitride ceramic powder with high content of conventional metal impurities. Meanwhile, the silicon nitride powder produced by the direct nitriding method needs to be controlled in particle size by combining air flow grinding with wet sanding. The production process of the silicon nitride ceramic product comprises the following steps: jet milling of silicon nitride → batching of auxiliary agent → wet grinding → spray granulation → press molding → processing and sintering. In the process, on one hand, more impurities are introduced by physical grinding, and on the other hand, the grinding process consumes power and time, and the production cost is obviously increased.
In order to solve the problems in the above processes, the conventional method is to add wear-resistant polyurethane material or silicon nitride liner plate into the grinding cylinder or the crushing equipment, for example, patent CN207138031U discloses that a polyurethane liner is arranged in the grinding cavity, so that although the wear-resistant liner material is added, the problem of impurity contamination caused by grinding still exists in the process.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of silicon nitride composite formula powder for reducing impurity introduction, the silicon nitride composite formula powder prepared by the preparation method and a preparation device thereof.
The technical scheme of the invention is as follows:
a preparation method of silicon nitride composite formula powder comprises the following steps:
and 4, transferring the separated solid phase into a sintering furnace for decomposition and calcination to obtain the silicon nitride composite formula powder.
Preferably, in step 1, the diluent is at least one of cyclohexane, toluene, dichloromethane and cyclopentane, the sintering aid is at least one of alumina and yttria, the particle size of the sintering aid is in the range of 0.5 μm to 1 μm, and the content of silicon tetrachloride is in the range of 2wt% to 50wt%, the content of diluent is in the range of 49.8wt% to 97.9wt%, and the content of sintering aid is in the range of 0.1wt% to 2wt%, based on the total weight of silicon tetrachloride, diluent and sintering aid.
Preferably, in the step 2, the flow rate of the ammonia gas is 1m/s-50m/s, and the silicon imine solid material generated by the ammonia gas slowly introduced into the reaction kettle for reaction is dispersed on the surface of the sintering aid in the mixed slurry; the first concentration is 10wt% to 15wt% based on the total weight of the slurry.
Preferably, in step 1 and step 2, the method further comprises self-circulating the slurry in the reaction kettle so that solid-phase particles in the reaction slurry are uniformly suspended in the liquid-phase system.
Preferably, in step 4, the separated solid phase is a solid phase in which a silicon imide having a particle size in the range of 10 to 100nm is uniformly dispersed on the surface of the sintering aid.
Preferably, in step 4, the decomposition calcination is performed in a nitrogen or inert gas atmosphere, and the decomposition calcination temperature is in the range of 1200 ℃ to 1600 ℃.
The preparation method of the silicon nitride composite formula powder has the following beneficial effects:
the sintering aid is added into a reaction liquid phase system in advance, the sintering aid is uniformly dispersed in a silicon tetrachloride liquid phase system under the stirring action, and the silicon imine generated by ammonolysis reaction after the ammonia gas is introduced is completely dispersed on the surface of the sintering aid, so that in the decomposition and calcination process, the silicon imine combined with the sintering aid is beneficial to crystallization and molding of silicon nitride to obtain superfine silicon nitride composite formula powder, further refining and grinding are not needed, the introduction of external impurities is greatly reduced or avoided, and the production efficiency is improved.
The invention also provides silicon nitride composite formula powder which is prepared by the method and comprises silicon nitride and a sintering aid.
The invention also provides a preparation device of the silicon nitride composite formula powder, which comprises the following components:
the reaction kettle is used for uniformly mixing the silicon tetrachloride, the diluent and the sintering aid and reacting the mixed slurry with ammonia gas;
a solid-liquid separation device for solid-liquid separation of the slurry obtained by the reaction; and
and the sintering furnace is used for decomposing the solid phase separated by calcination.
Preferably, the reaction kettle is a helical ribbon type slurry stirring tank type reaction kettle,
the solid-liquid separation device is a rake-blade dryer, a horizontal screw centrifuge or a high-efficiency precision filter,
the sintering furnace is a closed push plate type resistance furnace.
Preferably, the preparation device further comprises a slurry circulating pump, the slurry circulating pump is used for self-circulating the reaction slurry in the reaction kettle, an inlet pipe of the slurry circulating pump is connected with a discharge hole of the reaction kettle, and the discharge hole of the slurry circulating pump is connected with a feed inlet of the reaction kettle.
Preferably, the reaction kettle is internally provided with a spiral stirrer which is driven by a motor.
Drawings
FIG. 1 shows a flow chart of a method for preparing a silicon nitride composite formulation powder;
fig. 2 shows a schematic view of a manufacturing apparatus for silicon nitride composite recipe powder.
In the figure, 1 is a reaction kettle, 2 is a slurry circulating pump, 3 is a buffer bin, 4 is a helical ribbon stirrer, M is a motor, V1 is a first valve, V2 is a second valve, V3 is a third valve, V4 is a fourth valve, V5 is a fifth valve, S-1 is a first pipeline, S-2 is a second pipeline, S-3 is a third pipeline, and S-4 is a fourth pipeline.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be further clearly and completely described below with reference to the accompanying drawings and specific examples of the present invention.
Because the existing method for preparing the silicon nitride composite formula powder inevitably needs grinding and refining, more impurities are introduced. Therefore, the invention provides a preparation method of silicon nitride composite formula powder, which comprises the following steps:
and 4, transferring the separated solid phase into a sintering furnace for decomposition and calcination to obtain the silicon nitride composite formula powder.
Correspondingly, the silicon nitride composite formula powder is prepared by the method and comprises silicon nitride and a sintering aid.
Correspondingly, the invention also provides a preparation device of the silicon nitride composite formula powder, which comprises the following components:
the reaction kettle is used for uniformly mixing the silicon tetrachloride, the diluent and the sintering aid and reacting the mixed slurry with ammonia gas;
a solid-liquid separation device for solid-liquid separation of the slurry obtained by the reaction; and
and the sintering furnace is used for decomposing the solid phase separated by calcination.
Example 1
Referring to fig. 1, the embodiment provides a preparation method of silicon nitride composite formula powder, which includes the following steps:
and 4, transferring the separated solid phase into a sintering furnace for decomposition and calcination to obtain the silicon nitride composite formula powder.
In this embodiment, in step 1, the diluent is at least one of cyclohexane, toluene, dichloromethane and cyclopentane, the sintering aid is at least one of alumina and yttria, the particle size of the sintering aid is in the range of 0.5 μm to 1 μm, and the content of silicon tetrachloride is in the range of 2wt% to 50wt%, the content of diluent is in the range of 49.8wt% to 97.9wt%, and the content of sintering aid is in the range of 0.1wt% to 2wt%, based on the total weight of silicon tetrachloride, diluent and sintering aid.
In step 2, silicon tetrachloride (SiCl) 4 ) With ammonia (NH) 3 ) A polymerization reaction occurs, the reaction formula of which is as follows:
SiCl 4 (l)+NH 3 (g)→Si[(NH) 2 ] n +NH 4 Cl(s)
wherein the flow rate of the ammonia gas is 1m/s-50m/s, the silicon imine solid material generated by ammonia gas reaction is slowly introduced into the reaction kettle to be dispersed on the surface of the sintering aid in the mixed slurry, the introduction of the ammonia gas is stopped when the first concentration is 10wt% -15wt% of the total weight of the slurry to stop the reaction, and the generated silicon imine powder is uniformly dispersed on the surface of the sintering aid in the liquid phase suspension system. In step 1 and step 2, the method further comprises the step of self-circulating the slurry in the reaction kettle so that solid-phase particles in the reaction slurry can be uniformly suspended in a liquid-phase system.
In step 4, the separated solid phase is a solid phase in which the silamine is uniformly dispersed on the surface of the sintering aid, and the particle size of the silamine is in the range of 10-100 nm.
And 4, performing decomposition and calcination in the atmosphere of nitrogen or inert gas, and in the decomposition and calcination process, finishing the conversion of the surface silamine of the sintering aid to the high alpha-phase silicon nitride powder by combining the silamine with the sintering aid solid powder through pyrolysis and crystallization. The decomposition calcination temperature is in the range of 1200-1600 ℃. The obtained silicon nitride composite formula powder comprises silicon nitride and a sintering aid, and the effective component is silicon nitride.
The embodiment also provides silicon nitride composite formula powder prepared by the method, which comprises silicon nitride and a sintering aid.
According to the preparation method of the silicon nitride composite formula powder, the sintering aid is added into the reaction liquid phase system in advance, the sintering aid is uniformly dispersed in the silicon tetrachloride liquid phase system under the stirring effect, and the silicon imine generated by the ammonolysis reaction after the ammonia gas is introduced is completely dispersed on the surface of the sintering aid, so that in the decomposition and calcination process, the silicon imine combined with the sintering aid is beneficial to obtaining the superfine silicon nitride composite formula powder by silicon nitride crystallization molding, further refining and grinding are not needed, the introduction of external impurities is greatly reduced or avoided, and the production efficiency is improved.
Example 2
As shown in fig. 2, the present embodiment discloses a device for preparing silicon nitride composite formula powder, comprising:
a reaction kettle 1, which is used for uniformly mixing silicon tetrachloride, a diluent and a sintering aid and reacting the mixed slurry with ammonia gas;
a solid-liquid separation device for solid-liquid separation of the slurry obtained by the reaction; and
and the sintering furnace is used for decomposing the solid phase separated by calcination.
Wherein the reaction kettle 1 is a spiral belt type slurry stirring tank type reaction kettle, the solid-liquid separation device is a rake blade type dryer, a horizontal spiral centrifugal machine or a high-efficiency precision filter, and the sintering furnace is a closed push plate type resistance furnace.
In some embodiments, the preparation device further comprises a slurry circulating pump 2 for self-circulating the slurry in the reaction kettle 1, an inlet pipe of the slurry circulating pump 2 is connected with the discharge port of the reaction kettle, and the discharge port of the slurry circulating pump 2 is connected with the feed port of the reaction kettle.
In some embodiments, the reactor 1 is provided with a helical agitator 4, which is driven by a motor M.
The device of the embodiment can be used for preparing the silicon nitride composite formula powder by the method in the embodiment 1, and the silicon nitride composite formula powder comprises silicon nitride and a sintering aid.
Example 3
The embodiment discloses a preparation method of silicon nitride composite formula powder, which adopts the device in the embodiment 2, and as shown in fig. 2, the specific process is as follows:
first, the first valve V1 was opened, 198kg of silicon tetrachloride and 202kg of cyclohexane were added to the screw-type slurry stirred tank reactor (i.e., the reaction tank 1) through the fourth conduit S-4, and then 2.27kg of alumina and 2.73kg of yttrium oxide (average particle diameter: 0.8 μm) were added thereto through the surge bin 3. And simultaneously starting the slurry circulating pump 2, opening the third valve V3 and the fourth valve V4, and allowing the slurry in the helical ribbon type slurry stirring tank type reaction kettle to perform self-circulation operation through the third pipeline S-3, so that a silicon imine prepolymer (with the average particle size of 80 nm) generated by the reaction is uniformly dispersed in a liquid phase material system in the helical ribbon type slurry stirring tank type reaction kettle and attached to the surface of the sintering aid suspended particles, and is not precipitated at the bottom of the helical ribbon type slurry stirring tank type reaction kettle. And (3) closing the first valve V1 (the fifth valve V5 is in a closed state), starting a helical ribbon stirring motor (namely a motor M) to drive a helical ribbon stirrer 4 in the helical ribbon slurry stirring tank type reaction kettle, and controlling the rotating speed to be 20rpm so as to uniformly mix the solid-liquid phase materials added into the helical ribbon slurry stirring tank type reaction kettle. Then the second valve V2 is opened, ammonia gas is introduced into the helical ribbon type slurry stirring tank type reaction kettle at the speed of 15m/S through the first pipeline S-1, and the introduction of the ammonia gas is stopped until the concentration of solid phase in the slurry reaches 15 percent of the total weight of the slurry. And then, closing the fourth valve V4, opening the fifth valve V5, conveying the prepared mixture containing the prepolymer after full reaction to a horizontal screw centrifuge through a second pipeline S-2 by using a slurry circulating pump 2 for solid-liquid separation, calcining the separated solid powder system of the prepolymer silicon imine and the sintering aid in a closed push-plate type resistance furnace at the temperature of 1500 ℃ in the nitrogen atmosphere, and completing the decomposition and crystallization of the silicon imine to obtain the high alpha-phase silicon nitride composite formula powder containing the sintering aid.
Example 4
The embodiment discloses a preparation method of silicon nitride composite formula powder, which adopts the device in the embodiment 2, and as shown in fig. 2, the specific process is as follows:
first, the first valve V1 was opened, and 8.1kg of silicon tetrachloride and 396.5kg of toluene were added to the screw-type slurry stirred tank reactor (i.e., reactor 1) through the fourth line S-4, and then 0.4kg of alumina (average particle diameter: 0.5 μm) was added thereto through the surge bin 3. And simultaneously starting the slurry circulating pump 2, opening the third valve V3 and the fourth valve V4, and allowing the slurry in the helical ribbon type slurry stirring tank type reaction kettle to perform self-circulation operation through the third pipeline S-3, so that a silicon imine prepolymer (with the average particle size of 10 nm) generated by the reaction is uniformly dispersed in a liquid phase material system in the helical ribbon type slurry stirring tank type reaction kettle and attached to the surface of suspended particles of the sintering aid, and is not precipitated at the bottom of the helical ribbon type slurry stirring tank type reaction kettle. And (3) closing the first valve V1 (the fifth valve V5 is in a closed state), starting a helical ribbon stirring motor (namely a motor M) to drive a helical ribbon stirrer 4 in the helical ribbon slurry stirring tank type reaction kettle, and controlling the rotating speed to be 20rpm so as to uniformly mix the solid-liquid phase materials added into the helical ribbon slurry stirring tank type reaction kettle. Then the second valve V2 is opened, ammonia gas is introduced into the helical ribbon type slurry stirring tank type reaction kettle at the speed of 10m/S through the first pipeline S-1, and the introduction of the ammonia gas is stopped until the concentration of solid phase in the slurry reaches 10 percent of the total weight of the slurry. And then, closing the fourth valve V4, opening the fifth valve V5, conveying the prepared mixture containing the prepolymer after full reaction to a horizontal screw centrifuge through a second pipeline S-2 by using a slurry circulating pump 2 for solid-liquid separation, calcining the separated solid powder system of the prepolymer silicon imine combined with the sintering aid in a sealed push plate type resistance furnace at the temperature of 1200 ℃ under the argon atmosphere, and completing the decomposition and crystallization of the silicon imine to obtain the high alpha-phase silicon nitride composite formula powder containing the sintering aid.
Example 5
The embodiment discloses a preparation method of silicon nitride composite formula powder, which adopts the device in the embodiment 2, and as shown in fig. 2, the specific process is as follows:
first, the first valve V1 was opened, 202.5kg of silicon tetrachloride and 201.69kg of methylene chloride were added to a screw-type slurry stirred tank reactor (i.e., reaction tank 1) through the fourth conduit S-4, and then 0.81kg of alumina (average particle diameter: 1 μm) was added thereto through the surge bin 3. And simultaneously starting the slurry circulating pump 2, opening the third valve V3 and the fourth valve V4, and allowing the slurry in the helical ribbon type slurry stirring tank type reaction kettle to perform self-circulation operation through the third pipeline S-3, so that a silicon imine prepolymer (with the average particle size of 100 nm) generated by the reaction is uniformly dispersed in a liquid phase material system in the helical ribbon type slurry stirring tank type reaction kettle and attached to the surface of the sintering aid suspended particles, and is not precipitated at the bottom of the helical ribbon type slurry stirring tank type reaction kettle. And (3) closing the first valve V1 (the fifth valve V5 is in a closed state), starting a helical ribbon stirring motor (namely a motor M) to drive a helical ribbon stirrer 4 in the helical ribbon slurry stirring tank type reaction kettle, and controlling the rotating speed to be 20rpm so as to uniformly mix the solid-liquid phase materials added into the helical ribbon slurry stirring tank type reaction kettle. Then the second valve V2 is opened, ammonia gas is introduced into the helical ribbon type slurry stirred tank reactor through the first pipeline S-1 at the speed of 1m/S, and the introduction of the ammonia gas is stopped until the concentration of the solid phase in the slurry reaches 12 percent of the total weight of the slurry. And then, closing a fourth valve V4, opening a fifth valve V5, conveying the prepared mixture containing the prepolymer after full reaction to a high-efficiency precision filter through a second pipeline S-2 by using a slurry circulating pump 2 for solid-liquid separation, and calcining the separated solid powder system of the prepolymer and the sintering aid in a closed push-plate type resistance furnace at 1600 ℃ in the nitrogen atmosphere to complete the decomposition and crystallization of the silicon imine, thereby obtaining the high alpha-phase silicon nitride composite formula powder containing the sintering aid.
Example 6
The embodiment discloses a preparation method of silicon nitride composite formula powder, which adopts the device in the embodiment 2, and as shown in fig. 2, the specific process is as follows:
first, the first valve V1 was opened, 194.4kg of silicon tetrachloride and 202.5kg of cyclopentane were added to a screw-type slurry stirred tank reactor (i.e., reaction tank 1) through the fourth conduit S-4, and then 8.1kg of yttrium oxide (average particle diameter: 1 μm) was added thereto through the surge bin 3. And simultaneously starting the slurry circulating pump 2, opening the third valve V3 and the fourth valve V4, and allowing the slurry in the helical ribbon type slurry stirring tank type reaction kettle to perform self-circulation operation through the third pipeline S-3, so that a silicon imine prepolymer (with the average particle size of 100 nm) generated by the reaction is uniformly dispersed in a liquid phase material system in the helical ribbon type slurry stirring tank type reaction kettle and attached to the surface of the sintering aid suspended particles, and is not precipitated at the bottom of the helical ribbon type slurry stirring tank type reaction kettle. And (3) closing the first valve V1 (the fifth valve V5 is in a closed state), starting a helical ribbon stirring motor (namely a motor M) to drive a helical ribbon stirrer 4 in the helical ribbon slurry stirring tank type reaction kettle, and controlling the rotating speed to be 20rpm so as to uniformly mix the solid-liquid phase materials added into the helical ribbon slurry stirring tank type reaction kettle. Then the second valve V2 is opened, ammonia gas is introduced into the helical ribbon type slurry stirred tank reactor through the first pipeline S-1 at the speed of 1m/S, and the introduction of the ammonia gas is stopped until the concentration of solid phase in the slurry reaches 10 percent of the total weight of the slurry. And then, closing the fourth valve V4, opening the fifth valve V5, conveying the prepared mixture containing the prepolymer after full reaction to a rake dryer through a second pipeline S-2 by using a slurry circulating pump 2 for solid-liquid separation, calcining the separated solid powder system of the prepolymer silicon imine combined with the sintering aid in an argon atmosphere at 1600 ℃ in a closed push plate type resistance furnace, and completing the decomposition and crystallization of the silicon imine to obtain the high alpha-phase silicon nitride composite formula powder containing the sintering aid.
The density of the silicon nitride composite formula powder obtained in the embodiments 3 to 6 can reach 3.2g/cm 3 . Because the sintering aid is added into the reaction liquid phase system in advance, the sintering aid is uniformly dispersed in the silicon tetrachloride liquid phase system under the stirring action, and the silicon imine generated by the ammonolysis reaction after the ammonia gas is introduced is completely dispersed on the surface of the sintering aid, the silicon imine combined with the sintering aid is beneficial to the crystallization molding of the silicon nitride to obtain the superfine silicon nitride complex in the decomposition and calcination processThe formula powder is mixed, further refining and grinding are not needed, the introduction of external impurities is greatly reduced or avoided, and meanwhile, the production efficiency is improved.
The embodiments of the present invention are not limited to the embodiments shown in the specific embodiments, and other embodiments can be derived by those skilled in the art according to the technical solutions of the present invention, and also belong to the technical innovation scope of the present invention.
Claims (11)
1. A preparation method of silicon nitride composite formula powder comprises the following steps:
step 1, adding silicon tetrachloride, a diluent and a sintering aid into a reaction kettle, and mixing to form uniform mixed slurry;
step 2, slowly introducing ammonia gas into the reaction kettle for reaction until the concentration of the solid phase in the slurry reaches a first concentration;
step 3, conveying the slurry obtained by the reaction to a solid-liquid separation device for solid-liquid separation; and
and 4, transferring the separated solid phase into a sintering furnace for decomposition and calcination to obtain the silicon nitride composite formula powder.
2. The method according to claim 1, wherein, in step 1,
the diluent is at least one of cyclohexane, toluene, dichloromethane and cyclopentane,
the sintering aid is at least one of alumina and yttrium oxide, the grain size of the sintering aid is in the range of 0.5-1 μm, and
the content of silicon tetrachloride is in the range of 2wt% to 50wt%, the content of diluent is in the range of 49.8wt% to 97.9wt%, and the content of sintering aid is in the range of 0.1wt% to 2wt%, based on the total weight of silicon tetrachloride, diluent, and sintering aid.
3. The method as claimed in claim 1, wherein in the step 2, the flow rate of the ammonia gas is 1m/s to 50m/s, and the solid silicon imine generated by the reaction of the ammonia gas is slowly introduced into the reaction kettle, and is dispersed on the surface of the sintering aid in the mixed slurry, wherein the first concentration is 10wt% to 15wt% based on the total weight of the slurry.
4. The method of claim 1, further comprising self-circulating the slurry in the reaction tank in step 1 and step 2 to uniformly suspend the solid particles in the reaction slurry in the liquid phase system.
5. The method according to any one of claims 1 to 4, wherein in step 4, the separated solid phase is a solid phase in which a silicon imide having a particle size in the range of 10 to 100nm is uniformly dispersed on the surface of the sintering aid.
6. The method according to claim 1, wherein in step 4, the decomposition calcination is performed in a nitrogen or inert gas atmosphere, and the decomposition calcination temperature is in the range of 1200 ℃ to 1600 ℃.
7. The method according to claim 1, wherein the method uses a silicon nitride composite formula powder preparation device comprising:
the reaction kettle (1) is used for uniformly mixing silicon tetrachloride, a diluent and a sintering aid and enabling the mixed slurry to react with ammonia gas to form mixed slurry, wherein a first pipeline (S-1), a second pipeline (S-2), a third pipeline (S-3), a fourth pipeline (S-4) and a buffer bin (3) are arranged on the reaction kettle, the first pipeline is used for introducing ammonia gas, the second pipeline is used for discharging the mixed slurry obtained after reaction, the third pipeline is used for enabling the slurry in the reaction kettle to perform self-circulation operation, the fourth pipeline is used for introducing the silicon tetrachloride and the diluent, and the buffer bin is used for adding the sintering aid;
the solid-liquid separation device is connected with the second pipeline and is used for carrying out solid-liquid separation on the slurry obtained by the reaction; and
and the sintering furnace is used for decomposing the solid phase separated by calcination to obtain the silicon nitride composite formula powder.
8. The method according to claim 7, characterized in that the reaction vessel (1) is a helical ribbon slurry stirred tank reactor,
the solid-liquid separation device is a rake-blade dryer, a horizontal screw centrifuge or a high-efficiency precision filter,
the sintering furnace is a closed push plate type resistance furnace.
9. The method according to claim 7, characterized in that the preparation device further comprises a slurry circulating pump (2) for self-circulating the reaction slurry in the reaction kettle (1), an inlet pipe of the slurry circulating pump (2) is connected with a discharge port of the reaction kettle, and a discharge port of the slurry circulating pump (2) is connected with a feed port of the reaction kettle.
10. A method according to claim 7, characterized in that the reaction vessel (1) is provided with a helical agitator (4) which is driven by a motor (M).
11. A silicon nitride composite formulated powder prepared by the method of any one of claims 1-10, comprising silicon nitride and a sintering aid.
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