CN111233589B - Preparation method of ultra-large particle hexanitrohexaazaisowurtzitane - Google Patents
Preparation method of ultra-large particle hexanitrohexaazaisowurtzitane Download PDFInfo
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Abstract
The invention belongs to the field of energetic materials, and particularly relates to a preparation method of ultra-large particle hexanitrohexaazaisowurtzitane. The method for preparing the ultra-large particle hexanitrohexaazaisowurtzitane provided by the invention has the advantages that the seed crystal with a specific particle size range is added into a saturated solution, then the non-solvent is rapidly added into the saturated solution, so that the non-solvent and the mixed solution are rapidly and uniformly mixed to form a uniform supersaturated state in the whole range, and the uniform growth of the seed crystal in the whole range is realized. The particle size of the seed crystal is adjusted to prepare the ultra-large particle hexanitrohexaazaisowurtzitane crystal with the average particle size of 400-600 mu m, and the results of the examples show that the experimental magnitude can reach 50 kg level at most, the prepared hexanitrohexaazaisowurtzitane crystal has good shape consistency, the yield can reach more than 60 percent, and the aim of industrial batch production is fulfilled.
Description
Technical Field
The invention belongs to the field of energetic materials, and particularly relates to a preparation method of ultra-large particle hexanitrohexaazaisowurtzitane.
Background
Hexanitrohexaazaisowurtzitane (HNIW, CL-20), a white crystalline, high energy density compound with cage type polycyclic ammonium nitrate structure, is the currently known non-nuclear mono-explosive with the highest energy and the strongest power which can be practically used, and has been widely noticed by the world since the first synthesis by Ph.Nielsen (Nielsen) in 1987.
In practical applications, particularly in casting formulations, to achieve high energy levels, it is necessary to use CL-20 in the form of a graded blend of different particle sizes, particularly large particles, to achieve high solids content casting formulations.
Chinese patent CN101624394 provides a sphericized epsilon-type hexanitrohexaazaisowurtzitane crystal and a preparation method thereof. The production of the spherical epsilon-type hexanitrohexaazaisowurtzitane is carried out by adding a crystal production control agent to a saturated solution, adding an antisolvent to form a supersaturated solution, subsequently adding seed crystals to the supersaturated solution, and continuously dropwise adding the antisolvent until CL-20 in the solution is completely precipitated. The spheroidized crystal has no sharp edges and corners, has the shape of a polyhedral sphere and has the granularity of about 20-500 mu m.
Chinese patent CN103539800A provides a preparation method of large-particle hexanitrohexaazaisowurtzitane. Adding a non-solvent into a saturated solution to form a supersaturated solution, then adding seed crystals into the supersaturated solution, continuously dropwise adding the non-solvent, stirring, filtering, washing and drying to obtain the hexanitrohexaazaisowurtzitane with the average particle size of more than 350 mu m.
Although the two methods can be used for preparing the hexanitrohexaazaisowurtzitane crystal with a specific particle size range, the experimental magnitude is only hectogram at most, and when the process is amplified to kilogram level, the hexanitrohexaazaisowurtzitane crystal prepared by the two methods is easy to have twinning phenomenon, has poor appearance consistency and low yield, and is not easy to realize the aim of industrial batch production.
Disclosure of Invention
The invention aims to solve the technical problems and provides a preparation method of ultra-large particle hexanitrohexaazaisowurtzitane, the experimental magnitude of the preparation method can reach 50 kg, the average particle size of the prepared hexanitrohexaazaisowurtzitane crystal is 400-600 mu m, the morphology consistency is good, the yield can reach more than 60%, and the aim of industrial batch production can be achieved.
In order to achieve the above object, the present invention provides a method for preparing ultra-large particles of hexanitrohexaazaisowurtzitane, which comprises the following steps:
(1) dissolving hexanitrohexaazaisowurtzitane in a recrystallization solvent to obtain a hexanitrohexaazaisowurtzitane saturated solution;
(2) adding large-particle hexanitrohexaazaisowurtzitane seed crystals into the saturated hexanitrohexaazaisowurtzitane solution to obtain a hexanitrohexaazaisowurtzitane suspension, wherein the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystals is 250-300 mu m;
(3) adding a non-solvent into the hexanitrohexaazaisowurtzitane suspension in a natural feeding manner, carrying out heat preservation, and carrying out solid-liquid separation to obtain ultralarge particle hexanitrohexaazaisowurtzitane, wherein the feeding speed of the non-solvent is 20-40L/min, and the adding position of the non-solvent is below the liquid level of the hexanitrohexaazaisowurtzitane suspension; the density of the non-solvent is less than the density of the recrystallization solvent; the average particle size of the ultra-large particle hexanitrohexaazaisowurtzitane is 400-600 mu m.
Preferably, the preparation method of the large-particle hexanitrohexaazaisowurtzitane seed crystal in the step (2) comprises the following steps:
a) dissolving hexanitrohexaazaisowurtzitane in a recrystallization solvent to obtain an initial hexanitrohexaazaisowurtzitane saturated solution;
b) adding a hexanitrohexaazaisowurtzitane seed crystal into the initial hexanitrohexaazaisowurtzitane saturated solution to obtain an initial hexanitrohexaazaisowurtzitane suspension; the average particle size of the hexanitrohexaazaisowurtzitane seed crystal is 125-180 mu m;
c) adding a non-solvent into the initial hexanitrohexaazaisowurtzitane suspension in a natural feeding manner, and after heat preservation, carrying out solid-liquid separation to obtain large-particle hexanitrohexaazaisowurtzitane seed crystals, wherein the feeding speed of the non-solvent is 20-40L/min; the adding position of the non-solvent is positioned below the liquid level of the initial hexanitrohexaazaisowurtzitane suspension; the density of the non-solvent is less than the density of the recrystallization solvent; the large-particle hexanitrohexaazaisowurtzitane particles have an average particle diameter of 250 to 300 μm.
Preferably, in the step (2), the mass ratio of the hexanitrohexaazaisowurtzitane to the large-particle hexanitrohexaazaisowurtzitane seed crystal is 30: (5-10);
in the step b), the mass ratio of the hexanitrohexaazaisowurtzitane to the hexanitrohexaazaisowurtzitane seed crystal is 30: (5-10).
Preferably, the volume ratio of the recrystallization solvent to the non-solvent is independently 1: 1.25 to 2.5.
Preferably, the temperature of the saturated solution of hexanitrohexaazaisowurtzitane in the step (1) and the temperature of the initial saturated solution of hexanitrohexaazaisowurtzitane in the step a) are independently 20 to 45 ℃.
Preferably, the temperature of the hexanitrohexaazaisowurtzitane suspension in the step (2) and the temperature of the initial hexanitrohexaazaisowurtzitane suspension in the step b) are independently 20 to 45 ℃.
Preferably, the temperature of the heat preservation in the step (3) and the temperature of the heat preservation in the step c) are independently 20-45 ℃.
Preferably, the heat preservation time in the step (3) and the heat preservation time in the step c) are 24-48 hours independently.
Preferably, the recrystallization solvent is one or more of a polar ester solvent and a polar ketone solvent independently.
Preferably, the recrystallization solvent is independently one or more of ethyl acetate, methyl acetate, acetone, and methyl ethyl ketone.
Preferably, the non-solvent is independently one or more of an alkane and a cycloalkane.
Preferably, the non-solvent is independently one or more of hexane, heptane, octane and cyclohexane.
The preparation method of the ultra-large particle hexanitrohexaazaisowurtzitane provided by the invention comprises the following steps: firstly, dissolving hexanitrohexaazaisowurtzitane in a recrystallization solvent to obtain hexanitrohexaazaisowurtzitane saturated solution; adding large-particle hexanitrohexaazaisowurtzitane seed crystals into the saturated hexanitrohexaazaisowurtzitane solution to obtain a hexanitrohexaazaisowurtzitane suspension, wherein the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystals is 250-300 mu m; finally, adding a non-solvent into the hexanitrohexaazaisowurtzitane suspension in a natural feeding manner, carrying out heat preservation, and carrying out solid-liquid separation to obtain the ultralarge-particle hexanitrohexaazaisowurtzitane, wherein the feeding speed of the non-solvent is 20-40L/min, and the adding position of the non-solvent is below the liquid level of the hexanitrohexaazaisowurtzitane suspension; the density of the non-solvent is less than the density of the recrystallization solvent; the average particle size of the ultra-large particle hexanitrohexaazaisowurtzitane is 400-600 mu m. According to the invention, firstly, seed crystals with large particle sizes are added into a saturated solution to prepare turbid liquid, then a non-solvent is rapidly added into the saturated solution, the non-solvent and the turbid liquid are rapidly and uniformly mixed, so that the turbid liquid in a reactor rapidly forms a uniform supersaturated state in the whole range, the seed crystals in the whole range in the reactor can uniformly and rapidly grow, the seed crystals with large particle sizes rapidly grow in a uniform and stable supersaturated state environment, and the ultra-large particle hexanitrohexaazaisowurtzitane product is obtained. Meanwhile, a non-solvent is added into the suspension in a submerged mode, the density of the non-solvent is smaller than that of the recrystallization solvent, the non-solvent is rapidly added into the hexaazaisowurtzitane suspension in a natural flow addition mode with the flow acceleration of 20-40L/min, the non-solvent and the suspension can be rapidly and uniformly mixed, so that the suspension in the reactor can rapidly form a uniform supersaturated state in the whole range, uniform and rapid growth of the crystal seeds in the whole range in the reactor can be realized, the phenomenon of twin crystals is avoided when the local over-saturation distribution in the reactor is not uniform, the overall difference of the growth speed of the crystal seeds is large, and the appearance of the crystals is extremely poor when the experimental magnitude is increased to the kilogram magnitude. The results of the examples show that the average particle size of the ultra-large particle hexanitrohexaazaisowurtzitane crystal prepared by the method is within the range of 400-600 mu m, the experimental magnitude can reach 50 kg at most, the morphology consistency of the prepared hexanitrohexaazaisowurtzitane crystal is good, the yield can reach more than 60%, and the aim of industrial batch production is fulfilled.
Drawings
FIG. 1 is an SEM image of the ultra-large particle size hexanitrohexaazaisowurtzitane prepared in example 1;
FIG. 2 is an SEM image of the oversized particles of hexanitrohexaazaisowurtzitane obtained in comparative example 1.
Detailed Description
The invention provides a preparation method of ultra-large particle hexanitrohexaazaisowurtzitane, which comprises the following steps:
(1) dissolving a saturated amount of hexanitrohexaazaisowurtzitane in a recrystallization solvent to obtain a hexanitrohexaazaisowurtzitane saturated solution;
(2) adding large-particle hexanitrohexaazaisowurtzitane seed crystals into the saturated hexanitrohexaazaisowurtzitane solution to obtain a hexanitrohexaazaisowurtzitane suspension, wherein the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystals is 250-300 mu m;
(3) adding a non-solvent into the hexanitrohexaazaisowurtzitane suspension in a natural feeding manner, carrying out heat preservation, and carrying out solid-liquid separation to obtain ultralarge particle hexanitrohexaazaisowurtzitane, wherein the feeding speed of the non-solvent is 20-40L/min, and the adding position of the non-solvent is below the liquid level of the hexanitrohexaazaisowurtzitane suspension; the density of the non-solvent is less than the density of the recrystallization solvent; the average particle size of the ultra-large particle hexanitrohexaazaisowurtzitane is 400-600 mu m.
In the present invention, a sufficient amount (a saturated amount or a supersaturated amount) of hexanitrohexaazaisowurtzitane is added to a recrystallization solvent and dissolved at a temperature of 20 to 45 ℃ to obtain a saturated hexanitrohexaazaisowurtzitane solution. In the present invention, there is no particular requirement for the process of dissolving hexanitrohexaazaisowurtzitane, and the method of dissolving is well known to those skilled in the art, and specifically, the method of dissolving can be carried out by stirring. In the present invention, the recrystallization solvent is preferably one or more of polar ester solvents and polar ketone solvents, and is more preferably one or more of ethyl acetate, methyl acetate, acetone, and methyl ethyl ketone. In the present invention, the source of the hexanitrohexaazaisowurtzitane is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, when a supersaturated amount of hexanitrohexaazaisowurtzitane is added, it is preferred that after the hexanitrohexaazaisowurtzitane is completely dissolved, the excess hexanitrohexaazaisowurtzitane in the system is filtered to obtain a saturated hexanitrohexaazaisowurtzitane solution. The filtration mode in the invention has no special requirement, and the filtration mode known by the technicians in the field can be adopted, and concretely, the vacuum filtration mode can be adopted. In the present invention, the temperature of the saturated hexanitrohexaazaisowurtzitane solution is preferably 20 to 45 ℃, and more preferably 25 to 35 ℃.
After a saturated solution of the hexanitrohexaazaisowurtzitane is obtained, adding large-particle hexanitrohexaazaisowurtzitane crystal seeds into the saturated solution; in the examples of the present invention, the saturated hexanitrohexaazaisowurtzitane solution is fed into a crystallizer, and the large-particle hexanitrohexaazaisowurtzitane seed crystal is added at a temperature of 20 to 45 ℃ to obtain a hexanitrohexaazaisowurtzitane suspension. In the invention, the stirring speed of the crystallizer is preferably 150-250 rpm, more preferably 175-235 rpm, and more preferably 205-220 rmp, and the stirring time is preferably 10-20 min, and more preferably 12-18 min. In the present invention, the temperature of the suspension of the hexanitrohexaazaisowurtzitane is preferably 20 to 45 ℃, and more preferably 25 to 35 ℃.
In the invention, the crystallizer has no special requirement, and can be a crystallizer well known by the technicians in the field, and particularly, the crystallizer used in the invention is a semispherical and mirror-surface stainless steel crystallizer.
In the invention, the method for adding the large-particle hexanitrohexaazaisowurtzitane crystal seed has no special requirement, and the large-particle hexanitrohexaazaisowurtzitane crystal seed can be added at one time by adopting a filling mode which is well known to a person skilled in the art.
In the present invention, the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystal is preferably in the range of 250 to 300. mu.m. In the present invention, the mass ratio of the hexanitrohexaazaisowurtzitane to the large-particle hexanitrohexaazaisowurtzitane seed crystal is preferably 30: (5-10), and more preferably 30: (6-8).
In the present invention, the source of the large-particle hexanitrohexaazaisowurtzitane seed crystal is not particularly limited, and the large-particle hexanitrohexaazaisowurtzitane seed crystal can be prepared by a preparation method well known to those skilled in the art, and the preparation method of the large-particle hexanitrohexaazaisowurtzitane seed crystal preferably comprises the following steps:
a) dissolving hexanitrohexaazaisowurtzitane in a recrystallization solvent to obtain an initial hexanitrohexaazaisowurtzitane saturated solution;
b) adding a hexanitrohexaazaisowurtzitane seed crystal into the initial hexanitrohexaazaisowurtzitane saturated solution to obtain an initial hexanitrohexaazaisowurtzitane suspension; the average particle size of the hexanitrohexaazaisowurtzitane seed crystal is 125-180 mu m;
c) adding a non-solvent into the initial hexanitrohexaazaisowurtzitane suspension in a natural feeding manner, and after heat preservation, carrying out solid-liquid separation to obtain large-particle hexanitrohexaazaisowurtzitane seed crystals, wherein the feeding speed of the non-solvent is 20-40L/min; the adding position of the non-solvent is positioned below the liquid level of the initial hexanitrohexaazaisowurtzitane suspension; the density of the non-solvent is less than the density of the recrystallization solvent; the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystal is 250 to 300 mu m.
In the present invention, a sufficient amount (a saturated amount or a supersaturated amount) of hexanitrohexaazaisowurtzitane is added to a recrystallization solvent and dissolved at a temperature of 20 to 45 ℃ to obtain the initial saturated hexanitrohexaazaisowurtzitane solution. In the present invention, there is no particular requirement for the process of dissolving hexanitrohexaazaisowurtzitane, and the method of dissolving the hexanitrohexaazaisowurtzitane may be a method known to those skilled in the art, specifically, a method of dissolving the hexanitrohexaazaisowurtzitane by stirring may be used. In the present invention, the recrystallization solvent is preferably one or more of polar ester solvents and polar ketone solvents, and is more preferably one or more of ethyl acetate, methyl acetate, acetone, and methyl ethyl ketone. In the present invention, the source of the hexanitrohexaazaisowurtzitane is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the present invention, when a supersaturated amount of hexanitrohexaazaisowurtzitane is added, it is preferred that after the completion of the dissolution of hexanitrohexaazaisowurtzitane, the excess hexanitrohexaazaisowurtzitane in the system is filtered to obtain an initial saturated hexanitrohexaazaisowurtzitane solution. The filtration mode in the invention has no special requirement, and the filtration mode known by the technicians in the field can be adopted, and concretely, the vacuum filtration mode can be adopted. In the present invention, the temperature of the initial saturated hexanitrohexaazaisowurtzitane solution is preferably 20 to 45 ℃, and more preferably 25 to 35 ℃.
After obtaining an initial saturated hexanitrohexaazaisowurtzitane solution, adding hexanitrohexaazaisowurtzitane seed crystals into the initial saturated solution; in the examples of the present invention, the initial saturated hexanitrohexaazaisowurtzitane solution is fed to a crystallizer, and the hexanitrohexaazaisowurtzitane seed crystal is added thereto at a temperature of 20 to 45 ℃ to obtain an initial hexanitrohexaazaisowurtzitane suspension. In the invention, the stirring speed of the crystallizer is preferably 150-250 rpm, more preferably 175-235 rpm, and more preferably 205-220 rmp, and the stirring time is preferably 10-20 min, and more preferably 12-18 min. The temperature of the initial hexanitrohexaazaisowurtzitane suspension is preferably 20 to 45 ℃, and more preferably 25 to 35 ℃.
In the invention, the crystallizer has no special requirement, and can be a crystallizer well known by the technicians in the field, and particularly, the crystallizer used in the invention is a semispherical and mirror-surface stainless steel crystallizer.
In the present invention, there is no particular requirement for the method of adding the hexanitrohexaazaisowurtzitane seed crystal, and the hexanitrohexaazaisowurtzitane seed crystal may be added at a time by a filler method known to those skilled in the art. In the present invention, the source of the hexanitrohexaazaisowurtzitane seed crystal is not particularly limited, and the hexanitrohexaazaisowurtzitane seed crystal can be obtained by a production method or a purchase method known to those skilled in the art, and in the present invention, a commercially available product is preferably used, and specifically, the hexanitrohexaazaisowurtzitane seed crystal in the examples of the present invention is purchased from a national 375 factory.
In the present invention, the average particle size of the hexanitrohexaazaisowurtzitane seed crystal is preferably 125 to 180 μm, more preferably 132 to 165 μm, and still more preferably 140 to 155. mu.m. In the present invention, the mass ratio of the hexanitrohexaazaisowurtzitane to the hexanitrohexaazaisowurtzitane seed crystal is preferably 30: (5-10), and more preferably 30: (6-8).
In the present invention, after obtaining an initial hexanitrohexaazaisowurtzitane suspension, the non-solvent is added to the solution level of the initial hexanitrohexaazaisowurtzitane suspension by natural feeding. In an embodiment of the present invention, the non-solvent is added to the elevated tank of the crystallizer, and the non-solvent outlet is located below the liquid level of the initial hexanitrohexaazaisowurtzitane suspension, and the non-solvent is added to the initial hexanitrohexaazaisowurtzitane suspension by natural feeding at a temperature of 20 to 45 ℃ at a feeding rate of 20 to 40L/min, more preferably 23 to 38L/min, and still more preferably 25 to 34L/min. And (3) after the addition of the non-solvent is finished, timing and preserving heat for 24-48 h, preferably 28-34 h, more preferably 30-32 h, and then carrying out solid-liquid separation to obtain the large-particle hexanitrohexaazaisowurtzitane crystal seed.
In the present invention, the density of the non-solvent is less than that of the recrystallization solvent; the non-solvent is preferably one or more of an alkane and a cycloalkane, and is further preferably one or more of hexane, heptane, octane, and cyclohexane. In the present invention, the volume ratio of the recrystallization solvent to the non-solvent is preferably 1: 1.25 to 2.5, preferably 1.3 to 2.25, and more preferably 1.5 to 2.0. The source of the recrystallization solvent and the non-solvent in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the invention, no special requirement is imposed on the solid-liquid separation mode, and a solid-liquid separation mode well known to a person skilled in the art can be adopted, specifically, in the embodiment of the invention, vacuum filtration is carried out in a filter tank to obtain the large-particle hexanitrohexaazaisowurtzitane crystal seed.
In the present invention, after the solid-liquid separation, the solid phase fraction obtained is preferably dried and screened to obtain the large-particle hexanitrohexaazaisowurtzitane seed crystal. In the invention, the drying temperature is preferably 60-70 ℃, and the drying time is preferably 10-15 h. In the present invention, the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystal is preferably 250 to 300. mu.m, more preferably 265 to 283. mu.m.
In the present invention, a large-particle seed crystal of hexanitrohexaazaisowurtzitane obtained by the above method is added to the saturated hexanitrohexaazaisowurtzitane solution to obtain a hexanitrohexaazaisowurtzitane suspension, and a non-solvent is added to the hexanitrohexaazaisowurtzitane suspension at a position below the liquid surface thereof by natural feeding. In an embodiment of the present invention, the non-solvent is added to the elevated tank of the crystallizer, the non-solvent outlet is located below the liquid level of the hexanitrohexaazaisowurtzitane mixed solution, and the non-solvent is added to the hexanitrohexaazaisowurtzitane suspension by natural feeding at a temperature of 20 to 45 ℃ at a feeding rate of 20 to 40L/min, preferably 23 to 38L/min, more preferably 25 to 34L/min. And (3) after the addition of the non-solvent is finished, timing and preserving heat for 24-48 h, preferably 28-34 h, more preferably 30-32 h, and then carrying out solid-liquid separation to obtain the ultra-large particle hexanitrohexaazaisowurtzitane.
In the present invention, the density of the non-solvent is less than that of the recrystallization solvent; the non-solvent is preferably one or more of an alkane and a cycloalkane, and is further preferably one or more of hexane, heptane, octane, and cyclohexane. In the present invention, the volume ratio of the recrystallization solvent to the non-solvent is preferably 1: 1.25 to 2.5, preferably 1.3 to 2.25, and more preferably 1.5 to 2.0. The source of the recrystallization solvent and the non-solvent in the present invention is not particularly limited, and commercially available products known to those skilled in the art may be used.
In the invention, a non-solvent is fed into the liquid under the liquid surface of the hexanitrohexaazaisowurtzitane suspension at a speed of 20-40L/min; the density of the non-solvent is smaller than that of the recrystallization solvent, the flow rate is high, the non-solvent and the turbid liquid are quickly and uniformly mixed, so that the turbid liquid in the reactor quickly forms a uniform supersaturated state in the whole range, the seed crystals in the whole range of the crystallizer can uniformly and quickly grow through heat preservation treatment for 24-48 h, the seed crystals with large particle sizes can quickly grow in a uniform and stable supersaturated state environment, and the ultra-large particle hexanitrohexaazaisowurtzitane product is obtained; the average particle size of the ultra-large particle hexanitrohexaazaisowurtzitane is 400-600 mu m.
In the invention, no special requirement is imposed on the solid-liquid separation mode, and the solid-liquid separation mode known to a person skilled in the art can be adopted, specifically, in the embodiment of the invention, the ultralarge particle hexanitrohexaazaisowurtzitane is obtained by vacuum filtration in a filter tank.
In the present invention, after the solid-liquid separation, the solid phase fraction obtained is preferably dried to obtain ultra-large particles of hexanitrohexaazaisowurtzitane. In the invention, the drying temperature is preferably 60-70 ℃, more preferably 63-75 ℃, and the drying time is preferably 10-15 h, more preferably 12-13.5 h. In the invention, the average particle size of the ultra-large particle hexanitrohexaazaisowurtzitane is 400-600 mu m.
According to the invention, a non-solvent is added into the suspension in a submerged mode, because the density of the non-solvent is less than that of the recrystallization solvent, and the non-solvent is rapidly added into the hexaazaisowurtzitane suspension in a natural flow addition mode at the flow addition speed of 20-40L/min, the non-solvent and the suspension can be rapidly and uniformly mixed, so that the suspension in the reactor can rapidly form a uniform supersaturated state in the whole range, uniform and rapid growth of crystal seeds in the whole range in the reactor can be realized, the phenomenon that the local over-saturation distribution in the reactor is not uniform, the overall difference of the growth speed of the crystal seeds is large, and when the experimental magnitude is increased to kilogram level, the ultra-large average particle size of the hexaazaisowurtzitane product cannot reach the level of large particles or particles easily can be avoided. The experimental magnitude of the invention can reach 50 kg level at most, and the yield can reach more than 60 percent, thereby realizing the aim of industrialized mass production.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
At room temperature, 80L of ethyl acetate was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 150rpm, adding 5kg of seed crystals with the average particle size of 150 microns, stirring for 10min, adding 200L of n-octane into an overhead tank, placing an outlet below the liquid level of the saturated solution, opening a bottom valve of the overhead tank, adding the n-octane at a uniform speed at one time, adding for 5min, timing, keeping the temperature for 48h, filtering and drying to obtain the large-particle hexanitrohexaazaisowurtzitane.
Using the screened hexanitrohexaazaisowurtzitane with the average particle size of 300 mu m as a seed crystal; at room temperature, 80L of ethyl acetate was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 250rpm, adding 5kg of seed crystals with the average particle size of 300 mu m, stirring for 10min, adding 200L of n-octane into an overhead tank, placing an outlet below the liquid level of the saturated solution, starting a bottom valve of the overhead tank, adding the n-octane at a uniform speed for 5min at one time, timing and keeping the temperature for 48h after the addition is finished, filtering and drying to obtain the ultra-large particle hexanitrohexaazaisowurtzitane, wherein the average particle size of the prepared ultra-large particle hexanitrohexaazaisowurtzitane is 450 mu m, and an optical microscope picture is shown in figure 1.
Example 2
At room temperature, 80L of acetone was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 250rpm, adding 5kg of seed crystals with the average particle size of 150 mu m, stirring for 10min, adding 200L of n-heptane into an overhead tank, placing an outlet below the liquid level of the saturated solution, starting a bottom valve of the overhead tank, adding n-heptane at a uniform speed at one time, feeding for 5min, timing, keeping the temperature for 48h, filtering, and drying to obtain the large-particle hexanitrohexaazaisowurtzitane.
Using the screened hexanitrohexaazaisowurtzitane with the average particle size of 300 mu m as a seed crystal; at room temperature, 80L of acetone was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 250rpm, adding 5kg of seed crystals with the average particle size of 300 mu m, stirring for 10min, adding 200L of n-heptane into an overhead tank, placing an outlet below the liquid level of the saturated solution, starting a bottom valve of the overhead tank, adding n-heptane at a uniform speed at one time, feeding for 5min, timing, keeping the temperature for 48h after adding, filtering and drying to obtain the ultra-large particle hexanitrohexaazaisowurtzitane, wherein the average particle size of the prepared ultra-large particle hexanitrohexaazaisowurtzitane is 400 mu m.
Example 3
At room temperature, 80L of ethyl acetate was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 200rpm, adding 10kg of seed crystals with the average particle size of 150 microns, stirring for 5min, adding 200L of cyclohexane into an elevated tank, placing an outlet below the liquid level of the saturated solution, starting a bottom valve of the elevated tank, adding cyclohexane at a constant speed for 5min at one time, timing, keeping the temperature for 48h, filtering and drying to obtain the large-particle hexanitrohexaazaisowurtzitane.
Using the screened hexanitrohexaazaisowurtzitane with the average particle size of 280 mu m as a seed crystal; at room temperature, 80L of ethyl acetate was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 150rpm, adding 5kg of seed crystals with the average particle size of 280 microns, stirring for 10min, adding 200L of cyclohexane into an elevated tank, placing an outlet below the liquid level of the saturated solution, starting a bottom valve of the elevated tank, adding cyclohexane at a constant speed for 5min at one time, timing, keeping the temperature for 48h after adding, filtering and drying to obtain the ultra-large particle hexanitrohexaazaisowurtzitane, wherein the average particle size of the prepared ultra-large particle hexanitrohexaazaisowurtzitane is 425 microns.
Example 4
At room temperature, 80L of ethyl acetate was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 250rpm, adding 5kg of seed crystals with the average particle size of 150 mu m, stirring for 5min, adding 200L of n-octane into an overhead tank, placing an outlet below the liquid level of the saturated solution, starting a bottom valve of the overhead tank, adding the n-octane at a uniform speed at one time, feeding for 5min, timing, keeping the temperature for 48h, filtering, and drying to obtain the large-particle hexanitrohexaazaisowurtzitane.
Using the screened hexanitrohexaazaisowurtzitane with the average particle size of 280 mu m as a seed crystal; at room temperature, 80L of ethyl acetate was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 40 ℃, stirring at the speed of 180rpm, adding 5kg of seed crystals with the average particle size of 280 microns, stirring for 10min, adding 200L of n-octane into an overhead tank, placing an outlet below the liquid level of the saturated solution, starting a bottom valve of the overhead tank, adding the n-octane at a uniform speed for 5min at one time, timing and preserving heat for 48h after adding, filtering and drying to obtain the ultra-large particle hexanitrohexaazaisowurtzitane; the prepared ultra-large particle hexanitrohexaazaisowurtzitane has the average particle diameter of 480 mu m.
Comparative example 1
At room temperature, 80L of ethyl acetate was added to a dissolver, 30kg of the starting material CL-20 was added under stirring, and after complete dissolution, a saturated solution of CL-20 was obtained by filtration. Adding the saturated solution into a crystallizer, controlling the temperature to be 35 ℃, stirring at the speed of 150rpm, adding 10kg of seed crystals with the average particle size of 280 microns, stirring for 10min, adding 200L of n-octane into an overhead tank, placing an outlet above the liquid level of the saturated solution, starting a bottom valve of the overhead tank, adding n-octane at a uniform speed for 10min at one time, timing and preserving heat for 48h after adding, filtering, drying, and taking an optical microscope picture as shown in figure 2, wherein the average particle size of the prepared ultra-large particle hexanitrohexaazaisowurtzitane is 510 microns.
As can be seen from the results shown in FIGS. 1 and 2, when the experimental magnitude reaches the kilogram level, the crystal morphology consistency of the hexanitrohexaazaisowurtzitane prepared in example 1 of the present invention is better, while the product prepared in comparative example 1 has the goldenrain phenomenon and the morphology consistency is poorer.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A preparation method of ultra-large particle hexanitrohexaazaisowurtzitane is characterized by comprising the following steps:
(1) dissolving hexanitrohexaazaisowurtzitane in a recrystallization solvent to obtain a hexanitrohexaazaisowurtzitane saturated solution;
(2) adding large-particle hexanitrohexaazaisowurtzitane seed crystals into the saturated hexanitrohexaazaisowurtzitane solution to obtain a hexanitrohexaazaisowurtzitane suspension, wherein the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystals is 250-300 mu m;
(3) adding a non-solvent into the hexanitrohexaazaisowurtzitane suspension in a natural feeding manner, carrying out heat preservation, and carrying out solid-liquid separation to obtain ultralarge particle hexanitrohexaazaisowurtzitane, wherein the feeding speed of the non-solvent is 20-40L/min, and the adding position of the non-solvent is below the liquid level of the hexanitrohexaazaisowurtzitane suspension; the density of the non-solvent is less than the density of the recrystallization solvent; the average particle size of the ultra-large particle hexanitrohexaazaisowurtzitane is 400-600 mu m.
2. The method for preparing the oversized-particle hexanitrohexaazaisowurtzitane as claimed in claim 1, wherein the method for preparing the oversized-particle hexanitrohexaazaisowurtzitane seeds in the step (2) comprises the following steps:
a) dissolving hexanitrohexaazaisowurtzitane in a recrystallization solvent to obtain an initial hexanitrohexaazaisowurtzitane saturated solution;
b) adding a hexanitrohexaazaisowurtzitane seed crystal into the initial hexanitrohexaazaisowurtzitane saturated solution to obtain an initial hexanitrohexaazaisowurtzitane suspension; the average particle size of the hexanitrohexaazaisowurtzitane seed crystal is 125-180 mu m;
c) adding a non-solvent into the initial hexanitrohexaazaisowurtzitane suspension in a natural feeding manner, and after heat preservation, carrying out solid-liquid separation to obtain large-particle hexanitrohexaazaisowurtzitane seed crystals, wherein the feeding speed of the non-solvent is 20-40L/min; the adding position of the non-solvent is positioned below the liquid level of the initial hexanitrohexaazaisowurtzitane suspension; the density of the non-solvent is less than the density of the recrystallization solvent; the average particle size of the large-particle hexanitrohexaazaisowurtzitane seed crystal is 250 to 300 mu m.
3. The method for preparing a very large particulate hexanitrohexaazaisowurtzitane composition as claimed in claim 2, wherein in the step (2), the mass ratio of the hexanitrohexaazaisowurtzitane to the large particulate hexanitrohexaazaisowurtzitane seed crystals is 30: (5-10);
in the step b), the mass ratio of the hexanitrohexaazaisowurtzitane to the hexanitrohexaazaisowurtzitane seed crystal is 30: (5-10).
4. The process according to claim 1 or 2, wherein the volume ratio of the recrystallization solvent to the non-solvent is independently 1: (1.25-2.5).
5. The process according to claim 2, wherein the temperature of the saturated solution of hexanitrohexaazaisowurtzitane in step (1) and the temperature of the initial saturated solution of hexanitrohexaazaisowurtzitane in step a) are independently 20 to 45 ℃;
the temperature of the hexanitrohexaazaisowurtzitane suspension in the step (2) and the temperature of the initial hexanitrohexaazaisowurtzitane suspension in the step b) are independently 20-45 ℃;
the heat preservation temperature in the step (3) and the heat preservation temperature in the step c) are independently 20-45 ℃.
6. The method for preparing the ultra-large particle hexanitrohexaazaisowurtzitane composition as claimed in claim 2, wherein the incubation time in the step (3) and the incubation time in the step c) are independently 24-48 h.
7. The process of claim 1 or 2, wherein the recrystallization solvent is independently one or more of a polar ester solvent and a polar ketone solvent.
8. The process of claim 7, wherein the recrystallization solvent is independently one or more of ethyl acetate, methyl acetate, acetone, and methyl ethyl ketone.
9. The process according to claim 1 or 2, wherein the non-solvent is independently one or more of an alkane and a cycloalkane.
10. The process of claim 9, wherein the non-solvent is independently one or more of hexane, heptane, octane, and cyclohexane.
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