CN115724773A - Method for preparing superfine nitroguanidine by virtue of supergravity hydrolytic crystallization method - Google Patents
Method for preparing superfine nitroguanidine by virtue of supergravity hydrolytic crystallization method Download PDFInfo
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- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 66
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- 230000007062 hydrolysis Effects 0.000 claims abstract description 84
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 84
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- -1 nitroguanidine sulfate sulfuric acid Chemical compound 0.000 claims abstract description 43
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- 230000008025 crystallization Effects 0.000 claims abstract description 20
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 27
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 21
- 230000018044 dehydration Effects 0.000 claims description 20
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- 239000012267 brine Substances 0.000 claims description 15
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 15
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Abstract
The application provides a method for preparing superfine nitroguanidine by a supergravity hydrolytic crystallization method, which comprises the following steps: and respectively and continuously inputting water and the nitroguanidine sulfate sulfuric acid solution into a supergravity hydrolysis crystallizer for hydrolysis crystallization, and dehydrating, washing and drying a crystallization product to obtain the superfine nitroguanidine. The invention can directly hydrolyze and crystallize to obtain spherical nitroguanidine with 3-5 μm particles, which effectively meets the requirements of downstream high-end products; the process is simple, the target product is obtained in one step, and the method is very safe and environment-friendly; in addition, the method has the characteristics of operation continuity, simple and controllable reaction conditions, high reaction safety and the like, and can be directly applied to actual production.
Description
Technical Field
The invention belongs to the technical field of nitroguanidine preparation, and particularly relates to a method for preparing superfine nitroguanidine by a supergravity hydrolytic crystallization method.
Background
Nitroguanidine is an important industrial raw material, can be used for pesticides and medical intermediates, and can also be used as gas production drugs, rockets, missiles, explosives and other solid propellants and warhead charging of automobile safety airbags. The nitroguanidine has excellent comprehensive performance, can be used as an explosive and other explosive products, and can be used as an energetic additive of a low-characteristic signal propellant by utilizing the characteristics of moderate energy, low sensitivity and the like. Most of crystal forms of nitroguanidine prepared by the traditional method are acicular, and the nitroguanidine directly applied to explosives has the defects of poor free-running property, poor mechanical property and the like.
At present, superfine nitroguanidine is prepared at home and abroad mainly through a physical method and a chemical method, wherein the physical method mainly adopts an ultrasonic wave crushing technology, a grinding and refining technology and an impinging stream crushing and refining technology, and the chemical method mainly adopts a solvent-non-solvent recrystallization and refining technology and a micro-emulsification and refining technology, so that the two methods have the problems of high energy consumption and poor safety performance.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing superfine nitroguanidine by a hypergravity hydrolysis crystallization method.
The invention provides a method for preparing superfine nitroguanidine by a supergravity hydrolytic crystallization method, which comprises the following steps:
and respectively and continuously inputting water and the nitroguanidine sulfate sulfuric acid solution into a supergravity hydrolysis crystallizer for hydrolysis crystallization.
In an alternative embodiment, after the water and the nitroguanidine sulfate sulfuric acid solution are continuously fed into the high-gravity hydrolysis crystallizer for hydrolysis crystallization, the method further comprises the following steps: and dehydrating, washing and drying the crystallized product to obtain the superfine nitroguanidine.
In an alternative embodiment, the nitroguanidine sulfate sulfuric acid solution is prepared by the following steps:
adding 98% sulfuric acid into a dehydration kettle, stirring and cooling with a refrigerant;
when the temperature is lower than 40 ℃, guanidine nitrate is uniformly added;
and (4) preserving the heat after the addition is finished to obtain the nitroguanidine sulfate hydrochloride sulfuric acid solution.
In an alternative embodiment, the mass ratio of the 98% sulfuric acid to the guanidine nitrate is (1-3): 1.
In an alternative embodiment, the temperature is kept between 35 ℃ and 40 ℃ for 0.5 to 3 hours after the end of the feeding.
In an alternative embodiment, water and nitroguanidine sulfate sulfuric acid solution are continuously fed into a supergravity hydrolytic crystallizer for hydrolytic crystallization, respectively, and the method comprises the following steps:
adding a refrigerant into the supergravity hydrolysis crystallizer for cooling;
injecting process water into the hypergravity hydrolysis crystallizer;
when the water temperature in the hypergravity hydrolysis crystallizer is 5-25 ℃, adding nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer;
the nitroguanidine sulfate sulfuric acid solution is continuously hydrolyzed and crystallized under the action of supergravity to obtain the spherical nitroguanidine.
In an alternative embodiment, the mass ratio of the process water to the nitroguanidine sulfate sulfuric acid solution is (2-5): 1.
In an alternative embodiment, the cryogen is a chilled brine.
In an alternative embodiment, the temperature of the hydrolysis crystallization of the nitroguanidine sulfate sulfuric acid solution in the hypergravity hydrolysis crystallizer is controlled between 5 and 10 ℃.
In an alternative embodiment, the nitroguanidine has a pH of 6.5 to 7 after the washing step.
Based on the above embodiment, the invention provides a method for preparing ultrafine nitroguanidine by a supergravity hydrolysis crystallization method, which comprises the following steps: and respectively and continuously inputting water and the nitroguanidine sulfate sulfuric acid solution into a supergravity hydrolysis crystallizer for hydrolysis crystallization, and dehydrating, washing and drying a crystallization product to obtain the superfine nitroguanidine. Compared with the prior art, the invention has the following beneficial technical effects:
(1) The method prepares the ultrafine nitroguanidine from the nitroguanidine sulfate sulfuric acid solution through the hypergravity hydrolysis crystallizer, has the characteristics of continuous operation, simple and controllable reaction conditions, high reaction safety and the like, and can be directly applied to actual production;
(2) The spherical nitroguanidine with the particle size of 3-5 mu m can be directly hydrolyzed and crystallized by the supergravity hydrolytic crystallizer, so that the requirement of downstream high-end products is effectively met;
(3) The hypergravity environment in the hypergravity hydrolysis crystallizer is utilized, the coalescence among crystal nuclei can be prevented, the dispersity of nitroguanidine crystals in liquid is improved, the directional adhesion forming of free molecules on the crystal nucleus surface caused by hydrogen bond bonding force in the crystallization process of nitroguanidine is avoided, the final precipitation of needle-shaped crystals with large volume is avoided, and the growth of the crystal nuclei can be inhibited by the hypergravity environment. Under the condition of ultrahigh-speed operation, nitroguanidine molecules do not have the chance of long-time aggregation, crystal nuclei are difficult to form elongated crystals, products are quickly precipitated in a fine spherical crystal mode finally, and the particle size meets the use requirements of military industry;
(4) The method has simple process, obtains the target product in one step, is very safe and is environment-friendly; meanwhile, compared with the conventional hydrolysis crystallization method, the continuous production is realized by intermittent operation, the particle size of the nitroguanidine can not reach the standard from one time to one time, the particles are changed into spheres from needles, and the process of further grinding and crushing is omitted.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the application.
Drawings
In order to more clearly explain the technical solution of the present application, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious to those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow chart of a method for preparing ultrafine nitroguanidine by hydrolysis crystallization under supergravity according to an embodiment of the present invention;
FIG. 2 is an electron microscope scan of the product of example 1 of the present invention;
FIG. 3 is a chromatogram of the product of example 1 according to the present invention;
FIG. 4 is a chromatogram of a standard sample of the product of example 1.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
FIG. 1 is a schematic flow chart of a method for preparing ultrafine nitroguanidine by hydrolysis crystallization under supergravity according to an embodiment of the present invention; FIG. 2 is an electron microscope scan of the product of example 1 of the present invention; FIG. 3 is a chromatogram of the product of example 1 according to the present invention; FIG. 4 is a chromatogram of a standard sample of the product of example 1. The method for preparing ultrafine nitroguanidine by hydrolysis and crystallization under supergravity provided by the embodiment of the invention is described in detail below with reference to fig. 1 to 4.
As shown in figure 1, the method for preparing the superfine nitroguanidine by the hypergravity hydrolysis crystallization method comprises the following steps:
and respectively and continuously inputting water and the nitroguanidine sulfate sulfuric acid solution into a supergravity hydrolysis crystallizer for hydrolysis crystallization, and dehydrating, washing and drying a crystallization product to obtain the superfine nitroguanidine.
Specifically, the preparation method of the nitroguanidine sulfate sulfuric acid solution comprises the following steps: adding 98% sulfuric acid into a dehydration kettle, stirring, and cooling with frozen brine; when the temperature is lower than 40 ℃, uniformly adding guanidine nitrate by an auger, controlling the adding temperature to be 35-40 ℃, wherein the mass ratio of 98 percent sulfuric acid to guanidine nitrate is (1-3) to 1; and after the addition is finished, controlling the temperature to be between 35 and 40 ℃ and preserving the heat for 0.5 to 3 hours, wherein the further heat preservation time can be 1 hour, so as to obtain the nitroguanidine sulfate sulfuric acid solution.
Respectively and continuously inputting water and nitroguanidine sulfate sulfuric acid solution into a supergravity hydrolysis crystallizer for hydrolysis crystallization, and the method comprises the following steps: starting the hypergravity hydrolysis crystallizer, and adding frozen brine into the hypergravity hydrolysis crystallizer for cooling; starting a process water constant-flow centrifugal pump to inject process water into the hypergravity hydrolysis crystallizer; when the water temperature in the hypergravity hydrolysis crystallizer is 5-25 ℃, preferably 10 ℃, starting a material transferring pump of a dehydration kettle to add nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer; controlling the mass ratio of the process water to the nitroguanidine sulfate sulfuric acid solution to be (2-5): 1 by a mass flow meter, and controlling the internal temperature of the hypergravity hydrolysis crystallizer to be 5-10 ℃ by adjusting the flow of the frozen brine; at the moment, the nitroguanidine sulfate sulfuric acid solution is continuously hydrolyzed under the effect of supergravity and rapidly crystallized at low temperature to obtain the spherical nitroguanidine.
And (3) collecting a crystallized product flowing out of the supergravity hydrolysis crystallizer, adding the crystallized product into a centrifuge for dehydration, washing with primary water, stopping washing when the pH value of the spherical nitroguanidine is 6.5-7, and centrifugally spin-drying to remove water to obtain a superfine nitroguanidine product.
Example 1
(1) Adding 3000g of 98% sulfuric acid into a 5L dehydration four-mouth glass bottle dehydration kettle, starting stirring, cooling by using frozen saline water, uniformly adding 1000g of guanidine nitrate by using an auger when the temperature is reduced to 40 ℃, controlling the charging temperature to be 35-40 ℃, keeping the temperature for 1h at 35-40 ℃ after charging is finished, and dehydrating the guanidine nitrate by using concentrated sulfuric acid to obtain a nitroguanidine sulfate sulfuric acid solution;
(2) Starting the hypergravity hydrolysis crystallizer, and adding frozen brine into the hypergravity hydrolysis crystallizer to cool; starting a process water constant-flow centrifugal pump to inject process water into the hypergravity hydrolysis crystallizer; starting a dehydration kettle to transfer a material constant flow pump when the water temperature in the hypergravity hydrolysis crystallizer is 10 ℃, adding nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer, controlling the mass ratio of process water to the nitroguanidine sulfate sulfuric acid solution to be 3 by a mass flow meter, controlling the internal temperature of the hypergravity hydrolysis crystallizer to be 5-10 ℃ by adjusting the flow of frozen brine, and continuously hydrolyzing guanidine nitrate under the conditions of constant current and hypergravity and quickly crystallizing at low temperature to obtain spherical nitroguanidine;
(3) Collecting the spherical nitroguanidine flowing out of the supergravity hydrolysis crystallizer, adding the collected spherical nitroguanidine into a 5000L centrifuge in batches, dehydrating and washing with primary water, stopping washing when the pH value of the spherical nitroguanidine is 6.7, and centrifugally spin-drying to remove water to obtain a superfine nitroguanidine product;
(4) As shown in fig. 2 to 4, the content of the superfine nitroguanidine dry product is as follows: 99.2% (external standard method); average particle size: 4.4 μm; the length-diameter ratio of the crystal form is as follows: 5.2; the shape is as follows: and (4) a spherical shape.
Example 2
(1) Adding 2000g of 98% sulfuric acid into a 5L dehydration four-mouth glass bottle dehydration kettle, starting stirring, cooling by using frozen saline water, uniformly adding 1000g of guanidine nitrate by using an auger when the temperature is reduced to 40 ℃, controlling the feeding temperature to be 35-40 ℃, keeping the temperature for 1h at 35-40 ℃ after the feeding is finished, and dehydrating the guanidine nitrate by using concentrated sulfuric acid to obtain a nitroguanidine sulfate sulfuric acid solution;
(2) Starting a supergravity hydrolysis crystallizer, adding frozen brine into the supergravity hydrolysis crystallizer for cooling, and starting a process water constant-flow centrifugal pump to inject process water into the supergravity hydrolysis crystallizer; starting a dehydration kettle to transfer a material constant flow pump when the water temperature in the hypergravity hydrolysis crystallizer is 10 ℃, adding nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer, controlling the mass ratio of process water to the nitroguanidine sulfate sulfuric acid solution to be 3 by a mass flow meter, controlling the internal temperature of the hypergravity hydrolysis crystallizer to be 5-10 ℃ by adjusting the flow of frozen brine, and continuously hydrolyzing guanidine nitrate under the conditions of constant current and hypergravity and quickly crystallizing at low temperature to obtain spherical nitroguanidine;
(3) Collecting the spherical nitroguanidine flowing out of the supergravity hydrolysis crystallizer, adding the collected spherical nitroguanidine into a 5000L centrifuge in batches, dehydrating and washing with primary water, stopping washing when the pH value of the spherical nitroguanidine is 7, and centrifugally spin-drying to remove water to obtain a superfine nitroguanidine product;
(4) Content of superfine dry nitroguanidine: 98.5% (external standard method), average particle diameter: 4.8 μm, crystal aspect ratio: 6.4; the appearance is as follows: and (4) a spherical shape.
Example 3
(1) Adding 1000g of 98% sulfuric acid into a 5L dehydration four-mouth glass bottle dehydration kettle, starting stirring, cooling by using frozen saline, uniformly adding 1000g of guanidine nitrate by using an auger when the temperature is reduced to 40 ℃, controlling the charging temperature to be 35-40 ℃, keeping the temperature for 1h at 35-40 ℃ after the charging is finished, and dehydrating the guanidine nitrate by concentrated sulfuric acid to obtain a nitroguanidine sulfate sulfuric acid solution;
(2) Starting the hypergravity hydrolysis crystallizer, and adding frozen brine into the hypergravity hydrolysis crystallizer to cool; starting a process water constant-flow centrifugal pump to inject process water into the hypergravity hydrolysis crystallizer; starting a dehydration kettle to transfer a material constant flow pump when the water temperature in the hypergravity hydrolysis crystallizer is 10 ℃, adding nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer, controlling the mass ratio of process water to the nitroguanidine sulfate sulfuric acid solution to be 3 by a mass flow meter, controlling the internal temperature of the hypergravity hydrolysis crystallizer to be 5-10 ℃ by adjusting the flow of frozen brine, and continuously hydrolyzing guanidine nitrate under the conditions of constant current and hypergravity and quickly crystallizing at low temperature to obtain spherical nitroguanidine;
(3) Collecting the spherical nitroguanidine flowing out of the supergravity hydrolysis crystallizer, adding the collected spherical nitroguanidine into a 5000L centrifuge in batches, dehydrating and washing with primary water, stopping washing when the pH value of the spherical nitroguanidine is 6.5, and centrifugally spin-drying to remove water to obtain a superfine nitroguanidine product;
(4) Content of superfine dry nitroguanidine: 98.1% (external standard method); average particle size: 5.4 μm; the length-diameter ratio of the crystal form is as follows: 6.8; the appearance is as follows: and (4) a spherical shape.
Example 4
(1) Adding 3000g of 98% sulfuric acid into a 5L dehydration four-mouth glass bottle dehydration kettle, starting stirring, cooling by using frozen saline water, uniformly adding 1000g of guanidine nitrate by using an auger when the temperature is reduced to 40 ℃, controlling the feeding temperature to be 35-40 ℃, keeping the temperature for 1h at 35-40 ℃ after the feeding is finished, and dehydrating the guanidine nitrate by using concentrated sulfuric acid to obtain a nitroguanidine sulfate sulfuric acid solution;
(2) Starting the hypergravity hydrolysis crystallizer, and adding frozen brine into the hypergravity hydrolysis crystallizer for cooling; starting a process water constant-flow centrifugal pump to inject process water into the hypergravity hydrolysis crystallizer; starting a dehydration kettle to transfer a material constant flow pump when the water temperature in the hypergravity hydrolysis crystallizer is 10 ℃, adding a nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer, controlling the mass ratio of process water to the nitroguanidine sulfate sulfuric acid solution to be 2 by a mass flow meter, controlling the internal temperature of the hypergravity hydrolysis crystallizer to be 5-10 ℃ by adjusting the flow of frozen brine, and continuously hydrolyzing guanidine nitrate under the conditions of constant current and hypergravity and quickly crystallizing at low temperature to obtain spherical nitroguanidine;
(3) Collecting the spherical nitroguanidine flowing out of the supergravity hydrolysis crystallizer, adding the collected spherical nitroguanidine into a 5000L centrifuge in batches, dehydrating and washing with primary water, stopping washing when the pH value of the spherical nitroguanidine is 6.5, and centrifugally spin-drying to remove water to obtain a superfine nitroguanidine product;
(4) Content of superfine dry nitroguanidine: 98.9% (external standard method); average particle size: 5.6 μm; the length-diameter ratio of the crystal form is as follows: 6.4; the shape is as follows: a spherical shape.
Example 5
(1) Adding 3000g of 98% sulfuric acid into a 5L dehydration four-mouth glass bottle dehydration kettle, starting stirring, cooling by using frozen saline water, uniformly adding 1000g of guanidine nitrate by using an auger when the temperature is reduced to 40 ℃, controlling the charging temperature to be 35-40 ℃, keeping the temperature for 1h at 35-40 ℃ after charging is finished, and dehydrating the guanidine nitrate by using concentrated sulfuric acid to obtain a nitroguanidine sulfate sulfuric acid solution;
(2) Starting the hypergravity hydrolysis crystallizer, and adding frozen brine into the hypergravity hydrolysis crystallizer to cool; starting a process water constant-flow centrifugal pump to inject process water into the hypergravity hydrolysis crystallizer; starting a dehydration kettle to transfer a material constant flow pump when the water temperature in the hypergravity hydrolysis crystallizer is 10 ℃, adding nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer, controlling the mass ratio of process water to the nitroguanidine sulfate sulfuric acid solution to be 5 through a mass flow meter, controlling the internal temperature of the hypergravity hydrolysis crystallizer to be 5-10 ℃ through adjusting the flow of frozen brine, and continuously hydrolyzing guanidine nitrate under the conditions of constant current and hypergravity and quickly crystallizing at low temperature to obtain spherical nitroguanidine;
(3) Collecting the spherical nitroguanidine flowing out of the supergravity hydrolysis crystallizer, adding the collected spherical nitroguanidine into a 5000L centrifuge in batches, dehydrating and washing with primary water, stopping washing when the pH value of the spherical nitroguanidine is 6.5, and centrifugally spin-drying to remove water to obtain a superfine nitroguanidine product;
(4) Content of superfine dry nitroguanidine: 98.2% (external standard method); average particle size: 4.6 μm; the length-diameter ratio of the crystal form is as follows: 4.8; the appearance is as follows: a spherical shape.
Through the method for preparing the superfine nitroguanidine by hydrolysis and crystallization under the supergravity of the embodiments 1 to 5, the qualified superfine nitroguanidine products can be respectively obtained, the purity of the superfine nitroguanidine products can reach more than 98 percent, the particle size range is 3 to 5 mu m, and the shape of the crystal is spherical.
The foregoing summary, as well as the included examples, of preferred embodiments of the present invention will be more readily understood by reference to the following detailed description of the preferred embodiments of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
As used herein, the term "consisting of 8230; preparation" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 8230comprises" excludes any non-specified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230title" appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; no other elements are excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise specified, the range is intended to include the endpoints thereof, and all integers and fractions within the range.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
Approximating language, as used herein throughout the specification and claims, is intended to modify a quantity, such that the invention is not limited to the specific quantity, but includes portions that are literally received for modification without substantial change in the basic function to which the invention is related. Accordingly, the use of "about" to modify a numerical value means that the invention is not limited to the precise value. In some instances, the approximating language may correspond to the precision of an instrument for measuring the value. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to have no limitation on the number (i.e., number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
Claims (10)
1. A method for preparing superfine nitroguanidine by a hypergravity hydrolysis crystallization method is characterized by comprising the following steps:
and respectively and continuously inputting water and the nitroguanidine sulfate sulfuric acid solution into a supergravity hydrolysis crystallizer for hydrolysis crystallization.
2. The method for preparing superfine nitroguanidine according to claim 1, wherein after water and nitroguanidine sulfate sulfuric acid solution are continuously fed into a super-gravity hydrolysis crystallizer for hydrolysis crystallization, the method further comprises the following steps: and dehydrating, washing and drying the crystallized product to obtain the superfine nitroguanidine.
3. The method for preparing the superfine nitroguanidine according to the super-gravity hydrolysis crystallization method of claim 1, wherein the method for preparing the nitroguanidine sulfate sulfuric acid solution comprises the following steps:
adding 98% sulfuric acid into a dehydration kettle, stirring and cooling with a refrigerant;
when the temperature is lower than 40 ℃, guanidine nitrate is uniformly added;
and (4) preserving the heat after the addition is finished to obtain the nitroguanidine sulfate hydrochloride sulfuric acid solution.
4. The method for preparing the ultrafine nitroguanidine according to claim 3, wherein the mass ratio of the 98% sulfuric acid to the guanidine nitrate is (1-3): 1.
5. The method for preparing the superfine nitroguanidine by the hypergravity hydrolysis crystallization method according to claim 3, characterized in that the temperature is kept between 35 ℃ and 40 ℃ for 0.5 to 3 hours after the feeding is finished.
6. The method for preparing the ultrafine nitroguanidine according to claim 1, wherein the water and the nitroguanidine sulfate sulfuric acid solution are continuously fed into the supergravity hydrolytic crystallizer respectively for hydrolytic crystallization, and the method comprises the following steps:
adding a refrigerant into the hypergravity hydrolysis crystallizer for cooling;
injecting process water into the hypergravity hydrolysis crystallizer;
when the water temperature in the hypergravity hydrolysis crystallizer is 5-25 ℃, adding nitroguanidine sulfate sulfuric acid solution into the hypergravity hydrolysis crystallizer;
the nitroguanidine sulfate sulfuric acid solution is continuously hydrolyzed and crystallized under the action of supergravity to obtain the spherical nitroguanidine.
7. The method for preparing the ultrafine nitroguanidine according to the super-gravity hydrolysis crystallization method of claim 6, wherein the mass ratio of the process water to the nitroguanidine sulfate sulfuric acid solution is (2-5): 1.
8. The method for preparing ultra-fine nitroguanidine according to claim 3 or 6, wherein the refrigerant is frozen brine.
9. The method for preparing superfine nitroguanidine according to claim 6, wherein the temperature of the hydrolysis crystallization of the nitroguanidine sulfate sulfuric acid solution in the hypergravity hydrolysis crystallizer is controlled to be 5-10 ℃.
10. The method for preparing ultra-fine nitroguanidine according to claim 2, wherein the pH value of nitroguanidine after the washing step is 6.5-7.
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