CN112939816A - Production method for refining guanidine nitrate by one-step method - Google Patents
Production method for refining guanidine nitrate by one-step method Download PDFInfo
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- CN112939816A CN112939816A CN202110031247.XA CN202110031247A CN112939816A CN 112939816 A CN112939816 A CN 112939816A CN 202110031247 A CN202110031247 A CN 202110031247A CN 112939816 A CN112939816 A CN 112939816A
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- C07—ORGANIC CHEMISTRY
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- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/02—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups of guanidine from cyanamide, calcium cyanamide or dicyandiamides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/06—Purification or separation of guanidine
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Abstract
The invention discloses a production method for refining guanidine nitrate by a one-step method, which takes dicyandiamide and ammonium nitrate as initial raw materials to prepare a guanidine nitrate crude product, adopts natural cooling and frozen brine cooling crystallization to naturally cool to 30 ℃, the frozen brine cools to 10 ℃, and centrifugally separates to obtain the guanidine nitrate product. According to the production method for refining guanidine nitrate by one-step method provided by the invention, the content of the prepared guanidine nitrate product is higher than 99%, the yield is higher than 60%, and the refined mother solution can be recycled.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a production method for refining guanidine nitrate by a one-step method.
Background
Guanidine nitrate is an important intermediate material, is mainly used for synthesizing medical pesticide intermediates such as sulfadiazine and the like, can be used in the fields of rocket propellants, paint industry, photographic materials, disinfectants and the like, can also be used as a fuel of a gas generating agent in an automobile safety airbag, and provides higher quality requirements for the purity of guanidine nitrate due to increasingly refined requirements.
At present, guanidine nitrate is refined mainly by a hydrosolvent method and alkaline liquor, and if guanidine nitrate prepared by the method is not circularly applied and directly discharged and treated by mother liquor, the mother liquor contains a certain amount of guanidine nitrate products, so that the cost is wasted, the water treatment is difficult, and the problems of easy blockage of filtration, multiple operation processes, low guanidine nitrate purity and the like exist if the mother liquor is circularly applied for a long time.
Therefore, the problem to be solved by the technical personnel in the field is how to provide a production method for refining guanidine nitrate by a one-step method, which is simple to operate and qualified in product.
Disclosure of Invention
The invention aims to provide a production method for refining guanidine nitrate by a one-step method aiming at the defects in the prior art, the refined guanidine nitrate can be obtained by the one-step method by taking methanol as a solvent and adopting the modes of dissolution, cooling and crystallization, the obtained guanidine nitrate has high content and good crystal form, meets the product quality standard requirements, and the methanol can be recycled by vacuum concentration.
In order to achieve the purpose, the invention adopts the following technical scheme:
the production method of the one-step refined guanidine nitrate comprises the following steps:
s1, preparing a guanidine nitrate crude product by using dicyandiamide and ammonium nitrate in a molten state by adopting a continuous sectional heating method;
s2, adding absolute methanol into the guanidine nitrate crude product obtained in the step S1, stirring and dissolving, heating to 60-64 ℃, carrying out reflux reaction for 30-45min, cooling, crystallizing, and carrying out centrifugal separation to obtain the guanidine nitrate product.
Preferably, in step S1, the mass ratio of the dicyandiamide to the ammonium nitrate is: 1:(1.18-1.30).
Preferably, in step S1, the operation of the continuous stepwise heating method is: heating the mixture to the temperature of 120 ℃ and 130 ℃ by steam, heating the mixture to the temperature of 205 ℃ and 212 ℃, and preserving the heat for 10-15 min.
Preferably, in step S1, the temperature increase rate is: 8-10 ℃/min.
Preferably, in step S2, the mass ratio of the anhydrous methanol to the crude guanidine nitrate is: (5.6-6.2):1.
Preferably, in step S2, the cooling operation is: cooling to 30-35 deg.C by one or more of natural cooling, circulating water or frozen saline water, and cooling to 10-15 deg.C by frozen saline water.
The technical effect of adopting the technical scheme is as follows: the crystallization is less influenced by the cooling rate above 30 ℃, so that various cooling modes can be adopted, and when the temperature is lower than 30 ℃, the frozen brine can be rapidly cooled, so that guanidine nitrate is rapidly separated out, impurities are left in the solvent, and the purity of the guanidine nitrate product is improved.
Preferably, in step S2, after centrifugal separation, the refined mother liquor is recycled by vacuum concentration, and the residue is subjected to solid waste treatment, wherein the residue is mainly ammonium nitrate.
Preferably, in step S2, steam is turned on during dissolution, and the stirring rate is 200-350 r/min.
The invention also provides guanidine nitrate prepared by the production method for refining guanidine nitrate by the one-step method.
Through the technical scheme, compared with the prior art, the invention discloses a production method for refining guanidine nitrate by one-step method, which has the following technical effects:
(1) the production method for refining guanidine nitrate by one-step method provided by the invention improves the crystal form of guanidine nitrate, increases the content of guanidine nitrate and ensures that the product quality meets the product quality standard requirement.
(2) The invention provides a guanidine nitrate refining method with simple operation, which takes methanol as a solvent to prepare guanidine nitrate with higher content by a one-step method of dissolution, cooling crystallization and centrifugal separation, wherein the content of the obtained guanidine nitrate is higher than 99 percent, and the yield is higher than 60 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a process flow diagram of a production method of one-step refined guanidine nitrate in the embodiment of the invention.
Detailed Description
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 of the 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.
The embodiment of the invention provides a production method for refining guanidine nitrate by a one-step method, which comprises the following steps:
s1, preparing a guanidine nitrate crude product by using dicyandiamide and ammonium nitrate in a molten state by adopting a continuous sectional heating method;
s2, adding absolute methanol into the guanidine nitrate crude product obtained in the step S1, stirring and dissolving, heating to 62-X ℃, carrying out reflux reaction for 30-Xmin, cooling, crystallizing, and carrying out centrifugal separation to obtain the guanidine nitrate product.
In order to further optimize the above technical solution, in step S1, the mass ratio of dicyandiamide to ammonium nitrate is: 1:(1.18-1.30).
In order to further optimize the above technical solution, in step S1, the operation of the continuous stepwise heating method is as follows: heating the mixture to the temperature of 120 ℃ and 130 ℃ by steam, heating the mixture to the temperature of 205 ℃ and 212 ℃, and preserving the heat for 10-15 min.
In order to further optimize the above technical solution, in step S1, the temperature increase rate is: 8-10 ℃/min.
In order to further optimize the technical scheme, in step S2, the mass ratio of the anhydrous methanol to the crude guanidine nitrate is: (5.6-6.2):1.
In order to further optimize the above technical solution, in step S2, the cooling operation is: cooling to 30-45 deg.C by one or more of natural cooling, circulating water or frozen saline water, and cooling to 10-15 deg.C by frozen saline water.
In order to further optimize the above technical solution, in step S2, the cooling rate is: 2-10 ℃/min.
In order to further optimize the technical scheme, in step S2, after centrifugal separation, the refined mother liquor is recycled through vacuum concentration, and the kettle residue is treated by solid waste.
In order to further optimize the above technical solution, in step S2, steam is turned on during dissolution, and the stirring rate is 200-350 r/min.
Example 1
The embodiment provides a production method for refining guanidine nitrate by a one-step method, which comprises the following steps:
s1, adding dicyandiamide and ammonium nitrate into the reaction kettle, feeding the dicyandiamide and the ammonium nitrate according to the mass ratio of 1:1.18, and preparing a guanidine nitrate crude product in a molten state by adopting a continuous and segmented temperature rising method, wherein the heating adopts the continuous and segmented temperature rising method, steam is heated to 130 ℃, and the temperature is naturally raised to 205 ℃.
S2, adding the guanidine nitrate crude product obtained in the step S1 into industrial anhydrous methanol according to a certain proportion, feeding the industrial anhydrous methanol and the guanidine nitrate crude product according to the mass ratio of 5.6:1, stirring and dissolving, starting steam for heating when dissolving, raising the temperature to 62 ℃, and carrying out reflux reaction for 30 min; then naturally cooling to 30 ℃, cooling the frozen brine to 10 ℃, recrystallizing the guanidine nitrate, then centrifugally separating to obtain a guanidine nitrate product, recycling the refined mother liquor, and treating the kettle residue by solid waste.
The content of guanidine nitrate obtained in the embodiment is higher than 99% through detection, and the yield is higher than 60%.
Example 2
The embodiment provides a production method for refining guanidine nitrate by a one-step method, which comprises the following steps:
s1, adding dicyandiamide and ammonium nitrate into the reaction kettle, feeding the dicyandiamide and the ammonium nitrate according to the mass ratio of 1:1.30, and preparing a guanidine nitrate crude product in a molten state by adopting a continuous and segmented temperature rising method, wherein the heating adopts the continuous and segmented temperature rising method, steam is heated to 120 ℃, and the temperature is naturally raised to 212 ℃.
S2, adding the guanidine nitrate crude product obtained in the step S1 into industrial anhydrous methanol according to a certain proportion, feeding the industrial anhydrous methanol and the guanidine nitrate crude product according to the mass ratio of 6.2:1, stirring and dissolving, starting steam for heating when dissolving, raising the temperature to 62 ℃, and carrying out reflux reaction for 30 min; then the circulating water is cooled to 30 ℃, the frozen brine is cooled to 10 ℃, after the guanidine nitrate is recrystallized, the guanidine nitrate product is obtained by centrifugal separation, the refined mother liquor is recycled, and the kettle residue is treated by solid waste.
The content of guanidine nitrate obtained in the embodiment is higher than 99% through detection, and the yield is higher than 60%.
Example 3
The embodiment provides a production method for refining guanidine nitrate by a one-step method, which comprises the following steps:
s1, adding dicyandiamide and ammonium nitrate into the reaction kettle, feeding the dicyandiamide and the ammonium nitrate according to the mass ratio of 1:20, and preparing a guanidine nitrate crude product in a molten state by adopting a continuous segmented temperature rising method, wherein the heating adopts the continuous segmented temperature rising method, steam is heated to 125 ℃, and the temperature is naturally raised to 208 ℃.
S2, adding the guanidine nitrate crude product obtained in the step S1 into industrial anhydrous methanol according to a certain proportion, feeding the industrial anhydrous methanol and the guanidine nitrate crude product according to the mass ratio of 6.8:1, stirring and dissolving, starting steam for heating when dissolving, raising the temperature to 62 ℃, and carrying out reflux reaction for 30 min; then naturally cooling to 30 ℃, cooling the frozen brine to 10 ℃, recrystallizing the guanidine nitrate, then centrifugally separating to obtain a guanidine nitrate product, recycling the refined mother liquor, and treating the kettle residue by solid waste.
The content of guanidine nitrate obtained in the embodiment is higher than 99% through detection, and the yield is higher than 60%.
Comparative example 1
The comparative example provides a production method of refined guanidine nitrate, which mainly uses water as a solvent, and the water is heated to 70-80 ℃ to dissolve a guanidine nitrate crude product, the guanidine nitrate crude product is dissolved for 30-60min, a proper amount of sodium hydroxide solution is added to adjust the pH value to 9-10, impurities are removed by suction filtration, a proper amount of inorganic base is added to the filtrate, the filtrate is obtained by suction filtration, the filtrate is cooled, stirred and crystallized, and then is centrifuged to obtain a guanidine nitrate fine product, and the mother liquor is recycled and reused for 20-30 times.
In order to further illustrate the technical effects of the present invention, the applicant also measured the purified guanidine nitrate obtained in the above examples 1 to 3 and comparative example 1, and the results are shown in table 1.
TABLE 1 test result chart of the refined guanidine nitrate obtained in examples 1 to 3 and comparative example 1
As can be seen from the data in Table 1, compared with comparative example 1, the content of the refined guanidine nitrate obtained in examples 1 to 3 is obviously increased, and the content of other impurities is obviously reduced.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The production method for refining guanidine nitrate by one-step method is characterized by comprising the following steps:
s1, preparing a guanidine nitrate crude product by using dicyandiamide and ammonium nitrate in a molten state by adopting a continuous sectional heating method;
s2, adding absolute methanol into the guanidine nitrate crude product obtained in the step S1, stirring and dissolving, heating to 60-64 ℃, carrying out reflux reaction for 30-45min, cooling, crystallizing, and carrying out centrifugal separation to obtain the guanidine nitrate product.
2. The production method for refining guanidine nitrate according to the one-step method of claim 1, wherein in step S1, the mass ratio of dicyandiamide to ammonium nitrate is 1 (1.18-1.30).
3. The production method for refining guanidine nitrate according to the one-step method of claim 1, wherein in step S1, the continuous stepwise heating method is operated as follows: heating the mixture to the temperature of 120 ℃ and 130 ℃ by steam, heating the mixture to the temperature of 205 ℃ and 212 ℃, and preserving the heat for 10-15 min.
4. The production method for refining guanidine nitrate according to claim 1, wherein in step S1, the temperature increase rate is: 8-10 ℃/min.
5. The production method for refining guanidine nitrate by one-step method according to claim 1, wherein in step S2, the mass ratio of the anhydrous methanol to the crude guanidine nitrate is (5.6-6.2): 1.
6. The production method for refining guanidine nitrate according to claim 1, wherein in step S2, the temperature reduction operation is: cooling to 30-35 deg.C by one or more of natural cooling, circulating water or frozen saline water, and cooling to 10-15 deg.C by frozen saline water.
7. The production method for refining guanidine nitrate according to claim 6, wherein in step S2, the temperature decrease rate is: 2-10 ℃/min.
8. The production method for refining guanidine nitrate according to the one-step method of claim 1, wherein in step S2, after centrifugal separation, the refined mother liquor is recycled by vacuum concentration, and the still residue is treated by solid waste.
9. The method for producing refined guanidine nitrate according to claim 1, wherein in step S2, steam is turned on during dissolution, and the stirring rate is 200-350 r/min.
10. Guanidine nitrate produced by the method for producing a purified guanidine nitrate according to any one of claims 1 to 9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924337A (en) * | 2012-11-02 | 2013-02-13 | 南通天泽化工有限公司 | Production process of guanidine nitrate |
| CN103450048A (en) * | 2013-08-06 | 2013-12-18 | 南通天泽化工有限公司 | Continuous synthesis process of guanidine nitrate |
| CN103951592A (en) * | 2014-05-19 | 2014-07-30 | 宁夏贝利特化工有限公司 | Production technique of guanidine nitrate |
| CN111018747A (en) * | 2019-12-17 | 2020-04-17 | 南通天泽化工有限公司 | Method for refining guanidine nitrate |
| CN111087326A (en) * | 2020-01-13 | 2020-05-01 | 宁夏贝利特生物科技有限公司 | Method for refining guanidine nitrate |
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- 2021-01-11 CN CN202110031247.XA patent/CN112939816A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924337A (en) * | 2012-11-02 | 2013-02-13 | 南通天泽化工有限公司 | Production process of guanidine nitrate |
| CN103450048A (en) * | 2013-08-06 | 2013-12-18 | 南通天泽化工有限公司 | Continuous synthesis process of guanidine nitrate |
| CN103951592A (en) * | 2014-05-19 | 2014-07-30 | 宁夏贝利特化工有限公司 | Production technique of guanidine nitrate |
| CN111018747A (en) * | 2019-12-17 | 2020-04-17 | 南通天泽化工有限公司 | Method for refining guanidine nitrate |
| CN111087326A (en) * | 2020-01-13 | 2020-05-01 | 宁夏贝利特生物科技有限公司 | Method for refining guanidine nitrate |
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Application publication date: 20210611 |