CN114105826A - Method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid - Google Patents
Method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid Download PDFInfo
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- CN114105826A CN114105826A CN202111142624.3A CN202111142624A CN114105826A CN 114105826 A CN114105826 A CN 114105826A CN 202111142624 A CN202111142624 A CN 202111142624A CN 114105826 A CN114105826 A CN 114105826A
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- nitric acid
- liquid ammonia
- dilute nitric
- guanidine nitrate
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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
- C07C277/02—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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/18—Nitrates of ammonium
- C01C1/185—Preparation
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- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid. The method synthesizes the ammonium nitrate by utilizing the reaction of the gasified liquid ammonia and the dilute nitric acid, the exothermic reaction can bring out water, and then the ammonium nitrate and the dicyandiamide react to generate the guanidine nitrate.
Description
Technical Field
The invention relates to the technical field of chemical production, in particular to a method for directly producing guanidine nitrate by utilizing liquid ammonia and dilute nitric acid.
Background
Guanidine nitrate is an important pharmaceutical intermediate with a molecular formula of CH5N3·HNO3Molecular weight 122.08. As a white granular solid. Guanidine nitrate is soluble in water and alcohol, and insoluble in acetone, benzene and ether. The method is mainly used for synthesizing sulfonamides such as sulphaguanidine and the like, is also used as a raw material for manufacturing explosives, photographic materials and disinfectants, and can also be used as an analytical reagent for detecting guanidine salt in complex acid. Oxidative and toxic. Decompose and explode at high temperatures. The main application is as follows: is a new material of an automobile safety airbag, and is used for synthesizing pharmaceutical intermediates such as sulfadiazine and the like, rocket propellant, paint industry, photographic materials, disinfectants and other fields.
At present, guanidine nitrate is produced mainly by mixing ammonium nitrate and dicyandiamide, melting and heating the mixture in a reaction kettle to about 110 ℃, naturally heating the mixture to 200-220 ℃ by means of reaction heat release, preserving the temperature for a plurality of minutes, cooling and slicing the mixture, and finally obtaining a crude guanidine nitrate product.
Firstly, the ammonium nitrate as the raw material is a chemical with extremely high danger coefficient, and has great potential safety hazard in storage and transportation.
Therefore, the reduction of the safety problem in the production, storage and transportation of ammonium nitrate is also an urgent problem to be solved at present, guanidine nitrate is also a great explosive dangerous chemical, and the reduction of the danger in the production process is also a technical problem to be solved at present.
Storage and transport of ammonium nitrate
1. Characteristic of danger
Strong oxidizers, which promote a fire when they catch fire, can react violently with combustible powders and explode, can explode even when they are subjected to strong shocks, can explode when they are heated sharply, and can form explosive mixtures when they are mixed with reducing agents, organic substances, combustibles such as sulfur, phosphorus or metal powders.
2. Notes on storage
Ammonium nitrate is not resistant to high temperature, is easy to generate thermal decomposition, starts to generate decomposition at 110 ℃, is ignited when being heated at 160 ℃, and explodes at 210 ℃. So that ammonium nitrate is stored in a cool, ventilated storehouse. Away from the fire and heat source. The powder should be stored separately from the combustible (combustible) substances, reducing agents, acids and active metal powder, and is not mixed with the active metal powder. The reservoir should be provided with a suitable material to contain the leakage. Vibrations, impacts and friction are prohibited.
The ammonium nitrate warehouse management unit should make and strictly implement a regular inspection system, check the temperature and humidity in the warehouse, the stacking firmness and abnormal phenomena, and make inspection records to ensure that the temperature in the warehouse is lower than 30 ℃ and the humidity is lower than 80%.
The ammonium nitrate operation needs to strictly implement a double-person receiving and sending and double-person keeping system, and the ammonium nitrate warehouse needs to ensure that people are on duty within 24 hours, and the number of people on duty is not less than two.
3. Attention points to transportation
During railway transportation, the dangerous goods are strictly assembled according to a dangerous goods assembling table in a railway department (dangerous goods transportation rule). The container is separately shipped during transportation, and the container is ensured not to be leaked, collapsed, dropped and damaged during transportation. During transportation, fire fighting equipment of corresponding varieties and quantity should be equipped on the transportation vehicle. Strictly preventing acid, inflammable matters, organic matters, reducing agents, spontaneous combustion articles,
High-temperature inflammable materials and the like are used in combination, the speed of the vehicle is not too fast during transportation, the vehicle cannot be overtaken forcibly, and the transportation vehicle is thoroughly cleaned before and after loading and unloading, and organic matters, inflammable materials and other impurities are strictly forbidden to be mixed.
Hazard grade: first type of integral explosive hazardous article
Explosiveness: the explosive power is huge, and the explosive equivalent of 1.8 tons of ammonium nitrate is about 1 ton of TNT explosive
Liquid ammonia storage and transport
1. Attention points to transportation
And filling the liquid ammonia as toxic gas by using a steel cylinder or a tank car. The steel cylinder or tank car for filling is in accordance with the relevant regulations of 'gas cylinder safety supervision regulation', 'fixed pressure vessel safety technology supervision regulation' issued by the national labor bureau. The weight-filling factor was allowed to be 0.52 kg/L. The steel cylinders and tank cars for loading and transporting the liquid ammonia must meet the dangerous goods transportation rules set by the ministry of communication of the people's republic of China, and heating and smoke are avoided in the transportation process. The steel cylinder must be provided with a safety cap, and the cylinder is bound by a rubber ring or a straw rope to prevent violent impact and vibration. The liquid ammonia steel cylinder is stored on a storehouse or a platform with a shed. When the stacks are placed in the open air, the stacks are covered by a tent to prevent direct sunlight. Mainly by rail and road transport.
And (3) packaging marking: toxic gas
The packaging method comprises the following steps: a steel gas cylinder.
Pressure-resistant liquefied gas enterprise self-supply tank car capable of being used in railway transportation time limit
2. Notes on storage
Storing in a cool and ventilated storehouse. Away from the fire and heat source. The temperature of the storage is not more than 30 ℃. The food should be stored separately from oxidant, acid, halogen and edible chemicals, and should not be stored in a mixed manner. Explosion-proof lighting and ventilation facilities are adopted. Mechanical devices and tools that are prone to spark generation are prohibited. The reservoir should be equipped with leak emergency treatment equipment.
Hazard grade: second type third toxic gas
Explosiveness: is free of
Dilute nitric acid
Notes on storage
Storing in a cool and ventilated storehouse. Away from the fire and heat source. The storage temperature is not more than 30 ℃ and the relative humidity is not more than 80%. Keeping the container sealed. Should be stored separately with reducing agent, alkalies, alcohols, alkali metals, etc., rather than mixed with each other. The reservoir should be provided with leak emergency treatment equipment and appropriate containment materials.
Attention points to transportation
Loading the dilute nitric acid by a railway tank wagon, and conveying or storing the dilute nitric acid by a stainless steel or glass fiber reinforced plastic tank wagon or a storage tank. A small amount of the product is packaged by acid-resistant ceramic jars or glass bottles, and the net weight of each jar is 33-40 kg. The dilute nitric acid is sealed by gypsum. Each jar is loaded into a sturdy wooden box lined with fine coal slag or fine mineral slag for transport. The package should have an obvious "corrosive product" mark. Because the surface of the aluminum has an oxide film, the aluminum plays a role in passivation and is economical, so the aluminum is an ideal container for nitric acid. The individual protection prohibits direct skin contact, and acid and alkali resistant gloves, masks and other labor protection articles are needed to be carried during operation.
Hazard grade: corrosion products of the eighth group
Explosiveness: is free of
From the safety and convenience of the storage and transportation of the ammonium nitrate, the liquid ammonia and the dilute nitric acid, the dangerousness of the liquid ammonia and the dilute nitric acid is lower than that of the ammonium nitrate, the explosion risk is avoided, the storage and the transportation are in harsh conditions relative to the ammonium nitrate, and the liquid ammonia and the dilute nitric acid are very safe and convenient.
Therefore, it is a technical problem to be solved urgently by those skilled in the art to provide a novel method for preparing guanidine nitrate to reduce the risk in the production process thereof.
Disclosure of Invention
In view of the above, the present invention provides a new method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for directly producing guanidine nitrate by utilizing liquid ammonia and dilute nitric acid comprises the following steps: firstly, liquid ammonia is gasified into ammonia gas, then the ammonia gas is introduced into dilute nitric acid to react to generate ammonium nitrate, dicyandiamide is added into the ammonium nitrate to carry out melting and heat preservation, and guanidine nitrate is prepared by discharging and slicing.
Further, the method for directly producing guanidine nitrate by utilizing liquid ammonia and dilute nitric acid comprises the following steps:
(1) gasifying liquid ammonia by adopting a gasification device;
(2) gradually introducing the gasified liquid ammonia into a vacuum flask filled with dilute nitric acid to perform neutralization reaction, discharging heat in the reaction, and heating the reaction system to 70-150 ℃ by utilizing the reaction heat;
(3) keeping the temperature of the reaction system, completely gasifying and volatilizing the moisture to obtain ammonium nitrate in a molten state, and then adding dicyandiamide to perform an exothermic reaction;
(4) the reaction system is heated to 180 ℃ and 230 ℃ by utilizing the reaction heat release, and the temperature is kept;
(5) the materials are discharged into a cooling disc for cooling while the materials are hot, and then the materials are sliced to obtain the guanidine nitrate.
Further, the mass ratio of the liquid ammonia to the dilute nitric acid is 0.15-0.18: 1.
Furthermore, the mass concentration of the dilute nitric acid is 30-65%.
Further, the mass ratio of the liquid ammonia dosage to the dicyandiamide dosage is 0.35-0.45: 1.
Further, the heat preservation time in the step (4) is 5-20 min.
The beneficial effect of adopting the further scheme is that: the reaction speed of the melt synthesis of the guanidine nitrate is high, the heat preservation time is suitable within 5-20min, and the completeness of the reaction can be ensured.
Further, the cooling temperature in the step (5) is 20-25 ℃.
The invention has the beneficial effects that: the method for synthesizing the ammonium nitrate by using the gasified liquid ammonia and the dilute nitric acid to react to synthesize the ammonium nitrate, the water can be brought out by the exothermic reaction, and then the ammonium nitrate and the dicyandiamide react to generate the guanidine nitrate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, 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.
Example 1
After 135g of liquid ammonia is gasified, 875g of dilute nitric acid (the mass fraction is 60%) is added into a heat-preservation reaction bottle, the reaction releases heat, the temperature is 70 ℃, generated water vapor is removed, 340g of dicyandiamide is gradually added into the reaction bottle, and the system melting state is kept until dicyandiamide is added. The reaction of the system releases heat, the temperature rises, when the temperature rises to 230 ℃, the temperature is preserved for 10min, the materials are discharged into a cooling tray, and the materials are cooled, weighed and analyzed. 1000g of the product is obtained, and the content of guanidine nitrate is 92.4 percent.
Example 2
142g of liquid ammonia is gasified, 875g of dilute nitric acid (the mass fraction is 60%) is added into a heat-preservation reaction bottle, the reaction releases heat, the temperature is 150 ℃, generated water vapor is removed, 330g of dicyandiamide is gradually added into the reaction bottle, and the system is kept in a molten state until dicyandiamide is added completely. The reaction of the system releases heat, the temperature rises, when the temperature rises to 220 ℃, the temperature is preserved for 10min, the materials are discharged into a cooling tray, and the materials are cooled, weighed and analyzed. 989g of product is obtained, and the content of guanidine nitrate is 92.2%.
Example 3
After 152g of liquid ammonia is gasified, 875g of dilute nitric acid (the mass fraction is 60%) is added into a heat-preservation reaction bottle, the reaction releases heat, the temperature is 120 ℃, generated water vapor is removed, 350g of dicyandiamide is gradually added into the reaction bottle, and the system is kept in a molten state until dicyandiamide is added completely. The reaction of the system releases heat, the temperature rises, when the temperature rises to 200 ℃, the temperature is preserved for 10min, the materials are discharged into a cooling tray, and the materials are cooled, weighed and analyzed. 1004g of product is obtained, and the content of guanidine nitrate is 92.2 percent.
Example 4
After 135g of liquid ammonia is gasified, 875g of dilute nitric acid (the mass fraction is 60%) is added into a heat-preservation reaction bottle, the reaction releases heat, the temperature is 130 ℃, generated water vapor is removed, 340g of dicyandiamide is gradually added into the reaction bottle, and the system melting state is kept until dicyandiamide is added. The reaction of the system releases heat, the temperature rises, when the temperature rises to 180 ℃, the temperature is preserved for 10min, the materials are discharged into a cooling tray, and the materials are cooled, weighed and analyzed. 1000g of the product is obtained, and the content of guanidine nitrate is 91.7 percent.
Example 5
142g of liquid ammonia is gasified, 875g of dilute nitric acid (the mass fraction is 60%) is added into a heat-preservation reaction bottle, the reaction releases heat, the temperature is 140 ℃, generated water vapor is removed, 340g of dicyandiamide is gradually added into the reaction bottle, and the system melting state is kept until dicyandiamide is added. The reaction of the system releases heat, the temperature rises, when the temperature rises to 190 ℃, the temperature is preserved for 10min, the materials are discharged into a cooling tray, and the materials are cooled, weighed and analyzed. 1002g of product is obtained, and the content of guanidine nitrate is 91.6 percent.
Example 6
After 152g of liquid ammonia is gasified, 875g of dilute nitric acid (the mass fraction is 60%) is added into a heat-preservation reaction bottle, the reaction releases heat, the temperature is 90 ℃, generated water vapor is removed, 340g of dicyandiamide is gradually added into the reaction bottle, and the system melting state is kept until dicyandiamide is added. The reaction of the system releases heat, the temperature rises, when the temperature rises to 210 ℃, the temperature is preserved for 10min, the materials are discharged into a cooling tray, and the materials are cooled, weighed and analyzed. 997g of the product is obtained, and the content of guanidine nitrate is 92.8 percent.
Example tuning parameters are shown in table 1.
TABLE 1
The results of guanidine nitrate assay obtained in examples 1-6 are shown in Table 2.
TABLE 2
| Sequence number/item | Guanidine nitrate/g | Main content/%) | Dicyandiamide unit consumption (raw material/product) | Appearance of the product |
| Example 1 | 1000 | 92.4 | 0.340 | White crystal |
| Example 2 | 965 | 92.2 | 0.342 | White crystal |
| Example 3 | 1004 | 92.2 | 0.349 | White crystal |
| Example 4 | 1000 | 91.5 | 0.340 | White crystal |
| Example 5 | 997 | 91.6 | 0.341 | White crystal |
| Example 6 | 1002 | 92.8 | 0.340 | White crystal |
From the above results, it can be seen that the unit consumption of the final product (guanidine nitrate) can reach 0.34 by strictly controlling the process index, especially when the dicyandiamide is added in an amount of 340g at the holding temperature of 200 ℃ and 205 ℃ in example 6, the product quality is the best, the yield is the highest or the unit consumption is the lowest.
Therefore, the method directly utilizes the gasified liquid ammonia and the dilute nitric acid to react to produce the guanidine nitrate, not only can normally produce the guanidine nitrate, but also has lower unit consumption, and most importantly, directly avoids using the ammonium nitrate, so that the huge risk generated in the process of storing and transporting the ammonium nitrate is greatly reduced.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (7)
1. A method for directly producing guanidine nitrate by utilizing liquid ammonia and dilute nitric acid is characterized by comprising the following steps: firstly, liquid ammonia is gasified into ammonia gas, then the ammonia gas is introduced into dilute nitric acid to react to generate ammonium nitrate, dicyandiamide is added into the ammonium nitrate to carry out melting and heat preservation, and guanidine nitrate is prepared by discharging and slicing.
2. The method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid as claimed in claim 1, which comprises the following steps:
(1) gasifying liquid ammonia by adopting a gasification device;
(2) gradually introducing the gasified liquid ammonia into a vacuum flask filled with dilute nitric acid to perform neutralization reaction, discharging heat in the reaction, and heating the reaction system to 70-150 ℃ by utilizing the reaction heat;
(3) keeping the temperature of the reaction system, obtaining ammonium nitrate in a molten state after completely gasifying and volatilizing the moisture, and then adding dicyandiamide to perform a melting exothermic reaction;
(4) the reaction system is heated to 180 ℃ and 230 ℃ by utilizing the reaction heat release, and the temperature is kept;
(5) the materials are discharged into a cooling disc for cooling while the materials are hot, and then the materials are sliced to obtain the guanidine nitrate.
3. The method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid as claimed in claim 2, wherein the mass ratio of the liquid ammonia to the dilute nitric acid is 0.15-0.18: 1.
4. The method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid as claimed in claim 3, wherein the mass concentration of the dilute nitric acid is 30-65%.
5. The method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid as claimed in claim 2, wherein the mass ratio of the amount of liquid ammonia to the amount of dicyandiamide is 0.35-0.45: 1.
6. The method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid as claimed in claim 2, wherein the holding time in step (4) is 5-20 min.
7. The method for directly producing guanidine nitrate by using liquid ammonia and dilute nitric acid according to claim 2, wherein the cooling temperature in the step (5) is 20-25 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431301A (en) * | 1944-10-25 | 1947-11-18 | Honorary Advisory Council Sci | Preparation of guanidine nitrate |
| SU106838A1 (en) * | 1956-10-22 | 1956-11-30 | П.А. Воронин | The method of producing guanidine nitrate |
| US3009949A (en) * | 1958-04-09 | 1961-11-21 | Deere & Co | Production of guanidine salts |
| CN102924337A (en) * | 2012-11-02 | 2013-02-13 | 南通天泽化工有限公司 | Production 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 |
| CN113292459A (en) * | 2021-06-17 | 2021-08-24 | 湖南吴赣药业有限公司 | Continuous nitration method of guanidine nitrate |
-
2021
- 2021-09-28 CN CN202111142624.3A patent/CN114105826A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2431301A (en) * | 1944-10-25 | 1947-11-18 | Honorary Advisory Council Sci | Preparation of guanidine nitrate |
| SU106838A1 (en) * | 1956-10-22 | 1956-11-30 | П.А. Воронин | The method of producing guanidine nitrate |
| US3009949A (en) * | 1958-04-09 | 1961-11-21 | Deere & Co | Production of guanidine salts |
| CN102924337A (en) * | 2012-11-02 | 2013-02-13 | 南通天泽化工有限公司 | Production 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 |
| CN113292459A (en) * | 2021-06-17 | 2021-08-24 | 湖南吴赣药业有限公司 | Continuous nitration method of guanidine nitrate |
Non-Patent Citations (1)
| Title |
|---|
| 燃料化学工业部科学技术情报研究所: "《国外石油化工流程图解》", 3 December 1972 * |
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