CN1021732C - Process for continuous preparation of nitroguanidine in pipe - Google Patents
Process for continuous preparation of nitroguanidine in pipe Download PDFInfo
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- CN1021732C CN1021732C CN 87103545 CN87103545A CN1021732C CN 1021732 C CN1021732 C CN 1021732C CN 87103545 CN87103545 CN 87103545 CN 87103545 A CN87103545 A CN 87103545A CN 1021732 C CN1021732 C CN 1021732C
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- nitroguanidine
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- nitric acid
- washing water
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Abstract
The present invention relates to a technique for the continuous preparation of nitroguanidine in a pipe. Guanidine nitrate is continuously sent into a premixer by a solid feeder for mixing the guanidine nitrate with nitric acid which continuously flows into the premixer, and the nitroguanidine is obtained in the pipe under the conditions of the reaction temperature of 30 to 50 DEG C, the stay time of 25 to 35 minutes and the dilution temperature of-5 to 5 DEG C; the purity of the nitroguanidine is over 99%, and the yield of the nitroguanidine is over 90%. The technique has the advantages of compact structure, small space occupation, simple operation and convenient automation control.
Description
The invention belongs to a kind of method for preparing nitroguanidine, adopted the continuous processing of duct type.Nitroguanidine is a kind of explosive substance, because its products of combustion is littler than the corrodibility of other propelling charge with identical energy, thereby is widely used as the component of gun propellant, again because its sensitivity is low, specific volume is big, the explosion velocity height, thereby can be used as the composition that hangs down Vulnerability Explosive again.For these reasons, the research of the manufacturing process of nitroguanidine comes into one's own always, the past, the method of producing nitroguanidine mostly adopts vitriol oil evaporation both at home and abroad, though this method technology is simple, productive rate is also than higher, but Dilution of sulphuric acid to 25% need be separated nitroguanidine to get off, produce a large amount of dilute sulphuric acids thus, power consumption is big when concentrating.In order to overcome this shortcoming, Britain Matthias Thoma declared the patent for preparing nitroguanidine with the nitric acid nitrating Guanidinium nitrate in 1978, and GB2006201 number, adopt the interruption legal system to be equipped with nitroguanidine technology, be unfavorable for realizing the production automation.We find that nitroguanidine can part decompose in concentrated nitric acid, when temperature is higher than 45 ℃, the reaction times, the nitroguanidine yield obviously descended greater than 30 minutes; Find that also solubleness and the temperature relation of nitroguanidine in rare nitric acid is very big, at washing process because the dissolving of nitroguanidine reduces yield greatly.Can make qualified product without recrystallization though this patent is mentioned, not mentionedly how remove residual acid problem in the lattice.
The objective of the invention is to overcome decomposition and the dissolving in rare nitric acid of nitroguanidine, and remove residual acid between lattice, realize the production serialization, make standard compliant crystallization nitroguanidine with short-cut method at concentrated nitric acid.
Enforcement the invention reside in feeder for solid materials (1), Guanidinium nitrate (6) sent in the premixed device (2) to mix with the nitric acid of the concentration that continuously flows into 〉=97% continuously make nitric acid/Guanidinium nitrate mass ratio equal 2～3/1, through screw-pushing type agitator (3) deliver to carry out in the pipeline reactor (4) nitrated (7), Guanidinium nitrate in concentrated nitric acid at first by the nitrate of nitrated one-tenth nitroguanidine, after the cooling dilution, promptly from reaction solution, crystallize out, after filtration, washing is hydrolyzed into nitroguanidine, drying makes finished product, and its reaction formula is as follows:
Characteristics of the present invention are to adopt duct type continuous nitrification technology, are based on to have found that nitroguanidine can decompose this brass tacks in concentrated nitric acid.The selected reaction times of still formula flow reactor is mean residence time, the partial reaction liquid residence time is greater than mean residence time, there is the partial nitro guanidine to decompose, and another part reaction solution residence time is less than mean residence time, then reaction is incomplete, and both of these case all can cause the nitroguanidine yield to descend.The duct type continuous reaction process has just overcome this shortcoming, and liquid mobile thrust in pipeline provides by spiral thruster in the premixed device, thereby does not produce " dead angle ".Whole reaction system can remain on the optimum response state, i.e. nitric acid/Guanidinium nitrate=2.0～3.0/1(mass ratio) 30～50 ℃ of temperature of reaction; 25～35 minutes residence time; Concentration of nitric acid 〉=97%; Dilution temperature-5～5 ℃; Dilution water and nitric acid mass ratio=1: 1.
Another characteristics of the present invention can adopt washing water to recycle to reduce the solution loss of nitroguanidine, promptly the 4th the new water of usefulness (15) is washed, the 4th washing water (13) are used for the third time, washing water (12) are done to use for the second time for the third time, washing water (11) are made usefulness for the first time for the second time, and washing water (10) are made dilution water usefulness for the first time, can keep water balance like this, the gained concentration of nitric acid is about 50%, can directly enter waste acid recovery system.
Another characteristics of the present invention are residual acids of removing between the nitroguanidine lattice, and these residual acids can not be used the usual method flush away, can adopt the vacuum high-temperature oven drying method, vacuum tightness 〉=6000mmHg, and 80～120 ℃ of temperature through 4～8 hours, can be removed residual acid.
The present invention also goes for strict controlled temperature and reaction times, can obtaining close effect through the existing explosive continuous production device of transforming.
Duct type continuous processing compact construction of the present invention, it is little that equipment occupies the space, easy and simple to handle, easily be automated control, the nitroguanidine productive rate all can surpass 90%, and product need not change crystalline substance can reach standard-required, it is little that nitric acid reclaims energy consumption, and available usual method reclaims, thereby cost can descend greatly, and gained nitroguanidine quality index of the present invention is as shown in the table.(table is seen the literary composition back)
Embodiment
Commercially available Guanidinium nitrate (dullness 〉=96%) is dried after feeder for solid materials (1) adds to the speed of Guanidinium nitrate (6) with 310 Grams Per Minutes in the premixed device (2), with 97% concentrated nitric acid (5) uniform mixing that flows into the speed of 780 ml/min, deliver to through spiral propeller (3) and to carry out nitrated (7) in the pipeline reactor (4), pipeline reactor is with 40～45 ℃ of hot water circulation, keep temperature of reaction at 45 ℃, after reaction in 30 minutes, continuously flow in the dilution machine (8), the dilution temperature is 0 ℃, the nitrate of nitroguanidine is separated out from nitric acid with fine crystallization, flowing into filter (9) again filters, through four washings (10-13), the washing water consumption is identical with the concentrated nitric acid consumption, and washing water recycle.The nitroguanidine of gained carries out vacuum-drying (14), vacuum tightness 650 mmhg, and 110 ℃ of bake out temperatures, drying time 8 hours promptly gets the nitroguanidine finished product, total recovery 92.1%, product dullness 99.2%.
The total fugitive constituent acidity pH water insoluble matter dullness (%) of sequence number outward appearance granularity (μ)
（%） （%）
1 white crystals 3.10 0.17 0.03 5.0 0.04 99.79
2 white crystals 2.50 0.16 0.02 5.1 0.08 99.68
Claims (3)
1, a kind of preparation has the method for the nitroguanidine of following formula,
This method comprises the nitrate that generates nitroguanidine with the nitrated Guanidinium nitrate of concentrated nitric acid, through cooling dilution post crystallization, washing is hydrolyzed into nitroguanidine after filtration, make finished product after the vacuum-drying, it is characterized in that Guanidinium nitrate being delivered to premixed device (2) continuously with feeder for solid materials (1), mix with the concentration that continuously flows into 〉=97% nitric acid, make nitric acid/Guanidinium nitrate mass ratio equal 2～3/1, through spiral propelling agitator (3), deliver to pipeline reactor (4), 30～50 ℃ of temperature of reaction, 25～35 minutes residence time, dilution temperature-5～5 ℃, dilution water and nitric acid mass ratio=1: 1.
2, according to the method for claim 1, it is characterized in that it is that the 4th the new water of usefulness (15) is washed that the nitroguanidine washing water recycle, the 4th washing water (13) are used for the third time, washing water (12) are done to use for the second time for the third time, washing water (11) are made usefulness for the first time for the second time, and washing water (10) do dilution is for the first time used.
3, according to the method for claim 1, it is characterized in that the oven dry of nitroguanidine oven dry employing vacuum high-temperature, vacuum tightness is the 600-650 mmhg, 80～120 ℃ of temperature kept 4～8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103545 CN1021732C (en) | 1987-05-18 | 1987-05-18 | Process for continuous preparation of nitroguanidine in pipe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87103545 CN1021732C (en) | 1987-05-18 | 1987-05-18 | Process for continuous preparation of nitroguanidine in pipe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87103545A CN87103545A (en) | 1988-11-30 |
| CN1021732C true CN1021732C (en) | 1993-08-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87103545 Expired - Fee Related CN1021732C (en) | 1987-05-18 | 1987-05-18 | Process for continuous preparation of nitroguanidine in pipe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021732C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497579B (en) * | 2009-03-26 | 2012-05-23 | 里程 | Green process for producing nitroguanidine |
| CN102827038B (en) * | 2012-08-28 | 2014-02-05 | 西安近代化学研究所 | Preparation process for nitroguanidine |
| CN103193682B (en) * | 2013-03-28 | 2015-08-26 | 常州大学 | In Continuous Flow micro passage reaction, Guanidinium nitrate acidifying Dehydration is for the method for nitroguanidine |
| CN103787922B (en) * | 2014-03-04 | 2016-06-01 | 新昌县鸿吉电子科技有限公司 | A kind of Industrial Catalysis method of synthesizing nitryl substitution compound |
| CN104860849A (en) * | 2015-06-04 | 2015-08-26 | 西安近代化学研究所 | Continuous crystallization process for preparing nitroguanidine through nitric acid method |
| CN110204461B (en) * | 2019-05-15 | 2022-04-05 | 西安万德能源化学股份有限公司 | Nitroguanidine crystal and microchannel crystallization process and device of nitroguanidine |
-
1987
- 1987-05-18 CN CN 87103545 patent/CN1021732C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN87103545A (en) | 1988-11-30 |
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