CN102295583A - Novel method for preparing biurea by using ketazine - Google Patents
Novel method for preparing biurea by using ketazine Download PDFInfo
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- CN102295583A CN102295583A CN2011101755039A CN201110175503A CN102295583A CN 102295583 A CN102295583 A CN 102295583A CN 2011101755039 A CN2011101755039 A CN 2011101755039A CN 201110175503 A CN201110175503 A CN 201110175503A CN 102295583 A CN102295583 A CN 102295583A
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- ketazine
- hydrazo
- dicarbonamide
- urea
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Abstract
The invention relates to a novel method for preparing biurea by using ketazine, comprising the following steps: first adding sulfuric acid or hydrochloric acid having the same molar content with ketazine in ketazine to generate pure hydrazine sulfate or hydrazine hydrochloride, then adding urea solid at one time, rapidly heating up to 105-120 DEG C to obtain biurea. The method has the advantages that: 1, by using ketazine and sulfuric acid (hydrochloric acid ) to generate hydrazine sulfate (hydrazine hydrochloride), long hydrolysis and concentration process existing in traditional technology are avoided, the method has rapid reaction, the prepared hydrazine sulfate has high purity, and the prepared biruea has high yield; 2, by letting hydrazine sulfate and urea be subject to reaction, the heating speed is rapid, the purity of the product is high, and the yield of the prepared biruea reaches more than 85%; and 3, the by-product ammonium salt can be subject to recovery of ammonia with ammonia distillation technology and then returns to a synthesizer of ketazine, so that the cyclic utilization of all materials are realized.
Description
Technical field
The present invention relates to produce the method for hydrazo-dicarbonamide, mainly is a kind of novel method of utilizing ketazine to prepare hydrazo-dicarbonamide.
Background technology
The English name of hydrazo-dicarbonamide is biurea, and chemical name is the hydrazo diformamide, and molecular formula is C2H6N4O2, and chemical formula is H2NCONH-NHCON2H.It is mainly used in and produces ADC whipping agent (Cellmic C 121), also can be used for airstrip, the super highway, and gear anti-skidding, senior fireproofing of cable is anti-to be melted.
The method of producing hydrazo-dicarbonamide at present is mainly hydrazine hydrate and urea condensation generation hydrazo-dicarbonamide, and domestic hydrazine hydrate generally is to adopt Wyler's process, and promptly urea and hypochlorite oxidation generate hydrazine hydrate; The external general ketazine hydrolysis of adopting, carry dense, refining back becomes the hydrazine hydrate finished product, this process generally needs the long reaction times, though someone proposes to adopt acid condensation, promptly regulate hydrolyzed solution pH 1-4 with sulfuric acid, really improved the reaction times, but owing to add sulfuric acid is a small amount of, have a spot of ammonium sulfate in the hydrazo-dicarbonamide generative process in the solution, recycle these small amount of ammonium sulfate if take efforts, difficulty is bigger on technology, and cost is higher, therefore the general producer that adopts acid condensation to produce hydrazo-dicarbonamide directly discharges rare ammoniumsulphate soln, and this has not only caused the pollution of environment to destroy, and is the waste to resource.
Summary of the invention
Purpose of the present invention will overcome the deficiency of above-mentioned technology just, and provide a kind of novel method of utilizing ketazine to prepare hydrazo-dicarbonamide, this method adopts ketazine and sulfuric acid (hydrochloric acid) to generate hydrazonium sulfate (hydrazine hydrochloride), pure hydrazonium sulfate (hydrazine hydrochloride) becomes hydrazo-dicarbonamide with urea condensation, because it is normal adding the amount of sulfuric acid (hydrochloric acid), therefore rest solution is pure ammonium sulfate (ammonium chloride) solution behind the end reaction, ammonium sulfate (ammonium chloride) adopts the milk of lime ammonia distillation process to reclaim ammonia, the ammonia that reclaims can return the production of carrying out ketazine in the ketazine synthesizer, can reach whole circulations of material like this.This technology has reduced acetone azine hydrolysis on the traditional technology, extracting and concentrating technology, and the reaction times is shorter, reacts completely the product purity height.Though increased ammonia distillation process, production cost is low than traditional technology.And this technology is if in west areas such as Qinghai, owing to be located in the plateau, so ammonia still process can adopt nature to steam to shine, and that more has superiority on cost.
The present invention solves the technical scheme that its technical problem adopts: this novel method of utilizing ketazine to prepare hydrazo-dicarbonamide, and this method comprises following step:
(1), at first in the 1L there-necked flask, adds the 200-500mL ketazine;
(2), under 60-90 ℃, according to mol ratio acetone azine: the ratio of sulfuric acid (or hydrochloric acid)=1: 1, drip normal acid solution, make ketazine and sour complete reaction, generate pure hydrazonium sulfate or hydrazine hydrochloride; Ketazine and vitriolic temperature of reaction are 60-90 ℃, avoid reaction temperature to spend that low acetone can't steam or the volatilization of the too high ketazine of temperature.
(3), treat that acid dropwises, according to mol ratio acetone azine: the ratio of urea=1: 2.5-3.5, the load weighted urea of disposable adding is rapidly heated;
(4), when treating that solution temperature arrives 105-120 ℃ in the there-necked flask, pick up counting continuation stirring 1-3h with the white precipitate generation;
(5), the white precipitate that obtains, filter, wash twice with water, in 50 ℃ baking oven, dry, obtain hydrazo-dicarbonamide.
The structure of described ketazine is:
Wherein, R1 and R2 can be identical, also can be different, and R1R2 can be a methyl, ethyl, propyl group, other alkyl and aryl.
After step (5), ammonium salt as by-product by is pure ammonium salt, and filtrate can adopt unslaked lime to carry out ammonia still process, and the ammonia that obtains can be used for the production of ketazine, realizes the recycle of material.
Used acid can be adopted the sulfuric acid or the hydrochloric acid soln of different concns.
Among the present invention, the urea of adding is solid, and purpose is to increase concentration of reactants, and yield is raise; After urea solid added there-necked flask, temperature was elevated to 105-120 ℃ fast, and avoiding slowly heats up causes the decomposition of urea.
Core of the present invention is that ketazine and equivalent sulfuric acid (hydrochloric acid) generate pure hydrazonium sulfate (hydrazine hydrochloride) earlier, and hydrazonium sulfate (hydrazine hydrochloride) becomes hydrazo-dicarbonamide with urea condensation again.The invention has the advantages that: 1. adopt ketazine and sulfuric acid (hydrochloric acid) to generate hydrazonium sulfate (hydrazine hydrochloride), shortened the reaction times, the hydrazonium sulfate purity height that obtains, transformation efficiency height.2. adopt hydrazonium sulfate (hydrazine hydrochloride) and urea to react, heat-up rate is fast, the product purity height, and the hydrazo-dicarbonamide yield that obtains is more than 85%.3. the ammonium salt of by-product can carry out the recycling of ammonia by the unslaked lime ammonia distillation process, can realize whole recycles of material.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with for example.Should be appreciated that described hereinly, and be not used in qualification the present invention for example only in order to explaining the present invention.
Embodiment 1
Get the there-necked flask of a 1L, add 200mL acetone azine, the sulfuric acid 500mL of preparation 1+1, get the 160mL sulphuric acid soln, dropwise add in the there-necked flask, temperature of reaction is set to 60 ℃, treat that sulfuric acid dropwises, weighing 173g urea, disposable joining in the there-necked flask, oil bath temperature improves rapidly, when treating that temperature rises to 105 ℃, keep continuing under this temperature to stir, white precipitate will occur about ten minutes, continue to stir 2h, filter, wash twice with water, filtrate is carried out ammonia still process, and white precipitate is put into baking oven, 50 ℃ are dried by the fire 8h down, recording fusing point is 248 ℃, determines that white mass is a hydrazo-dicarbonamide, productive rate 85%.
Embodiment 2
Get the there-necked flask of a 1L, add the 200mL butanone azine, the sulfuric acid 500mL of configuration 1+2, get the 240mL sulphuric acid soln, dropwise add in the there-necked flask, temperature of reaction is set to 70 ℃, treat that sulfuric acid dropwises, weighing 173g urea, disposable joining in the there-necked flask, oil bath temperature improves rapidly, when treating that temperature rises to 110 ℃, keep continuing under this temperature to stir, white precipitate will occur about five minutes, continue to stir 2h, filter, wash twice with water, filtrate is carried out ammonia still process, and white precipitate is put into baking oven, 50 ℃ of baking 8h, fusing point is 248 ℃, determines that white mass is a hydrazo-dicarbonamide, productive rate 86%.
Embodiment 3
Get the there-necked flask of a 1L, add 200mL acetone azine, the hydrochloric acid 500mL of configuration 1+1, get the 260mL hydrochloric acid soln, dropwise add in the there-necked flask, temperature of reaction is set to 80 ℃, treat that hydrochloric acid dropwises, weighing 173g urea, disposable joining in the there-necked flask, oil bath temperature improves rapidly, when treating that temperature rises to 112 ℃, be that the adularescent precipitation produces, continue to be warming up to 120 ℃, and keep stirring 1h under this temperature, filter, wash twice with water, filtrate is carried out ammonia still process, and white precipitate is put into baking oven, 50 ℃ of baking 8h, fusing point is 248 ℃, determines that white mass is a hydrazo-dicarbonamide, productive rate 88%.
Be understandable that, for a person skilled in the art, technical scheme of the present invention and inventive concept be equal to replacement or change the protection domain that all should belong to the appended claim of the present invention.
Claims (4)
1. novel method of utilizing ketazine to prepare hydrazo-dicarbonamide, it is characterized in that: this method comprises following step:
(1), at first in the 1L there-necked flask, adds the 200-500mL ketazine;
(2), under 60-90 ℃, according to mol ratio acetone azine: the ratio of sulfuric acid (or hydrochloric acid)=1: 1, drip normal acid solution, generate pure hydrazonium sulfate or hydrazine hydrochloride;
(3), treat that acid dropwises, according to mol ratio acetone azine: the ratio of urea=1: 2.5-3.5, the load weighted urea of disposable adding is rapidly heated;
(4), when treating that solution temperature arrives 105-120 ℃ in the there-necked flask, pick up counting continuation stirring 1-3h with the white precipitate generation;
(5), the white precipitate that obtains, filter, wash twice with water, in 50 ℃ baking oven, dry, obtain hydrazo-dicarbonamide.
2. the novel method of utilizing ketazine to prepare hydrazo-dicarbonamide according to claim 1 is characterized in that: after step (5), filtrate adds unslaked lime and carries out ammonia still process, reclaims ammonia.
3. the novel method of utilizing ketazine to prepare hydrazo-dicarbonamide according to claim 1 is characterized in that: the sulfuric acid or the hydrochloric acid soln that adopt different concns.
4. the novel method of utilizing ketazine to prepare hydrazo-dicarbonamide according to claim 1 is characterized in that: the urea of adding is solid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101755039A CN102295583A (en) | 2011-06-25 | 2011-06-25 | Novel method for preparing biurea by using ketazine |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011101755039A CN102295583A (en) | 2011-06-25 | 2011-06-25 | Novel method for preparing biurea by using ketazine |
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| CN102295583A true CN102295583A (en) | 2011-12-28 |
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| CN2011101755039A Pending CN102295583A (en) | 2011-06-25 | 2011-06-25 | Novel method for preparing biurea by using ketazine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130849A (en) * | 2015-10-10 | 2015-12-09 | 杭州海虹精细化工有限公司 | Environment-friendly technology for unitedly preparing ADC foaming agent and ammonium chloride by using ketazine as raw material |
| CN112047312A (en) * | 2020-09-30 | 2020-12-08 | 重庆腾泽化学有限公司 | Preparation method of hydrazine sulfate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB740676A (en) * | 1953-06-05 | 1955-11-16 | Us Rubber Co | Method for the preparation of hydrazodicarbonamide |
| US3972878A (en) * | 1974-02-08 | 1976-08-03 | Produits Chimiques Ugine Kuhlmann | Method for preparing azines and hydrazones |
| CN1396126A (en) * | 2001-07-16 | 2003-02-12 | 巨化集团公司 | Process and gas-film air tower for treating hydrazine contained sewage generated in production of azodimethylamide |
| CN1425648A (en) * | 2001-12-14 | 2003-06-25 | 化学工业部西南化工研究设计院 | Process for preparing biurea |
| CN101219973A (en) * | 2008-01-22 | 2008-07-16 | 浙江海虹控股集团有限公司 | A kind of preparation method of biurea |
-
2011
- 2011-06-25 CN CN2011101755039A patent/CN102295583A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB740676A (en) * | 1953-06-05 | 1955-11-16 | Us Rubber Co | Method for the preparation of hydrazodicarbonamide |
| US3972878A (en) * | 1974-02-08 | 1976-08-03 | Produits Chimiques Ugine Kuhlmann | Method for preparing azines and hydrazones |
| CN1396126A (en) * | 2001-07-16 | 2003-02-12 | 巨化集团公司 | Process and gas-film air tower for treating hydrazine contained sewage generated in production of azodimethylamide |
| CN1425648A (en) * | 2001-12-14 | 2003-06-25 | 化学工业部西南化工研究设计院 | Process for preparing biurea |
| CN101219973A (en) * | 2008-01-22 | 2008-07-16 | 浙江海虹控股集团有限公司 | A kind of preparation method of biurea |
Non-Patent Citations (1)
| Title |
|---|
| 游贤德: "国内偶氮二甲酰胺发泡剂生产与应用", 《化学推进剂与高分子材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105130849A (en) * | 2015-10-10 | 2015-12-09 | 杭州海虹精细化工有限公司 | Environment-friendly technology for unitedly preparing ADC foaming agent and ammonium chloride by using ketazine as raw material |
| CN112047312A (en) * | 2020-09-30 | 2020-12-08 | 重庆腾泽化学有限公司 | Preparation method of hydrazine sulfate |
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Application publication date: 20111228 |