CN100348578C - Equipment of preparing birueal by using carbamide as raw material - Google Patents
Equipment of preparing birueal by using carbamide as raw material Download PDFInfo
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- CN100348578C CN100348578C CNB2005100877809A CN200510087780A CN100348578C CN 100348578 C CN100348578 C CN 100348578C CN B2005100877809 A CNB2005100877809 A CN B2005100877809A CN 200510087780 A CN200510087780 A CN 200510087780A CN 100348578 C CN100348578 C CN 100348578C
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Abstract
The present invention relates to equipment of preparing birueal by using carbamide as raw materials, which conforms to the requirements of economy and environment. The equipment comprises a pyrolyzing furnace, a recrystallization reactor, a first reactor, a second rector and an ammonia evaporator, wherein the pyrolyzing furnace is used for preparing biuret and ammonia by using pyrolyzed urea, and the recrystallization reactor is used for purifying the biuret obtained from the pyrolyzing furnace; the first reactor is used for preparing the metallic salt of halobiuret by the reaction of the biuret with metallic halate compounds or halogen and alkali, the second reactor is used for synthesizing birueal by the reaction of the metallic salt of halobiuret and the ammonia, and the ammonia evaporator is used for separating excessive ammonia from the birueal and delivering the separated ammonia to an ammonia concentrator.
Description
Invention field
The present invention relates to prepare as starting raw material the method and apparatus of hydrazo-dicarbonamide with urea, relate in particular to the method and apparatus that conforms with economy and environmental demand ground preparation hydrazo-dicarbonamide, it is by preparing biuret with urea, and the ammonia react that obtains in the biuret that obtains and the biuret building-up process is realized.
Background of invention
Hydrazo-dicarbonamide (HDCA) is the useful compound that a kind of conduct is used to prepare the raw material of azodicarbonamide, and azodicarbonamide can be widely used as pore forming material.As shown in reaction formula 1 below, by obtaining azodicarbonamide (2) with the oxygenant oxidation hydrazo-dicarbonamide (1) that is fit to.
[reaction formula 1]
The ordinary method of preparation hydrazo-dicarbonamide comprises following method: (i) use hydrazine as starting raw material, and (ii) directly synthetic from urea, (iii) make Urea,amino-with urea, then the Urea,amino-that obtains is changed into hydrazo-dicarbonamide, (iv) use biuret as starting raw material.
In using the method for hydrazine (reaction formula 2), prepare hydrazo-dicarbonamide by making 1 mole hydrazine (3) and 2 moles urea (4) reaction as starting raw material.
[reaction formula 2]
The advantage of above-mentioned reaction is that method is simple, and is synthetic and expensive but shortcoming is that the starting raw material hydrazine is difficult to.The exemplary process of preparation hydrazine comprises Raschig process (Raschig process) and uses the method for ketazine.Yet, also exist the hydrazine that makes by these methods to need the problem of concentration and hydrolysis treatment.Therefore, cost of energy and practical cost are too high, thereby manufacturing cost increases.In addition, also can make hydrazine by the urea method, the urea method is to instigate urea and clorox and sodium hydroxide reaction.But this method needs excessive sodium hydroxide, and the cost of removing the yellow soda ash by product is very high, and needs the number of chemical material to remove by product.Therefore, this method is considered to uneconomic, does not also conform with environmental demand.
Following reaction formula 3 shows the directly method of synthetic hydrazo-dicarbonamide of urea of using.Shown in reaction formula 3,3 moles urea and 4 moles sodium hydroxide, 1 mole chlorine reaction make 1 mole hydrazo-dicarbonamide.But, since need excessive reactant and process very complexity make preparation cost higher, so this method also is inappropriate.Another important problem is that a large amount of ammonia forms as by product, and this does not conform with environmental demand.
[reaction formula 3]
Following reaction formula 4 shows the method for another kind of synthetic hydrazo-dicarbonamide.This method comprises the steps: to make Urea,amino-with urea, subsequently the Urea,amino-that makes is changed into hydrazo-dicarbonamide.Shown in reaction formula 4, by making urea and sodium hypochlorite reaction make the monochloro-urea sodium salt, the reaction of monochloro-urea sodium salt and excess of ammonia makes intermediate (Urea,amino-) in the presence of catalyzer, and the Urea,amino-that obtains then makes final product (hydrazo-dicarbonamide) with the urea reaction.
[reaction formula 4]
Yet, because this reaction need be more than 500 times excess ammonia or by using expensive catalysts to make Urea,amino-, so the economical efficiency of reaction is also lower for every part of monochloro-urea sodium salt.Another problem is owing to the other reaction that needs Urea,amino-is changed into hydrazo-dicarbonamide subsequently, so all processes is longer.
Below reaction formula 5 show method with the synthetic hydrazo-dicarbonamide of biuret (International Application PCT/KR00/00180).It comprises the steps: by making the reaction of biuret and metal hypohalite (MOX) make a halo biuret metal-salt, makes the halo biuret metal-salt that obtains and ammonia react to prepare hydrazo-dicarbonamide subsequently.
[reaction formula 5]
Yet, since as the biuret of starting raw material very expensive or its contain plurality of impurities, and biuret and ammonia react synthesize hydrazo-dicarbonamide and need other ammonia, so that the above-mentioned problem for preparing the method for hydrazo-dicarbonamide as starting raw material with biuret is is uneconomical, do not conform with environmental demand.
Summary of the invention
An object of the present invention is to provide and a kind ofly conform with economy and environmental demand and use cheap and facile urea to prepare the method for hydrazo-dicarbonamide as starting raw material.
Another object of the present invention provides the method and apparatus of preparation hydrazo-dicarbonamide, and it can minimize the amount of by product and starting raw material.
A further object of the present invention provides by carrying out the method and apparatus that whole process prepares the hydrazo-dicarbonamide with higher yields in a continuous manner.
For realizing these purposes, the invention provides a kind of method for preparing hydrazo-dicarbonamide, it comprises the steps: biuret and ammonia by pyrolysis urea preparation formula 1, by make the reaction of the biuret that obtains and metal hypohalous acid compound or with a halo biuret metal-salt of halogen and alkali reaction preparation formula 2 or formula 3, and make a halo biuret metal-salt and an ammonia react that obtains.
[formula 1]
[formula 2]
[formula 3]
In superincumbent formula 2 and the formula 3, M represents metal, and X represents halogen.Preferably, the urea pyrolysis temperature is 100～300 ℃, removes deammoniation and an ammonia of removing and a halo biuret reacting metal salt when carrying out pyrolytic process.
The present invention also provides a kind of equipment for preparing hydrazo-dicarbonamide, and it comprises the pyrolysis oven that is used for preparing by the pyrolysis urea biuret and ammonia; The recrystallization reactor that is used for the biuret that purifying obtains from pyrolysis oven; Be used for by making the reaction of biuret and metal hypohalous acid compound or making first reactor of a halo biuret metal-salt with halogen and alkali reaction; Be used for by making a halo biuret metal-salt and ammonia react synthesize second reactor of hydrazo-dicarbonamide; And be used for isolating excess of ammonia and isolated ammonia being transported to the ammonia evaporator of ammonia thickener from hydrazo-dicarbonamide.
Preferably, the ammonia thickener is used for the ammonia that concentrates excess of ammonia and obtain from pyrolysis oven, and spissated ammonia is transported to second reactor.Pyrolysis oven can comprise and be used for and will do not inject the into air injector of pyrolysis oven with the rare gas element of isocyanate reaction, and can comprise the device that is used for reducing pressure and ammonia is removed from pyrolysis oven.
Brief Description Of Drawings
In conjunction with the drawings and will help to understand more completely the present invention and attached advantage thereof, wherein to the better understanding of following detailed description:
Fig. 1 is the synoptic diagram that shows the equipment that is used to prepare hydrazo-dicarbonamide in embodiment of the present invention.
Detailed description of the invention
From below in conjunction with can more being expressly understood the present invention the detailed description of accompanying drawing.
For preparing hydrazo-dicarbonamide of the present invention, the at first biuret and the ammonia of preparation formula 1 representative by pyrolysis urea under the temperature that is higher than the urea fusing point.Usually biuret can be used as medicine and the precursor of weedicide and the reagent that is used for analyzing widely, also by a large amount of feeds as ruminating animal, also is used in the various Plastic Resins field.In addition, it is reported that some derivative of biuret can be used as physiology healing potion or chemotherapeutic agents.Following reaction formula 6 shows the method for synthesizing biuret by the pyrolysis urea.
[reaction formula 6]
Shown in reaction formula 6, the urea that pyrolysis is 2 moles obtains biuret by eliminating ammonia.More specifically, shown in following reaction formula 7, can infer at first and form isocyanic acid and ammonia by the pyrolysis urea, isocyanic acid and other urea reaction then, thus obtain the target product biuret.
[reaction formula 7]
Advantage by the synthetic biuret of pyrolysis urea is that reaction is simple, the processing ease of reaction process, but it is lower to the transformation efficiency of biuret that its shortcoming is urea, and this is the reason that forms plurality of impurities such as triuret, tricyanic acid owing to biuret and isocyanate reaction in the biuret forming process.If elevated temperature and reaction of propagation time also increase as impurity such as triuret, tricyanic acids so to improve transformation efficiency.If reduce temperature to reduce impurity, speed of reaction will be very low so, thereby make method uneconomical.In the present invention, for the productive rate that improves biuret and reduce impurity, temperature preferably remains on 100～300 ℃, more preferably remains on 130～170 ℃.
In addition, if be not injected into into reactor with the rare gas element of isocyanate reaction such as air and nitrogen, and/or reduce the pressure of reactor, the ammonia by product that forms in reaction process so can be removed from reactor effectively.Speed of reaction can be enhanced then, and the formation of impurity also reduces.In addition, the liquid phase organic compound that can be transformed into rare gas element in high-temperature reactor can be used as inert gas source.
In addition, can use the catalyzer that is used to improve pyrolytic reaction speed if desired.Preferably useful as catalysts is inorganic acid catalyst such as nitric acid, hydrochloric acid, sulfuric acid, acid type catalyzer such as thionyl chloride, and phosphorus containg substances such as sodium phosphate.The preferred amounts of catalyzer is to be 0.001～0.5 mole for 1 mole of urea, and preferred amount is to be 0.01～0.3 mole for 1 mole of urea.
By making the reaction of the biuret that makes and metal hypohalous acid compound or can preparing a halo biuret metal-salt of following formula 2 or formula 3 with halogen and alkali reaction.
[formula 2]
[formula 3]
In superincumbent formula 2 and the formula 3, M represents metal, and X represents halogen.Show that by the direct method that makes the reaction of biuret and metal hypohalous acid compound prepare a halo biuret metal-salt in reaction formula 8, specific embodiment shows in reaction formula 9.
[reaction formula 8]
Or
In the superincumbent reaction formula, M represents metal, and X represents halogen.
[reaction formula 9]
Or
With reference to top reaction formula 9, biuret and sodium hypochlorite reaction form chloro biuret sodium salt.Because top reaction is thermopositive reaction, so preferably reaction system remains on lesser temps.But the chloro biuret sodium salt that obtains is stable for appropriate heat, so it can at room temperature prepare.Preferably temperature of reaction is lower than 60 ℃, more preferably-10～60 ℃, most preferably is-5～35 ℃.Consider economical efficiency and operation possibility, the reaction mol ratio of 1 mole of urea metal hypohalite is preferably 0.1～2.When reacting mol ratio less than 1 mole, can the excessive biuret of recycling.In above-mentioned reaction when the reaction mol ratio less than 0.1 or temperature of reaction be lower than-10 ℃, the reaction times is with long.If the reaction mol ratio surpasses 2, preparation cost increases and side reaction can take place so.In addition, if temperature of reaction surpasses 60 ℃, a halo biuret metal-salt that makes so can decompose, and this is owing to its at high temperature unsettled reason.Zhi Bei chloro biuret sodium salt can directly use or preserve be used for ensuing reaction under these conditions.
Show in reaction formula 10 by the method that makes biuret and halogen and alkali reaction prepare a halo biuret metal-salt of top formula 2 or formula 3.Shown in reaction formula 10, in biuret and halogen such as chlorine reaction or halogen compounds reaction and after making a halo biuret (5), can make a halo biuret metal-salt by being added in the halo biuret (5) that makes such as the alkali of metal hydroxides (for example sodium hydroxide, potassium hydroxide, calcium hydroxide) etc.
[reaction formula 10]
In the superincumbent reaction formula 10, M represents metal, and X represents halogen.
Consider that the reaction that is used to prepare a halo biuret (5) is thermopositive reaction, think that it is favourable suitable speed of reaction and reaction stability being arranged and keep lower temperature of reaction, particularly temperature of reaction is less than 60 ℃, is preferably-10～60 ℃, most preferably is-5～30 ℃.Selectively, at first prepare a halo biuret metal-salt, the product reaction that makes halogen then and make by mixed metal hydroxides and biuret.Because this reaction also is thermopositive reaction, so also should keep lower temperature of reaction, particularly temperature of reaction is-10～60 ℃, more preferably-5～30 ℃.In the superincumbent reaction, when temperature of reaction is lower than 10 ℃, when temperature of reaction surpasses 60 ℃, it will decompose to thermally labile owing to a halo biuret metal-salt with oversize in the reaction times.Shown in reaction formula 11, a halo biuret metal-salt that obtains can be 3-one halo biuret metal-salt (6) or 1-one halo biuret metal-salt (7).
Be the preparation hydrazo-dicarbonamide, a halo biuret metal-salt that makes and the ammonia react that in the pyrolysis urea, forms.Reaction mechanism inferred to the Favorskii reacting phase shown in the reaction formula 12 like or similar to the Hoffman rearrangement reaction in the reaction formula 13.
[reaction formula 12]
[reaction formula 13]
With reference to top reaction formula 12, by the intermolecular reaction of electronegative nitrogen-atoms in a halo biuret metal-salt (8), when forming nitrogen-nitrogen key, eliminate metal halogen compound and can form unsettled diazacyclo propane ketone (diaziridinone) derivative (9).Diazacyclo propane ketone derivatives (9) easily and the ammonia react of higher level of reactivity, thereby make hydrazo-dicarbonamide.In addition,, can infer a halo biuret metal-salt and can change into the compound that contains isocyanate groups with reference to top reaction formula 13, the isocyanate compound that changes into can with the ammonia react of higher level of reactivity to form hydrazo-dicarbonamide.
In a halo biuret metal-salt and reaction as the ammonia of urea pyrolysis byproducts, consider temperature of reaction and efficient, preferred temperature of reaction is 0～150 ℃, more preferably 30～150 ℃.When temperature of reaction was lower than 0 ℃, speed of reaction was too slow and economic benefit is relatively poor, when top temperature of reaction is higher than 150 ℃, because equipment must be designed to bear the interior pressure that is produced by the ammonia evaporation, so equipment cost increases.
In addition, ammonia can be used with the form of gaseous ammonia or liquefied ammonia or ammoniacal liquor compound.The preferred excess of ammonia that uses is to improve speed of reaction.For 1 mole of one halo biuret metal-salt, the amount of ammonia can be 1～1000 mole, more preferably 2～500 moles, most preferably is 5～100 moles.Except with 1 moles of ammonia of a halo biuret reacting metal salt of 1 mole, excess of ammonia can reclaim and be used for ensuing reaction once more.Higher when temperature of reaction, when using a large amount of ammonia simultaneously, the pressure that can improve reaction system is to prevent the ammonia evaporation.Can improve speed of reaction and efficient like this, the preferred pressure scope is 1～100kgf/cm
2
According to the present invention, do not use catalyzer can realize high yield.If yet use catalyzer, because the reaction times can be shortened, reaction efficiency can be enhanced, so catalyzer is very useful.The example of catalyzer comprises at least a compound that is selected from vitriol, muriate, carbonate or the oxyhydroxide of basic metal or amphoteric metal and contains the organic compound of metal.For 1 mole of one halo biuret metal-salt, the preferred amounts of catalyzer is 0.001～1 mole, is more preferably 0.01～0.5 mole.About catalyzer, can add such as mineral acids such as sulfuric acid, hydrochloric acid or nitric acid, for 1 mole of one halo biuret metal-salt, the amount of mineral acid is 0.05～3.0 mole.
Solvent about reactant (biuret) or whole reaction system can make water.If desired, about second kind of solvent, can add at least a solvent that is selected from polar solvent such as methyl alcohol, ethanol, propyl alcohol, Virahol, tetrahydrofuran (THF), acetonitrile and aprotic solvent such as dimethyl formamide, dimethyl sulfoxide (DMSO), N,N-DIMETHYLACETAMIDE.Be not particularly limited the amount of second kind of solvent, but preferred amount is 0.1～50 times of the water gross weight, preferred amount is 0.2～3.0.In addition, second kind of solvent can begin as solvent in reaction and add, or adds after mixing biuret solution and chlorine bleach liquor.
Prepare the reaction of hydrazo-dicarbonamide generally as reaction formula 14 shown in urea as starting raw material according to the present invention.In addition, the equipment for preparing hydrazo-dicarbonamide according to embodiment of the present invention shows in Fig. 1.
[reaction formula 14]
As shown in Figure 1, the equipment for preparing hydrazo-dicarbonamide according to embodiment of the present invention comprises the pyrolysis oven 10 that is used for preparing by the pyrolysis urea biuret and gaseous ammonia.Preferably pyrolysis oven 10 comprises and is used for rare gas element is injected the into air injector 12 of pyrolysis oven 10, maybe can comprise being used for reducing the pressure of pyrolysis oven 10 and easily removing the device (figure does not show) of deammoniation from pyrolysis oven 10.Do not comprise air, nitrogen and in pyrolysis oven 10, can be transformed into the liquid phase organic compound of rare gas element with the non-limitative example of the rare gas element of isocyanate reaction.
Preferably the ammonia of removing from described pyrolysis oven 10 is transported to ammonia thickener 20, and the effect of ammonia thickener 20 is the excess ammonia after concentrating the ammonia that transports from pyrolysis oven 10 and hydrazo-dicarbonamide and forming.Impurity in the biuret that makes in pyrolysis oven 10 such as tricyanic acid and triuret can be isolated by recrystallization device, and then are transported to first reactor 40, and this recrystallization device comprises recrystallization reactor 30 and such as water traps such as whizzer 32.
(for example be sent to the purified biuret of first reactor 40 and metal hypohalous acid compound, NaOCl) reaction or with halogen (for example, chlorine) and alkali reaction to prepare a halo biuret metal-salt, a halo biuret metal-salt that will make then is transported to second reactor 50.One halo biuret metal-salt and ammonia react be with the preparation hydrazo-dicarbonamide, and preferably from ammonia thickener 20 supply ammonia.The hydrazo-dicarbonamide and the excess of ammonia that obtain are transported to ammonia evaporator 52.Ammonia evaporator 52 makes the excess of ammonia evaporation, and is transported to ammonia thickener 20 through the ammonia of evaporation.Isolated hydrazo-dicarbonamide is through being purified such as water traps such as strainer 54 from excess of ammonia.
As reaction formula 13 and shown in Figure 1, hydrazo-dicarbonamide can prepare with a kind of successive method from the starting raw material urea according to the present invention.Because all processes carries out continuously, so can improve preparation efficiency.In addition, can reduce preparation cost by significantly reducing needed material quantity, this be owing to a halo biuret metal-salt can with the reason of the ammonia react that in the formation of biuret, generates as by product.Like this, do not meet the by product ammonia of environmental requirement by use and can meet environmental requirement ground preparation hydrazo-dicarbonamide.
The invention provides preferred embodiment and preparation example for understanding better hereinafter.Yet the present invention should not be understood that to be limited to the following examples.
[preparation example 1～4: the preparation of biuret]
The urea that in the four-hole round-bottomed flask, adds 500g (8.33 moles), vigorous stirring, and air is injected into the bottom of flask with the speed shown in the following table 1.By heating temperature of reaction remained on simultaneously in 5 hours under 140 ℃ and react.After reaction was finished, by the solids component that uses liquid-phase chromatographic analysis to obtain, the result showed in the table 1 below.
[table 1]
| Preparation example | Air rate of injection (L/ minute) | Urea content (weight %) | Biuret Content (weight %) | Tricyanic acid and other solid content (weight %) |
| 1 | 0 | 62 | 35 | 3 |
| 2 | 1 | 41 | 55 | 4 |
| 3 | 2 | 38 | 60 | 2 |
| 4 | 4 | 37 | 61 | 2 |
[preparation example 5～7: the preparation of biuret]
Except changing temperature of reaction and the air rate of injection being remained on 2L/min reaction was carried out 3 hours, prepared biuret by the method identical with preparation example 1.After reaction was finished, by the solids component that uses liquid-phase chromatographic analysis to obtain, the result showed in the table 2 below.
[table 2]
| Preparation example | Temperature of reaction (℃) | Urea content (weight %) | Biuret Content (weight %) | Tricyanic acid and other solid content (weight %) |
| 4 | 150 | 47 | 50 | 3 |
| 5 | 160 | 38.5 | 57 | 4.3 |
| 6 | 170 | 28 | 65 | 7 |
[preparation example 8～10: the preparation of biuret]
Except by making pressure be reduced to force value shown in following table 3 replacing air injects with vacuum pump, prepare biuret by the method identical with preparation example 1.After reaction was finished, by the solids component that uses liquid-phase chromatographic analysis to obtain, the result showed in the table 3 below.
[table 3]
| Preparation example | Pressure (mmHg) | Urea content (weight %) | Biuret Content (weight %) | Tricyanic acid and other solid content (weight %) |
| 8 | 380 | 56 | 50 | 4 |
| 9 | 190 | 41.5 | 55 | 3.5 |
| 10 | 100 | 40 | 57 | 3 |
[preparation example 11～13: the preparation of biuret]
Except 1 mole urea being used 0.05 mole different catalysts and the air rate of injection is remained on the 2L/min, prepare biuret by the method identical with preparation example 1.After reaction was finished, by the solids component that uses liquid-phase chromatographic analysis to obtain, the result showed in the table 4 below.
[table 4]
| Preparation example | Catalyzer | Urea content (weight %) | Biuret Content (weight %) | Tricyanic acid and other solid content (weight %) |
| 11 | Sulfuric acid | 34 | 62 | 4 |
| 12 | Sodium phosphate | 36 | 61 | 3 |
| 13 | Thionyl chloride | 35 | 62 | 3 |
[preparation example 14: chloro biuret sodium salt synthetic]
7% biuret slurries 423.1g (0.287 mole) is joined in the glass reactor of 2L, be cooled to 5 ℃ under stirring.In reactor, add 12% aqueous sodium hypochlorite solution, and the temperature of reaction of system is remained below 5 ℃.After adding, by iodometry and liquid-phase chromatographic analysis reaction soln.The chlorine that obtains is 3.37%, and corresponding productive rate is 98%.
[preparation example 15: chloro biuret sodium salt synthetic]
7% biuret slurries 423.1g (0.287 mole) is joined in the glass reactor of 2L, be cooled to 5 ℃ under stirring.In reactor, add 10.3% aqueous sodium hydroxide solution 223g (0.575 mole), add the gaseous chlorine of 20.3g (0.287 mole), and the temperature of reaction of system is remained below 10 ℃.After adding, by iodometry and liquid-phase chromatographic analysis reaction soln.The chlorine that obtains is 3.0%, and corresponding productive rate is 98%.
[preparation example 16: chloro biuret sodium salt synthetic]
7% biuret slurries 423.1g (0.287 mole) is joined in the glass reactor of 2L, be cooled to 5 ℃ under stirring.The gaseous chlorine that in reactor, adds 20.3g (0.287 mole), and the temperature of reaction of system remained below 10 ℃.After adding gaseous chlorine, add 10.3% aqueous sodium hydroxide solution 223g (0.575 mole), simultaneously vigorous stirring and temperature of reaction remained below 5 ℃.After adding, by iodometry and liquid-phase chromatographic analysis reaction soln.The chlorine that obtains is 3.0%, and corresponding productive rate is 98%.
[embodiment 1-9: hydrazo-dicarbonamide synthetic]
593.1g is joined in the autoclave of 2L by the chloro biuret sodium salt that top preparation example 14 makes, be cooled to 10 ℃ under stirring.The temperature of reaction of solution is remained below 10 ℃, in solution, add the ammoniacal liquor of 600g (8.8 moles) 25% under the vigorous stirring.Change temperature of reaction and react under the reaction times.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in table 5.
[table 5]
| Embodiment | Reaction conditions (temperature, time) | Productive rate (%) |
| 1 | 30 ℃, 1 hour | 85 |
| 2 | 30 ℃, 2 hours | 90 |
| 3 | 30 ℃, 3 hours | 89 |
| 4 | 60 ℃, 1 hour | 91 |
| 5 | 60 ℃, 2 hours | 89 |
| 6 | 60 ℃, 3 hours | 90 |
| 7 | 90 ℃, 1 hour | 88 |
| 8 | 90 ℃, 2 hours | 89 |
| 9 | 90 ℃, 3 hours | 90 |
[embodiment 10-18: hydrazo-dicarbonamide synthetic]
Except adding 0.05 mole of different catalysts as shown in table 6, react by the method identical with embodiment 4.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in the table 6 below.
[table 6]
| Embodiment | Used catalyzer | Productive rate (%) |
| 10 | ZnCl 2 | 94 |
| 11 | Zn(OH) 2 | 92 |
| 12 | AlCl 3 | 90 |
| 13 | BaCl 2 | 91 |
| 14 | CdCl 2 | 92 |
| 15 | ZnSO 4 | 93 |
| 16 | ZnCl 2+AlCl 3(0.025 mole every kind) | 96 |
| 17 | ZnCl 2+BaCl 2(0.025 mole every kind) | 94 |
| 18 | ZnCl 2+CdCl 2(0.025 mole every kind) | 96 |
[embodiment 19-27: hydrazo-dicarbonamide synthetic]
593.1g is joined in the autoclave of 2L by the chloro biuret sodium salt that preparation example 15 makes, be cooled to 10 ℃ under stirring.The temperature of reaction of solution is remained below 10 ℃, add the ammoniacal liquor of 600g (8.8 moles) 25% under the vigorous stirring.Change temperature of reaction and react under the reaction times.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in the table 7 below.
[table 7]
| Embodiment | Reaction conditions (temperature, time) | Productive rate (%) |
| 19 | 30 ℃, 1 hour | 78 |
| 20 | 30 ℃, 2 hours | 89 |
| 21 | 30 ℃, 3 hours | 89 |
| 22 | 60 ℃, 1 hour | 88 |
| 23 | 60 ℃, 2 hours | 90 |
| 24 | 60 ℃, 3 hours | 90 |
| 25 | 90 ℃, 1 hour | 87 |
| 26 | 90 ℃, 2 hours | 86 |
| 27 | 90 ℃, 3 hours | 89 |
[embodiment 28-36: hydrazo-dicarbonamide synthetic]
Except adding 0.05 mole of different catalysts shown in following table 8, react by the method identical with embodiment 22.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in the table 8 below.
[table 8]
| Embodiment | Used catalyzer | Productive rate (%) |
| 28 | ZnCl 2 | 94 |
| 29 | Zn(OH) 2 | 91 |
| 30 | AlCl 3 | 89 |
| 31 | BaCl 2 | 91 |
| 32 | CdCl 2 | 93 |
| 33 | ZnSO 4 | 92 |
| 34 | ZnCl 2+AlCl 3(0.025 mole every kind) | 97 |
| 35 | ZnCl 2+BaCl 2(0.025 mole every kind) | 93 |
| 36 | ZnCl 2+CdCl 2(0.025 mole every kind) | 96 |
[embodiment 37-45: hydrazo-dicarbonamide synthetic]
593.1g is joined in the autoclave of 2L by the chloro biuret sodium salt that top preparation example 16 makes, be cooled to 10 ℃ under stirring.The temperature of reaction of solution is remained below 10 ℃, add the ammoniacal liquor of 600g (8.8 moles) 25% under the vigorous stirring.Change temperature of reaction and react under the reaction times.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in the table 9 below.
[table 9]
| Embodiment | Reaction conditions (temperature, time) | Productive rate (%) |
| 37 | 30 ℃, 1 hour | 79 |
| 38 | 30 ℃, 2 hours | 88 |
| 39 | 30 ℃, 3 hours | 89 |
| 40 | 60 ℃, 1 hour | 89 |
| 41 | 60 ℃, 2 hours | 90 |
| 42 | 60 ℃, 3 hours | 91 |
| 43 | 90 ℃, 1 hour | 88 |
| 44 | 90 ℃, 2 hours | 88 |
| 45 | 90 ℃, 3 hours | 89 |
[embodiment 46-54: hydrazo-dicarbonamide synthetic]
Except adding 0.05 mole of different catalysts shown in following table 10, react by the method identical with embodiment 40.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in the table 10 below.
[table 10]
| Embodiment | Used catalyzer | Productive rate (%) |
| 46 | ZnCl 2 | 93 |
| 47 | Zn(OH) 2 | 90 |
| 48 | AlCl 3 | 90 |
| 49 | BaCl 2 | 90 |
| 50 | CdCl 2 | 92 |
| 51 | ZnSO 4 | 89 |
| 52 | ZnCl 2+AlCl 3(0.025 mole every kind) | 95 |
| 53 | ZnCl 2+BaCl 2(0.025 mole every kind) | 93 |
| 54 | ZnCl 2+CdCl 2(0.025 mole every kind) | 94 |
[embodiment 55-58: hydrazo-dicarbonamide synthetic]
593.1g is joined in the autoclave of 2L by the chloro biuret sodium salt that top preparation example 14 makes, be cooled to 10 ℃ under stirring.The temperature of reaction of solution is remained below 10 ℃, the adding ammoniacal liquor of the amount shown in the table 11 below in 1 hour, pressing under the vigorous stirring.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in the table 11 below.
[table 11]
| Embodiment | Ammonia is to the mol ratio (%) of chloro biuret sodium salt | Productive rate (%) |
| 55 | 15 | 75 |
| 56 | 30 | 87 |
| 57 | 60 | 90 |
| 58 | 90 | 89 |
[embodiment 59-62: hydrazo-dicarbonamide synthetic]
593.1g is joined in the autoclave of 2L by the chloro biuret sodium salt that top preparation example 14 makes, stir down and be cooled to 10 ℃, press the various organic solvents shown in the amount adding table 12 that water weighs 0.5 times.The temperature of reaction of solution is remained below 10 ℃, in 1 hour, add the ammoniacal liquor of 600g 25% under the vigorous stirring.After reaction is finished, remove unreacted ammonia, and filtering reacting solution, obtaining water-fast hydrazo-dicarbonamide, the productive rate of calculating hydrazo-dicarbonamide also shows in the table 12 below.
[table 12]
| Embodiment | Used solvent | Productive rate (%) |
| 59 | Methyl alcohol | 90 |
| 60 | Dimethyl formamide | 94 |
| 61 | Tetrahydrofuran (THF) | 90 |
| 62 | Acetonitrile | 88 |
As mentioned above, use the present invention to prepare the method and apparatus of hydrazo-dicarbonamide, hydrazo-dicarbonamide can synthesize as starting raw material from cheap and facile urea.In addition, because the raw material of by product and use is minimized, so use high efficiency continuation method can conform with economy and environmental demand ground prepares hydrazo-dicarbonamide.
Claims (3)
1. equipment for preparing hydrazo-dicarbonamide, it comprises:
Be used for preparing the pyrolysis oven of biuret and ammonia by the pyrolysis urea;
The recrystallization reactor that is used for the biuret that purifying obtains from described pyrolysis oven;
Be used for by making the reaction of biuret and metal hypohalous acid compound or making first reactor of a halo biuret metal-salt with halogen and alkali reaction;
Be used for by making a halo biuret metal-salt and ammonia react synthesize second reactor of hydrazo-dicarbonamide; And
Be used for isolating excess of ammonia and isolated ammonia being transported to the ammonia evaporator of ammonia thickener from hydrazo-dicarbonamide, wherein the ammonia thickener is used for the ammonia that concentrates excess of ammonia and obtain from pyrolysis oven, and spissated ammonia is transported to second reactor.
2. the equipment of preparation hydrazo-dicarbonamide as claimed in claim 1, wherein said pyrolysis oven comprise and are used for and will inject the air injector of described pyrolysis oven with the rare gas element of isocyanate reaction.
3. the equipment of preparation hydrazo-dicarbonamide as claimed in claim 1, wherein said pyrolysis oven comprise the device that is used for reducing pressure and ammonia is removed from described pyrolysis oven.
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| CNB2005100877809A CN100348578C (en) | 2001-10-24 | 2001-10-24 | Equipment of preparing birueal by using carbamide as raw material |
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| CNB2005100877809A CN100348578C (en) | 2001-10-24 | 2001-10-24 | Equipment of preparing birueal by using carbamide as raw material |
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| CN01823726.6A Division CN1246293C (en) | 2001-10-24 | 2001-10-24 | Method and apparatus for preparing hydrazo-dicarbonamide using urea as starting material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0163526A1 (en) * | 1984-05-31 | 1985-12-04 | Olin Corporation | Process for preparing hydrazodicarbonamide |
| US4654441A (en) * | 1980-08-15 | 1987-03-31 | Moorman Manufacturing Company | Biuret production by controlled pyrolysis of urea |
| WO2001049652A1 (en) * | 2000-01-07 | 2001-07-12 | J & J Chemical Co., Ltd. | Method for synthesizing hydrazodicarbonamide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654441A (en) * | 1980-08-15 | 1987-03-31 | Moorman Manufacturing Company | Biuret production by controlled pyrolysis of urea |
| EP0163526A1 (en) * | 1984-05-31 | 1985-12-04 | Olin Corporation | Process for preparing hydrazodicarbonamide |
| WO2001049652A1 (en) * | 2000-01-07 | 2001-07-12 | J & J Chemical Co., Ltd. | Method for synthesizing hydrazodicarbonamide |
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