CN1049886C - Preparation of hydrazine hydrate by calcium-ammonia method - Google Patents
Preparation of hydrazine hydrate by calcium-ammonia method Download PDFInfo
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- CN1049886C CN1049886C CN92103142A CN92103142A CN1049886C CN 1049886 C CN1049886 C CN 1049886C CN 92103142 A CN92103142 A CN 92103142A CN 92103142 A CN92103142 A CN 92103142A CN 1049886 C CN1049886 C CN 1049886C
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- calcium
- hydrazine hydrate
- ammonia
- ammoniacal liquor
- losantin
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Abstract
The present invention relates to a method for preparing hydrazine hydrate by a calcium-ammonia method, particularly to a method that calcium hypochlorite solution (produced by introducing chlorine into calcium hydroxide pulp) directly reacts with ammonia water to produce the hydrazine hydrate. A Ferromolybdenum compound or a complex compound is used as a catalyst, the calcium hypochlorite reacts with the ammonia water to produce the hydrazine hydrate at the normal pressure and the temperature of 30 to 100 DEG C via two-stage reaction or one-stage reaction, and the ration of the calcium hypochlorite to the ammonia water is 1: 3 to 50; the obtained hydrazine hydrate (more than 5%) is produced after concentration. The yield of the hydrazine hydrate to chlorine gas reaches more than 60 %; the calcium oxide, ammonium bicarbonate and the surplus ammonia water can be recovered circularly for reuse. Compared with the method that sodium hypochlorite reacts with the ammonia water to produce hydrazine, the calcium-ammonia method reduces the cost of raw material; compared with the method of calcium hypochlorite-ketone, the calcium-ammonia method reduces the complex processes of 'ketazine', 'hydrolysis', etc.
Description
The invention belongs to one of preparation method of hydrazine hydrate.
Still have many countries to adopt clorox and ammoniacal liquor effect to obtain hydrazine hydrate (abbreviating the sodium ammonia process as) at present in the world.And disclosing on Japanese Patent Jp6124553 and the JP59186949 in the presence of carbonyl compound (as ketone, aldehyde), make corresponding ketazine by Losantin and ammoniacal liquor effect, obtain the method (abbreviating calcium ketone method as) of hydrazine hydrate again by this ketazine through hydrolysis.And adopt the present invention directly to prepare the method (abbreviation calcium ammonia process) of hydrazine hydrate with Losantin and ammoniacal liquor effect, yet there are no clear and definite report so far at home and abroad.
The calcium hydroxide costliness that the used sodium hydroxide of above-mentioned sodium ammonia process is more used than the calcium ammonia process many; And the technological line of calcium ketone method is very loaded down with trivial details, though ketone can be recycled, exists some to pay reaction in the process of preparation hydrazine hydrate, and because the participation of ketone, make reaction complicated, equipment heightens, simultaneously, for equipment requirements sealing and circulating or the like, these challenges technology has been proposed harsh requirement, and production security are poor undoubtedly, so the cost of the hydrazine hydrate of producing with this method is just high.
Problem at above-described sodium ammonia process and the existence of calcium ketone method, the present invention proposes and adopt calcium hydroxide, chlorine to produce Losantin, directly act on by Losantin and ammoniacal liquor again, with iron, molybdenum compound or complex compound is catalyzer, at normal pressure, under 30-100 ℃, make it the method (abbreviating the calcium ammonia process as) that water generation reaction closes hydrazine.
The technology contents of calcium ammonia process is as follows:
Chlorine is slowly fed in the slurries of calcium hydroxide, making available chlorine is the Losantin slurries of 80-200g/l.Weak ammonia (5-20%) being cooled to-5 ℃,, making it to generate ammonia chloride with the Losantin effect, the reaction process temperature is controlled at-5-+5 ℃.Its liquor capacity ratio carries out to wait mol.Then, this solution is added in strong aqua (25-28%), and add iron, molybdenum compound or complex compound and make catalyzer, at this moment, the volume ratio of Losantin and strong aqua can be 1: 3-1: 50.Stir a little, can heat, from 30-100 ℃.After the heating, to be cooled to room temperature, by the concentration of hydrazine hydrate that iodimetric analysis generates.More than be reflected in the sealed vessel and carry out, and derive the ammonia of being overflowed with conduit, water absorbs it.After this, filter its solution, for the first time remove the calcium slag, follow again, add an amount of the 1-1.5 of hydrazine content (be about doubly) bicarbonate of ammonia, boil to more than 85 ℃, and then filter, remove the calcium slag for the second time to its filtrate.Its concentrating filter liquor can get the hydrazine hydrate of 5% above concentration.In addition, its calcium slag makes it to generate calcium oxide through calcining (about 1000 ℃), and the carbonic acid gas of its secondary life of institute can feed in the ammoniacal liquor, makes bicarbonate of ammonia.Like this, calcium oxide, bicarbonate of ammonia, superfluous ammoniacal liquor is all recyclable to be recycled.Above-described Losantin and ammoniacal liquor act as the second order reaction process, also can adopt one-level (once) reaction process.
The calcium ammonia process is compared with calcium ketone method with the sodium ammonia process, and its outstanding advantage is arranged.Though calcium ammonia process and sodium ammonia process all are to generate chloramines earlier, again by chloramines and ammoniacal liquor effect, generate hydrazine hydrate.But show that with the electrochemical cyclic voltammetry test result in this experimental concentration scope, the chloramines rise time of calcium ammonia process is slow, extinction time is also long.As can be seen from Figure 1, the chloramines that the sodium ammonia process is generated just obviously generated in 3 minutes, had just disappeared after 10 minutes.And in Fig. 2, the chloramines that the calcium ammonia process is generated approximately through after 25 minutes, about-0.45 volt tangible reduction current peak just occurs, illustrates that the chloramines of valuable amount just forms.Thereupon, the reduction current peak value increases gradually, after about 35 minutes, maximum reduction current peak value occurs, illustrates that a large amount of chloramines form.After 45 minutes, reduction current just reduces gradually.Because the chloramines of calcium ammonia process generates and extinction time is long, therefore, not only be easy to the design and the operation of chemical-process equipment etc., and exist the internal potential of raising hydrazine hydrate recovery rate.The more important thing is that the used calcium hydroxide of the calcium ammonia process sodium hydroxide more used than the sodium ammonia process is much inexpensive.And " calcium " can also recycle.So the calcium ammonia process has the sodium of being better than ammonia process part.The calcium ammonia process is compared with calcium ketone method, and the former has avoided " ketazine " numerous assorted operations such as " hydrolysis " of the latter, has also avoided organic ketone in working cycle simultaneously, has problems such as side reaction and production security difference.
Exemplary embodiments of the present invention:
Getting 30 milliliters of ammoniacal liquor (13.3N) adds in 150 ml waters, be chilled to-5 ℃ with the salt ice bath, slowly add 100 milliliters of Losantins (available chlorine is 115.78/l), temperature of reaction is controlled at-5 ℃-+5 ℃, then, this reaction solution is poured in the three-necked bottle into (in the bottle 470ml 13.3N ammoniacal liquor and an amount of iron, molybdenum compound or complex compound catalyst being housed), the volume ratio of this Losantin and ammoniacal liquor can be controlled in 1: 3-1: 50.Our experiments show that hydrazine hydrate concentration is lower, its recovery rate is higher.Under the situation of sealing, derive ammonia and feed from eck of three-necked bottle and be equipped with the absorption bottle of 500 ml waters.And being heated to certain temperature rapidly, this temperature of reaction can be controlled in 30-100 ℃, is controlled at 50-70 ℃ and is optimum temps.Waiting to be chilled in the absorption bottle till the no ammonia bubble, open three-necked bottle, extract reaction solution 1 milliliter, is 6.67ml (0.1N iodine) by iodometric determination hydrazine hydrate content.After this, add bicarbonate of ammonia 4.0 grams and continue to be heated to 98 ℃, also can continue to absorb the ammonia that it is emitted.Then, filter it, remove the calcium slag.Filtrate is 15.2 milliliters (.1N iodine) through iodometric titrationiodimetry titration hydrazine hydrate content, and its volume is 310 milliliters.The ammonia absorption bottle is 15.4 milliliters with the titration of 0.4492N aqueous sulfuric acid.Its volume is 965 milliliters.As calculated, superfluous ammoniacal liquor recovery reaches 98%, and hydrazine hydrate is 61% to the chlorine recovery rate.This hydrazine hydrate is through concentrating the hydrazine hydrate that can get more than 5%.Use this hydrazine hydrate, carry out condensation, oxidation, can get hydrazo-dicarbonamide and AC whipping agent.Identify that through infrared spectra this hydrazo-dicarbonamide and AC whipping agent meet the standard spectrogram of infrared spectra.
Claims (4)
1. the technology with preparation of hydrazine hydrate by calcium-ammonia method is to use calcium hydroxide, chlorine is produced Losantin, again by Losantin and ammoniacal liquor effect, directly generate the method for hydrazine hydrate, it is characterized in that, in calcium hydroxide slurry, feed chlorine and get Losantin, again by Losantin and ammoniacal liquor, by certain volume ratio, at iron, molybdenum compound or complex compound exist down, through normal pressure, 30～100 ℃, after second order reaction or first order reaction process, can directly generate hydrazine hydrate, remove the calcium slag, can get concentration greater than the hydrazine hydrate more than 5%, calcium oxide after concentrating, bicarbonate of ammonia, it is superfluous that ammoniacal liquor is recoverable recycles.
2. the technology with preparation of hydrazine hydrate by calcium-ammonia method as claimed in claim 1 is characterized in that the volume ratio of Losantin and ammoniacal liquor is 1: 3～1: 50, and wherein the contained available chlorine of Losantin is 80～200 grams per liters.
3. the technology with preparation of hydrazine hydrate by calcium-ammonia method as claimed in claim 1 is characterized in that iron, molybdenum catalyst are meant iron, molybdenum compound or complex compound.
4. the technology with preparation of hydrazine hydrate by calcium-ammonia method as claimed in claim 1, it is characterized in that, material can be recycled, be the calcium slag through calcine calcium oxide and carbonic acid gas, carbonic acid gas by ammoniacal liquor absorb bicarbonate of ammonia, superfluous ammoniacal liquor is absorbed by water, so calcium oxide, bicarbonate of ammonia, superfluous ammoniacal liquor is recoverable recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92103142A CN1049886C (en) | 1992-04-24 | 1992-04-24 | Preparation of hydrazine hydrate by calcium-ammonia method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92103142A CN1049886C (en) | 1992-04-24 | 1992-04-24 | Preparation of hydrazine hydrate by calcium-ammonia method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1077948A CN1077948A (en) | 1993-11-03 |
| CN1049886C true CN1049886C (en) | 2000-03-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN92103142A Expired - Fee Related CN1049886C (en) | 1992-04-24 | 1992-04-24 | Preparation of hydrazine hydrate by calcium-ammonia method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041861A (en) * | 2013-01-24 | 2013-04-17 | 凤台县精华助剂有限公司 | Compound catalyst used in synthesis reaction of hydrazine hydrate |
| CN103482590B (en) * | 2013-07-23 | 2015-11-18 | 沈阳化工大学 | A kind of saponification slag prepares the method for hydrazine hydrate co-production calcium chloride |
| CN106865513B (en) * | 2017-02-14 | 2018-11-02 | 福建省泉州南飞鸟鞋业有限公司 | A kind of preparation method of hydrazine hydrate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59186949A (en) * | 1983-04-06 | 1984-10-23 | Nippon Carbide Ind Co Ltd | Separation of azine |
| JPS6124553A (en) * | 1984-07-13 | 1986-02-03 | Nippon Carbide Ind Co Ltd | Preparation of azine |
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1992
- 1992-04-24 CN CN92103142A patent/CN1049886C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59186949A (en) * | 1983-04-06 | 1984-10-23 | Nippon Carbide Ind Co Ltd | Separation of azine |
| JPS6124553A (en) * | 1984-07-13 | 1986-02-03 | Nippon Carbide Ind Co Ltd | Preparation of azine |
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| CN1077948A (en) | 1993-11-03 |
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