CN104528673B - A kind of method preparing hydrazine hydrate - Google Patents
A kind of method preparing hydrazine hydrate Download PDFInfo
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- CN104528673B CN104528673B CN201510024163.8A CN201510024163A CN104528673B CN 104528673 B CN104528673 B CN 104528673B CN 201510024163 A CN201510024163 A CN 201510024163A CN 104528673 B CN104528673 B CN 104528673B
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- benzophenone
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Abstract
The invention discloses a kind of method preparing hydrazine hydrate, benzophenone is added in reactor, with thorium oxide, ammonium chloride, Cu-lyt. is catalyst, speed with 0.5L/min after reactor evacuation is passed through ammonia in reactor continuously, in reactor, it is passed through oxidant oxygen with the speed of 2L/min simultaneously, under the conditions of 250 DEG C, react 8 12h and prepare benzophenone azino, polyethylene glycol oxide and DBSA are dispersed in mix homogeneously in benzophenone azino, mixture is sent into hydrolysis in atmospheric distillation tower obtain hydrazine hydrate finished product and reclaim benzophenone simultaneously.The present invention selects the oxygen of green non-pollution as oxidant, and technique is simple, easy to operate, and solves the liquid flooding problem in azino hydrolytic process, and the hydrazine hydrate purity of preparation is high, and low cost is worthy to be popularized.
Description
Technical field
The invention belongs to fine chemistry industry production field, be specifically related to a kind of method preparing hydrazine hydrate.
Background technology
Hydrazine hydrate industrial process mainly has Raschig process, urea method, ketazine process and hydrogen peroxide method 4 kinds at present.Draw
Western method is with ammonia for nitrogen source, generates hydrazine hydrate with hypochlorite oxidation ammonia.The method is because generating chloramines in course of reaction, therefore is somebody's turn to do
Method is also referred to as chloramine method.Obtain due to the method is 1～2% aqueous solution of hydrazine, needs evaporation and concentration can obtain vendible product
Product, therefore energy consumption is high, and by-product a large amount of NaCl, NH4The salt such as Cl, yield low (total recovery is 67%), institute is the most naughty
Eliminate.Urea method is the improvement to Raschig process, is as nitrogen source using carbamide, does oxidant with sodium hypochlorite equally, the work after improvement
Skill can get the hydrazine hydrate product that concentration is about 40%, and technique is more ripe, but equally exists energy consumption height, by-product compared with Raschig process
The problem that many, environmental protection pressure is big.Ketazine process is first to be proposed by Bayer A.G and realize industry in 20 century 70s
A kind of oxo-synthesis of hydrazine hydrate technique that metaplasia is produced, is under ketone (acetone, butanone etc.) existence condition, and sodium hypochlorite is anti-with ammonia
Should, generating intermediate product ketazine, ketazine under high pressure hydrolyzes, and it is the hydration of 80% that product concentrates available concentration through rectification
Hydrazine.The energy consumption of the method is about the 1/3 of Raschig process, and total recovery is close to 90%, and production technology is substantially better than Raschig process.And peroxidating
A kind of production technology that ketazine process is actually improved by hydrogen method, i.e. uses H2O2NaClO is replaced to do oxidant, it is to avoid
NaClO does oxidant and produces the problem of a large amount of by-product salt, and the environmental protection pressure concentration of hydrazine that is little and that ultimately produce is higher, and total recovery exists
More than 90%.At present, France Produit Chimiques, Ugine Kuhlmann company, atropic company, Lang Sheng company of Germany,
Mitsubishi gas chemical company all uses hydrogen peroxide method production technology to produce hydrazine hydrate.The beginning of the eighties in last century, the Ministry of Chemical Industry
Liming chemical Inst just has ketazine process to prepare the research report of hydrazine hydrate, and to the mid-80, the Ministry of Chemical Industry's southwest chemical industry grinds
Study carefully institute's success of the test hydrogen peroxide and butanone method produces hydrazine hydrate technique, but non-pilot scale.Existing the most domestic mainly use urea method
Technique produces hydrazine hydrate.
Summary of the invention
It is an object of the invention to be to provide a kind of more advanced hydrazine hydrate synthesis technique.This method is simple to operate to be obtained
Hydrazine hydrate purity high, not only solve the content requirement of hydrazine hydrate but also solve pollution problem, be also greatly reduced simultaneously
The cost produced and the consumption of resource.
The present invention is achieved through the following technical solutions:
A kind of method preparing hydrazine hydrate, it is characterized in that and adds in reactor by benzophenone, with thorium oxide,
Ammonium chloride, Cu-lyt. are catalyst and are simultaneously introduced in aforesaid reaction vessel, by after reactor evacuation with the speed of 0.5L/min
Degree is passed through ammonia in reactor continuously, is passed through oxidant oxygen with the speed of 2L/min, at 250 DEG C of bars in reactor simultaneously
Under part, reacting 8-12h, under thorium oxide and ammonium chloride catalytic action, benzophenone and ammonia carry out dehydrating condensation and generate hexichol Asia
Methylamine, under Cu-lyt. catalytic action, the further oxidative coupling of hexichol methylene amine generates benzophenone azino, and reaction terminates
After, reactor is naturally cooling to room temperature, isolates benzophenone azino；By nonionic surfactant polyethylene glycol oxide and 12
Alkyl benzene sulphonate is dispersed in mix homogeneously in benzophenone azino, mixture is sent into hydrolysis in atmospheric distillation tower and obtains hydrazine hydrate
Finished product also reclaims benzophenone simultaneously.
A kind of method preparing hydrazine hydrate of the present invention, is dispersed with the two of polyethylene glycol oxide and DBSA in hydrolysis
Benzophenone and water feed from the centre position of distillation column, and in reaction, bottom temperature is 150 DEG C, and tower top temperature is 100 DEG C, during hydrolysis
Between be 4 ~ 8 hours.
A kind of method preparing hydrazine hydrate of the present invention, the catalyst in reactor passes through centrifugation, and washing, for next
Secondary response.
The invention has the beneficial effects as follows: the method preparing hydrazine hydrate of the present invention, select the oxygen conduct of green non-pollution
Oxidant, technique is simple, easy to operate, and solves the liquid flooding problem in azino hydrolytic process, and the hydrazine hydrate purity of preparation is high,
Low cost, is worthy to be popularized.
Detailed description of the invention
Embodiment 1:
130 g benzophenones are added in reactor, are separately added into thorium oxide 1.5g, ammonium chloride 1.5g and Cu-lyt. 8g,
By airtight for reactor evacuation, be warming up to 250 DEG C, in reactor, be passed through ammonia continuously with the speed of 0.5L/min, simultaneously with
The speed of 2L/min is passed through oxygen in reactor, and reaction obtains the benzophenone connection that content is 65% for 8 hours with this understanding
Nitrogen, in the reaction, under thorium oxide and ammonium chloride catalytic action, benzophenone and ammonia carry out dehydrating condensation and generate hexichol methylene
Amine, under Cu-lyt. catalytic action, the further oxidative coupling of hexichol methylene amine generates benzophenone azino, after reaction terminates,
Reactor is naturally cooling to room temperature, isolates benzophenone azino, simultaneously by catalyst centrifugation, reclaims, be used for after washing
React next time.4g polyethylene glycol oxide and 4g DBSA mix homogeneously is added, by above-mentioned in benzophenone azino
Mixture and 200mL water add distillation column, and be hydrolyzed under normal pressure reaction, and feedboard is positioned at the centre position of tower, tower in reaction
Still temperature is 150 DEG C, and tower top temperature is 100 DEG C, and hydrolysis time is 4 hours, and hydrolyzate obtains hydrazine hydrate, is reclaimed by two propiophenones
Cycling and reutilization.
Embodiment 2:
260g benzophenone is added in reactor, is separately added into thorium oxide 2g, ammonium chloride 2g and Cu-lyt. 15g, will be anti-
Answer the airtight evacuation of still, be warming up to 250 DEG C, in reactor, be passed through ammonia continuously with the speed of 0.5L/min, simultaneously with 2L/
The speed of min is passed through oxygen in reactor, and reaction obtains the benzophenone azino that content is 65% for 10 hours with this understanding,
In the reaction, under thorium oxide and ammonium chloride catalytic action, benzophenone and ammonia carry out dehydrating condensation and generate hexichol methylene amine,
Under Cu-lyt. catalytic action, the further oxidative coupling of hexichol methylene amine generates benzophenone azino, after reaction terminates, and reactor
It is naturally cooling to room temperature, isolates benzophenone azino, simultaneously by catalyst centrifugation, reclaim after washing, for next time
Reaction.8g polyethylene glycol oxide and 8g DBSA mix homogeneously is added, by said mixture in benzophenone azino
Adding distillation column with 400mL water, be hydrolyzed under normal pressure reaction, and feedboard is positioned at the centre position of tower, bottom temperature in reaction
Being 150 DEG C, tower top temperature is 100 DEG C, and hydrolysis time is 6 hours, and hydrolyzate obtains hydrazine hydrate, and two propiophenones are reclaimed circulation again
Utilize.
Embodiment 3:
650 g benzophenones are added in reactor, is separately added into thorium oxide 8g, ammonium chloride 8g and Cu-lyt. 30g, will be anti-
Answer the airtight evacuation of still, be warming up to 250 DEG C, in reactor, be passed through ammonia continuously with the speed of 0.5L/min, simultaneously with 2L/
The speed of min is passed through oxygen in reactor, and reaction obtains the benzophenone azino that content is 60% for 12 hours with this understanding,
In the reaction, under thorium oxide and ammonium chloride catalytic action, benzophenone and ammonia carry out dehydrating condensation and generate hexichol methylene amine,
Under Cu-lyt. catalytic action, the further oxidative coupling of hexichol methylene amine generates benzophenone azino, after reaction terminates, and reactor
It is naturally cooling to room temperature, isolates benzophenone azino, simultaneously by catalyst centrifugation, reclaim after washing, for next time
Reaction.10g polyethylene glycol oxide and 10g DBSA mix homogeneously is added, by above-mentioned mixing in benzophenone azino
Thing and 1000mL water add distillation column, and be hydrolyzed under normal pressure reaction, and feedboard is positioned at the centre position of tower, tower reactor temperature in reaction
Degree is 150 DEG C, and tower top temperature is 100 DEG C, and hydrolysis time is 8 hours, and hydrolyzate obtains hydrazine hydrate, and two propiophenones are reclaimed circulation
Recycling.
Claims (1)
1. the method preparing hydrazine hydrate, it is characterised in that: benzophenone is added in reactor, with thorium oxide, ammonium chloride,
Cu-lyt. is catalyst and is simultaneously introduced in aforesaid reaction vessel, by after reactor evacuation with the speed of 0.5L/min to reaction
Still is passed through ammonia continuously, in reactor, is passed through oxidant oxygen with the speed of 2L/min, under the conditions of 250 DEG C, instead simultaneously
Answering 8-12h, under thorium oxide and ammonium chloride catalytic action, benzophenone and ammonia carry out dehydrating condensation and generate hexichol methylene amine,
Under Cu-lyt. catalytic action, the further oxidative coupling of hexichol methylene amine generates benzophenone azino, after reaction terminates, and reactor
It is naturally cooling to room temperature, isolates benzophenone azino；By nonionic surfactant polyethylene glycol oxide and detergent alkylate sulphur
Acid is dispersed in mix homogeneously in benzophenone azino, mixture is sent into hydrolysis in atmospheric distillation tower and obtains hydrazine hydrate finished product the most together
Shi Huishou benzophenone；Hydrolysis is dispersed with polyethylene glycol oxide and the benzophenone of DBSA and water from distillation column
Centre position feeds, and in reaction, bottom temperature is 150 DEG C, and tower top temperature is 100 DEG C, and hydrolysis time is 4 ~ 8 hours；In reactor
Catalyst by centrifugation, washing, for reacting next time.
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| JPS518251A (en) * | 1974-07-15 | 1976-01-23 | Hiroshi Hayashi | Benzofuenonajinno seizohoho |
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| JP3755543B2 (en) * | 1995-08-14 | 2006-03-15 | 三菱瓦斯化学株式会社 | Method for producing hydrated hydrazine |
| CN102328920A (en) * | 2011-07-11 | 2012-01-25 | 山东曹县斯递尔化工科技有限公司 | Process for preparing hydrazine hydrate by air oxidation method |
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