CN104555953A - Preparation method of hydrazine hydrate - Google Patents
Preparation method of hydrazine hydrate Download PDFInfo
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- CN104555953A CN104555953A CN201410536562.8A CN201410536562A CN104555953A CN 104555953 A CN104555953 A CN 104555953A CN 201410536562 A CN201410536562 A CN 201410536562A CN 104555953 A CN104555953 A CN 104555953A
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- hydrazine hydrate
- butanone
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Abstract
The invention belongs to the technical field of chemical synthesis, particularly relates to a preparation method of hydrazine hydrate and aims at improving production process of a hydrogen peroxide method and provides a hydrazine hydrate preparation method which is low in energy consumption, high in yield and free of pollution. The hydrazine hydrate preparation method provided by the invention comprises the following steps: carrying out reaction on ammonia, hydrogen peroxide and butanone in the presence of a catalyst to generate methyl ethyl azine; separating the methyl ethyl azine -containing upper oil phase from the catalyst-containing water phase; concentrating the catalyst-containing water phase to reuse; acid decomposing the methyl ethyl azine into hydrazonium salt and butanone, recycling the butanone, neutralizing the hydrazonium salt into hydrazine hydrate by alkali and distilling and recovering to obtain a hydrazine hydrate solution. The method can be used for preparing hydrazine hydrate and is high in yield and free of pollution.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to a kind of preparation method of hydrazine hydrate.
Background technology
Hydrazine hydrate has another name called hydrazine hydrate, is the monohydrate (N of hydrazine
2h
4h
2o), outward appearance is colourless transparent liquid, can mix arbitrarily, be insoluble to EC with water, alcohol.Hydrazine hydrate is a kind of important fine-chemical intermediate, and be widely used in synthetic pesticide, medicine, water conditioner, whipping agent, initiator and solidifying agent etc., exploitation prospect is wide.
The method of current domestic production hydrazine hydrate mostly is Wyler's process and produces, and also has part to adopt ketazine process to produce.Wherein, Wyler's process adopts urea and hypochlorite to carry out being obtained by reacting hydrazine hydrate in basic solution, and the hydrazine hydrate yield that the method obtains is lower, between 75-80% (in clorox).In reaction process, every mole of hydrazine hydrate needs consumption 4 moles of caustic soda, the also by-product inorganic salts such as a large amount of sodium carbonate, sodium-chlor, because obtained concentration of hydrazine hydrate is lower, a large amount of steam is consumed by evaporation, concentrated also needs, make the raw materials consumption of hydrazine hydrate, energy consumption all higher, do not meet the theory of national energy-saving reduction of discharging, recycling economy, will progressively be eliminated.Ketazine process is with ammonia, acetone and clorox for raw material carries out oxidizing reaction synthesis ketazine, then ketazine is hydrolyzed obtained hydrazine hydrate at high temperature under high pressure.Although the yield of the method is higher, but facility investment and the energy consumption of ketazine hydrolysis hydrazine hydrate processed are all higher, a large amount of brine wastes is also had to produce, because in brine waste, salt concn is higher, there is a large amount of organism, the intractability of waste water is very large, processing costs is very high, and domestic to there is no after process can the precedent of qualified discharge at present, there is certain problem of environmental pollution.
At present, developed countries generally adopts hydrogen peroxide method to prepare hydrazine hydrate.Hydrogen peroxide method is raw material with ammonia, butanone and hydrogen peroxide, first synthesizes butanone azine, then butanone azine is hydrolyzed obtained hydrazine hydrate at high temperature under high pressure.Reaction equation is as follows:
2NH
3+H
2O
2+2R
1R
2CO→R
1R
2C＝N-N＝CR
1R
2+4H
2O
R
1R
2C＝N-N＝CR
1R
2+3H
2O→N
2H
4·H
2O+2R
1R
2CO
Although the method does not produce brine waste, non-environmental-pollution problem, the hydrolytic process of butanone azine can produce more organic impurity, and the existence of these organic impuritys can reduce the yield of hydrazine hydrate, also can affect the quality of hydrazine hydrate.In order to these organic impuritys are removed from hydrazine hydrate, need a set of special hydrazine hydrate refining plant is installed, character in addition due to butanone azine is very stable, its hydrolysis reaction must carry out under higher temperature and pressure, the equipment requirements of hydrolysis device is higher, investment is comparatively large, and the steam energy consumption required for hydrolysis is also higher.
Summary of the invention
In view of this, the invention provides a kind of preparation method of hydrazine hydrate, the method can realize cleanly production, namely produce and problem of environmental pollution without brine waste, ketazine hydrolysis energy consumption can be reduced again, reduce facility investment, improving quality and the yield of hydrazine hydrate, is the improvement to hydrogen peroxide method production technique.
Technical scheme of the present invention is a kind of preparation method of hydrazine hydrate, comprises the steps:
A, ammonia, hydrogen peroxide and butanone to be reacted in the presence of a catalyst, generate butanone azine;
B, by the upper oil phase containing butanone azine with containing the aqueous phase separation of catalyzer;
C, the aqueous phase containing catalyzer is concentrated after be used in step a;
Sour adjust pH to 1 ~ 4 of oil phase of d, separation, butanone azine is acid hydrolysis as hydrazonium salt and butanone, is used in step a by butanone Distillation recovery;
E, solution adjust pH to 9 ~ 12 containing hydrazonium salt, hydrazonium salt is by alkali and rear generation hydrazine hydrate, and the hydrazine hydrate in solution and water are all distilled, distillation phlegma is hydrazine hydrate solution.
Concrete, described hydrogen peroxide is H
2o
2the aqueous solution, its mass percent is 20 ~ 90%.
Concrete, the catalyzer of every moles of hydrogen peroxide butanone of 0.2 ~ 5 mole in step a, the ammonia of 0.1 ~ 10 mole and 0.2 ~ 5 mole.
Preferably, the catalyzer of every moles of hydrogen peroxide butanone of 1.5 ~ 4 moles in step a, the ammonia of 01.5 ~ 4 mole and 1 ~ 3 mole.
Preferably, the catalyzed reaction of step a is carried out at ambient pressure, and temperature of reaction is 30 ~ 70 DEG C.
Concrete, described ammonia is ammoniacal liquor or ammonia.
Concrete, described catalyzer is at least one in acid amides, ammonium salt or nitrile.
Preferably, described acid amides is methane amide, ethanamide or propionic acid amide.
Preferably, described ammonium salt is ammonium formiate, ammonium acetate or propionic acid ammonium.
Preferably, described nitrile is acetonitrile or propionitrile.
When using catalyzer of more than two kinds, preferred amide uses together with the ammonium salt of its correspondence, and namely methane amide uses together with ammonium formiate, ethanamide uses together with ammonium acetate or propionic acid amide uses together with propionic acid ammonium.
Concrete, the acid regulating oil phase pH to adopt in steps d is at least one in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
Preferably, the acid regulating oil phase pH to adopt in steps d is hydrochloric acid.
Concrete, in step e, the pH of hydrazonium salt solution is adjusted to alkalescence, the alkali adopted is at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide or calcium oxide.
Preferably, pH is regulated to adopt calcium hydroxide in step e.
In step a of the present invention, ammonia, butanone and catalyzer can join in reaction solution with any order respectively or simultaneously, and hydrogen peroxide should slowly join in reaction solution, and various reactor can be adopted to react at ambient pressure.Catalytic reaction temperature range is wider, can carry out, preferably between 30 ~ 70 DEG C between 0 ~ 100 DEG C.
In the present invention, described ammonia is ammoniacal liquor or passes into ammonia.Ammoniacal liquor all will carry out using after gasification becomes ammonia before use, use ammonia to reduce and bring excess moisture into reactive system, be conducive to the concentration and recovery of catalyzer, than using, the energy consumption of ammoniacal liquor is low, but need at the beginning to add certain water in reactive system, to dissolve and to absorb ammonia in reaction.In reactive system, the concentration of ammonia is in constantly change.
In the present invention, regulate oil phase pH to slightly acidic, the acid adopted can be one or more of the mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, the preferred hydrochloric acid of the present invention.Reaction equation is as follows:
R
1R
2C＝N-N＝CR
1R
2+2HCl+2H
2O→2R
1R
2CO+N
2H
4·2HCl
Method of the present invention, is adjusted to alkalescence by the pH of hydrazonium salt solution, and the alkali adopted can be sodium hydroxide, one or more in potassium hydroxide, lithium hydroxide, calcium hydroxide, calcium oxide.Preferably calcium hydroxide of the present invention.Reaction equation is as follows:
N
2H
4·2HCl+Ca(OH)
2→N
2H
4·H
2O+CaCl
2+H
2O
The fractionation by distillation operation of hydrazine hydrate can adopt the evaporation technologies such as single-action, multiple-effect, heat pump to carry out.
Beneficial effect of the present invention:
The hydrolysis process of butanone azine in hydrogen peroxide method is improved to acidolysis process by the present invention, eliminate huge facility investment (being generally needs 5 continuous hydrolysis towers) and a large amount of steam consumption (hydrolysis system 1 ton of hydrazine hydrate needs the middle pressure steam of more than 10 tons) of hydrolysis device, reduce production cost; Owing to eliminating the hydrolyzing process of High Temperature High Pressure, thus avoid the generation of hydrolytic side reactions and product (as: isopropylcarbinol, isobutyl hydrazine, Diacetylmonoxime, pyrazoline race heterogeneous ring compound etc.) thereof, reduce the content of organic impurity in hydrazine hydrate, improve purity and the quality of hydrazine hydrate, eliminate treating process and the facility investment thereof of hydrazine hydrate; Preparation method of the present invention can carry out at ambient pressure simultaneously, and reaction conditions is gentle, and production process is safety and stability more, and hydrazine hydrate yield is greater than 85% (in hydrogen peroxide).
Accompanying drawing explanation
Fig. 1 process flow sheet of the present invention
Embodiment
Embodiment 1
With reference to the technical process of Fig. 1, produce.By 108g butanone, 34g methane amide and 170g massfraction be 20% ammoniacal liquor tape loaded reflux condensing tube, thermometer, dropping funnel and stirring four-hole boiling flask in, adding massfraction in dropping funnel is 30% hydrogen peroxide 56.7g (0.5mol).Heating in water bath, is raised to 45 DEG C by solution temperature, start to drip hydrogen peroxide, and controlling temperature of reaction is 45 DEG C, within 3 ~ 4 hours, drips off.After dropwising, temperature is risen to 50 DEG C, keep 50 DEG C to continue reaction 2 hours.After completion of the reaction, stop heating and stir, question response liquid cooling but proceeds in separating funnel afterwards, and by aqueous phase and separation of oil, in oil phase, butanone azine content is 69.2%.By aqueous phase distillation and concentration, reclaim ammonia, butanone and catalyzer.Oil phase is proceeded in the four-hole boiling flask of band distillation prolong, thermometer and stirring, open and stir, in oil phase, slowly add hydrochloric acid (15%), adjust ph is 1 ~ 2, then opens oil bath heating, air distillation, steamed by butanone in solution, butanone is reclaimed in condensation.In flask solution, add 30g calcium oxide regulates pH to be 10, and evenly rear unlatching oil bath heating to be mixed, distill at ambient pressure, by solution evaporate to dryness in flask, obtain phlegma, concentration of hydrazine hydrate is 152g/l, and yield is 86.9% (in hydrogen peroxide).
Embodiment 2
The ammoniacal liquor being 28% by 1100g butanone, 350g methane amide and 1360g massfraction load one with stir and reflux exchanger jacketed reactor in, have in chuck and control the refrigerant of temperature of reaction.Solution temperature is raised to 40 DEG C, starts to drip 566.7g hydrogen peroxide (30%), open refrigerant, controlling temperature of reaction is 40 DEG C, within 3 ~ 4 hours, drips off.After dropwising, temperature is risen to 45 DEG C, keep 45 DEG C to continue reaction 2.5 hours.After completion of the reaction, stop heating and stir, proceeded to by reaction solution in separating funnel, by aqueous phase and separation of oil, in oil phase, butanone azine content is 67.7%.By aqueous phase distillation and concentration, reclaim ammonia, butanone and catalyzer.Oil phase is proceeded in the jacketed reactor of band stirring and distiller condenser, have in chuck to the thermal oil of reactor heating.Open and stir, in oil phase, slowly add nitric acid (10%), adjust ph is 2 ~ 3, and then to reactor heating, air distillation, steams the butanone in solution, and butanone is reclaimed in condensation.In reactor solution, add 315g calcium oxide adjusts pH to be 12, to be mixed evenly after to solution heat temperature raising, distill at ambient pressure, by solution evaporate to dryness, obtain phlegma, concentration of hydrazine hydrate is 145.5g/l, and yield is 86.5% (in hydrogen peroxide).
Embodiment 3
Be that in the four-hole boiling flask of the ammoniacal liquor tape loaded reflux condensing tube of 25%, thermometer, dropping funnel and stirring, adding massfraction in dropping funnel is 90% hydrogen peroxide 37.8g (1mol) by 150g butanone, 52g ammonium acetate, 63g ethanamide and 156g mass percent concentration.Heating in water bath, is raised to 30 DEG C by solution temperature, start to drip hydrogen peroxide, and controlling temperature of reaction is 30 DEG C, within 3 ~ 4 hours, drips off.After dropwising, temperature is risen to 45 DEG C, keep 45 DEG C to continue reaction 3 hours.After completion of the reaction, stop heating and stir, proceeded to by reaction solution in separating funnel, by aqueous phase and separation of oil, in oil phase, butanone azine content is 95.5%.By aqueous phase distillation and concentration, reclaim ammonia, butanone and catalyzer.Oil phase is proceeded in the four-hole boiling flask of band distillation prolong, thermometer and stirring, open and stir, in oil phase, slowly add sulfuric acid (10%), adjust ph is 3 ~ 4, then opens oil bath heating, air distillation, steamed by butanone in solution, butanone is reclaimed in condensation.In flask solution, add sodium hydroxide solution regulates pH to be 9, and evenly rear unlatching oil bath heating to be mixed, distill at ambient pressure, by solution evaporate to dryness in flask, obtain phlegma, concentration of hydrazine hydrate is 150g/l, and yield is 85.2% (in hydrogen peroxide).
Embodiment 4
By in the four-hole boiling flask of the ammoniacal liquor tape loaded reflux condensing tube of 360g butanone, 123g acetonitrile and 340g mass percentage concentration 20%, thermometer, dropping funnel and stirring, adding massfraction in dropping funnel is 50% hydrogen peroxide 142g (1mol).Heating in water bath, is raised to 60 DEG C by solution temperature, start to drip hydrogen peroxide, and controlling temperature of reaction is 60 DEG C, within 3 ~ 4 hours, drips off.After dropwising, temperature is risen to 70 DEG C, keep 70 DEG C to continue reaction 1 hour.After completion of the reaction, stop heating and stir, question response liquid cooling but proceeds in separating funnel afterwards, and by aqueous phase and separation of oil, in oil phase, butanone azine content is 40.2%.By aqueous phase distillation and concentration, reclaim ammonia, butanone and catalyzer.Oil phase is proceeded in the four-hole boiling flask of band distillation prolong, thermometer and stirring, open and stir, in oil phase, slowly add phosphoric acid (50%), adjust ph is 3, then opens oil bath heating, air distillation, steamed by butanone in solution, butanone is reclaimed in condensation.In flask solution, add aqua calcis regulates pH to be 10, and evenly rear unlatching oil bath heating to be mixed, distill at ambient pressure, by solution evaporate to dryness in flask, obtain phlegma, concentration of hydrazine hydrate is 151g/l, and yield is 87.8% (in hydrogen peroxide).
Embodiment 5
By in the four-hole boiling flask of 288g butanone, 56g methane amide, 84g ammonium formiate and 120g water tape loaded reflux condensing tube, thermometer, dropping funnel and stirring, adding massfraction in dropping funnel is 50% hydrogen peroxide 68g (1mol).Solution temperature is raised to 50 DEG C, starts to pass into ammonia and drip hydrogen peroxide, controlling temperature of reaction is 50 DEG C, and led at 2 ~ 3 hours by 68g ammonia, hydrogen peroxide dripped off at 3 ~ 4 hours.After dropwising, temperature is risen to 60 DEG C, keep 60 DEG C to continue reaction 1.5 hours.After completion of the reaction, stop heating and stir, question response liquid cooling but proceeds in separating funnel afterwards, and by aqueous phase and separation of oil, in oil phase, butanone azine content is 52.3%.By aqueous phase distillation and concentration, reclaim ammonia, butanone and catalyzer.Oil phase is proceeded in the four-hole boiling flask of band distillation prolong, thermometer and stirring, open and stir, in oil phase, slowly add hydrochloric acid (15%), adjust ph is 4, then opens oil bath heating, air distillation, steamed by butanone in solution, butanone is reclaimed in condensation.In flask solution, add lithium hydroxide solution regulates pH to be 11, and evenly rear unlatching oil bath heating to be mixed, distill at ambient pressure, by solution evaporate to dryness in flask, obtain phlegma, concentration of hydrazine hydrate is 148g/l, and yield is 87.1% (in hydrogen peroxide).
Embodiment 6
By in the four-hole boiling flask of 180g butanone, 64g propionic acid ammonium, 85g propionic acid amide and 220g water tape loaded reflux condensing tube, thermometer, dropping funnel and stirring, adding massfraction in dropping funnel is 40% hydrogen peroxide 85g (1mol).Heating in water bath, is raised to 35 DEG C by solution temperature, start to pass into ammonia and drip hydrogen peroxide, and controlling temperature of reaction is 35 DEG C, and led at 2 ~ 3 hours by 86g ammonia, hydrogen peroxide dripped off at 3 ~ 4 hours.After dropwising, temperature is risen to 40 DEG C, keep 40 DEG C to continue reaction 4 hours.After completion of the reaction, stop heating and stir, reaction solution but proceeds in separating funnel by question response liquid cooling afterwards, and by aqueous phase and separation of oil, in oil phase, butanone azine content is 76.9%.By aqueous phase distillation and concentration, reclaim ammonia, butanone and catalyzer.Oil phase is proceeded in the four-hole boiling flask of band distillation prolong, thermometer and stirring, open and stir, in oil phase, slowly add hydrochloric acid (15%), adjust ph is 3, then opens oil bath heating, air distillation, steamed by butanone in solution, butanone is reclaimed in condensation.In flask solution, add potassium hydroxide solution regulates pH to be 10, and evenly rear unlatching oil bath heating to be mixed, distill at ambient pressure, by solution evaporate to dryness in flask, obtain phlegma, concentration of hydrazine hydrate is 146g/l, and yield is 86.1% (in hydrogen peroxide).
Claims (10)
1. a preparation method for hydrazine hydrate, is characterized in that, comprises the steps:
A, ammonia, hydrogen peroxide and butanone to be reacted in the presence of a catalyst, generate butanone azine;
B, by the upper oil phase containing butanone azine with containing the aqueous phase separation of catalyzer;
C, the aqueous phase containing catalyzer is concentrated after be used in step a;
Sour adjust pH to 1 ~ 4 of oil phase of d, separation, butanone azine is acid hydrolysis as hydrazonium salt and butanone, is used in step a by butanone Distillation recovery;
E, solution adjust pH to 9 ~ 12 containing hydrazonium salt, hydrazonium salt is by alkali and rear generation hydrazine hydrate, and the hydrazine hydrate in solution and water are all steamed out, distillation phlegma is hydrazine hydrate solution.
2. the preparation method of hydrazine hydrate as claimed in claim 1, is characterized in that: described hydrogen peroxide is H
2o
2the aqueous solution, its mass percent is 20 ~ 90%; Described ammonia is ammonia or ammoniacal liquor.
3. the preparation method of hydrazine hydrate as claimed in claim 1 or 2, is characterized in that: the catalyzer of every moles of hydrogen peroxide butanone of 0.2 ~ 5 mole in step a, the ammonia of 0.1 ~ 10 mole and 0.2 ~ 5 mole.
4. the preparation method of the hydrazine hydrate as described in any one of claims 1 to 3, is characterized in that: the catalyzer of every moles of hydrogen peroxide butanone of 1.5 ~ 4 moles in step a, the ammonia of 01.5 ~ 4 mole and 1 ~ 3 mole.
5. the preparation method of hydrazine hydrate as claimed in claim 4, it is characterized in that: the catalyzed reaction of step a is carried out at ambient pressure, temperature of reaction is 30 ~ 70 DEG C.
6. the preparation method of the hydrazine hydrate as described in any one of Claims 1 to 5, is characterized in that: described catalyzer is at least one in acid amides, ammonium salt or nitrile; Described acid amides is methane amide, ethanamide or propionic acid amide, and described ammonium salt is ammonium formiate, ammonium acetate or propionic acid ammonium, and described nitrile is acetonitrile or propionitrile.
7. the preparation method of the hydrazine hydrate as described in any one of claim 1 ~ 6, is characterized in that: the acid regulating oil phase pH to adopt in steps d is at least one in hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
8. the preparation method of hydrazine hydrate as claimed in claim 7, is characterized in that: the acid regulating oil phase pH to adopt in steps d is hydrochloric acid.
9. the preparation method of the hydrazine hydrate as described in claim 1 ~ 8, is characterized in that: in step e, the pH of hydrazonium salt solution is adjusted to alkalescence, and the alkali adopted is at least one in sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide or calcium oxide.
10. the preparation method of the hydrazine hydrate as described in any one of claim 9, is characterized in that: regulate pH to adopt calcium hydroxide in step e.
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| CN106865513A (en) * | 2017-02-14 | 2017-06-20 | 李亚杉 | A kind of preparation method of hydrazine hydrate |
| CN106986802A (en) * | 2017-05-22 | 2017-07-28 | 重庆丽澄环保科技有限公司 | A kind of method for synthesizing thiocarbohydrazide |
| CN107011207A (en) * | 2017-06-03 | 2017-08-04 | 重庆锦杉科技有限公司 | A kind of synthetic method of 2,4,6 trinitrophenyl-hydrazine |
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| CN115869885A (en) * | 2022-11-28 | 2023-03-31 | 郑州中科新兴产业技术研究院 | Homogeneous phase high-efficiency process and reaction device for synthesizing ketazine series |
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| CN106865513A (en) * | 2017-02-14 | 2017-06-20 | 李亚杉 | A kind of preparation method of hydrazine hydrate |
| CN106986802A (en) * | 2017-05-22 | 2017-07-28 | 重庆丽澄环保科技有限公司 | A kind of method for synthesizing thiocarbohydrazide |
| CN107033021A (en) * | 2017-05-24 | 2017-08-11 | 重庆锦杉科技有限公司 | A kind of preparation method of 2,4 dichloro phenyl hydrazine |
| CN107033022A (en) * | 2017-06-02 | 2017-08-11 | 重庆锦杉科技有限公司 | A kind of synthetic method of the isopropoxide phenylhydrazine of 2,4 dichloro 5 |
| CN107033023A (en) * | 2017-06-02 | 2017-08-11 | 重庆锦杉科技有限公司 | A kind of synthetic method of the hydroxyl phenylhydrazine of 2,4 dichloro 5 |
| CN107011207A (en) * | 2017-06-03 | 2017-08-04 | 重庆锦杉科技有限公司 | A kind of synthetic method of 2,4,6 trinitrophenyl-hydrazine |
| CN107021888A (en) * | 2017-06-03 | 2017-08-08 | 重庆锦杉科技有限公司 | A kind of synthetic method of 2,4 dinitrophenylhydrazine |
| CN107033024A (en) * | 2017-06-03 | 2017-08-11 | 重庆锦杉科技有限公司 | A kind of synthetic method of paranitrophenylhydrazine |
| CN107381523A (en) * | 2017-09-07 | 2017-11-24 | 盐城顺恒化工有限公司 | A kind of preparation method of hydrazine sulfate |
| CN108569681A (en) * | 2018-05-31 | 2018-09-25 | 邹西红 | A kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate |
| CN108586285A (en) * | 2018-05-31 | 2018-09-28 | 邹西红 | A kind of preparation method of ketazine |
| CN108793105A (en) * | 2018-05-31 | 2018-11-13 | 邹西红 | A kind of intermediate raw material repeated reproducibility method oxo-synthesis of hydrazine hydrate technique |
| CN113840799A (en) * | 2019-05-16 | 2021-12-24 | 阿科玛法国公司 | Improved process for making hydrazine hydrate with oxime recycle |
| CN113840799B (en) * | 2019-05-16 | 2023-11-28 | 阿科玛法国公司 | Improved process for preparing hydrazine hydrate with oxime recycle |
| CN115869885A (en) * | 2022-11-28 | 2023-03-31 | 郑州中科新兴产业技术研究院 | Homogeneous phase high-efficiency process and reaction device for synthesizing ketazine series |
| CN115869885B (en) * | 2022-11-28 | 2023-11-10 | 郑州中科新兴产业技术研究院 | Homogeneous phase high-efficiency process and reaction device for synthesizing ketazine series |
| CN115924864A (en) * | 2022-12-23 | 2023-04-07 | 中国天辰工程有限公司 | Method for preparing hydrazine hydrate by hydrolyzing azino butanone |
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