CN108569681A - A kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate - Google Patents
A kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/16—Hydrazine; Salts thereof
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Abstract
The invention discloses a kind of methods that peroxide regenerates oxo-synthesis of hydrazine hydrate, are catalyst with organic amine or derivatives thereof, and ketone and amide first carry out addition cyclization, generate 2 R3Hydroxyl 3R1R2Azepine propylene oxide；2‑R3Hydroxyl 3R1R2Azepine propylene oxide carries out condensation reaction with peroxide, generates 2 R of a pair of horses going side by side3Hydroxyl 3R1R2Azepine propylene oxide；It is quantitatively passed through liquefied ammonia again and carries out cracking acid-base neutralization reaction, generates ketazine intermediate and ammonium carboxylate salt；Ketazine hydrolysis generates hydrazine hydrate and ketone, regenerates ketone Returning utilization；Ammonium carboxylate salt dehydrating condensation regenerates amide Returning utilization；The bottom material after amide has been recycled with industrial hydrogen peroxide reaction regeneration into peroxide Returning utilization.The invention belongs to hydrazine hydrate preparing technical fields, and this method synthesis yield is high, and peroxide is renewable, reduces the participation of water in the reaction, reduces the generation of side reaction, improve product quality.
Description
Technical field
The invention belongs to the sides that hydrazine hydrate preparing technical field, in particular to a kind of peroxide regenerate oxo-synthesis of hydrazine hydrate
Method.
Background technology
Hydrazine hydrate also known as hydrazine hydrate are the sulfuric monohydrate (N of hydrazine2H4·H2O), appearance is colourless transparent liquid, can be with
Water, alcohol arbitrarily mix, and do not dissolve in ether and chloroform.Hydrazine hydrate is a kind of important industrial chemicals and the production of widely used chemical industry
Product, be produce foaming agent, pesticide, medicine, dyestuff, developer and reducing agent important source material, be additionally operable to manufacture high purity metal,
Synthetic fibers and rare element separation, the deoxidation of large-sized boiler water supply, the production etc. of rocket fuel and explosive.
At present the production method of hydrazine hydrate mainly have Raschig process, urea method, ketazine process (Bayer methods), peroxide passivation with
And air oxidation process etc..
Raschig process (Raschig) has at home and abroad substantially been eliminated at present.
Urea method is with hypochlorite to carry out that hydrazine hydrate is obtained by the reaction in alkaline solution using urea, what this method obtained
Hydrazine hydrate yield is between 75-80% (in terms of Cl)；Every mole of hydrazine hydrate needs to consume 4 moles of caustic soda, also pair in reaction process
The inorganic salts such as a large amount of sodium carbonate, sodium chloride are produced, the separation of by-product difficulty also needs to consume a large amount of steaming by evaporating, concentrating
Vapour so that the raw materials consumption of hydrazine hydrate, energy consumption are higher, do not meet national energy conservation and emission reduction, the theory of circular economy；Thus urinate
Plain method energy consumption and material consumption height, yield are low, and environmental protection pressure is bigger.
The high income of ketazine process (Bayer), the method are quickly grown at home in recent years, and ketazine is in the presence of ketone
Ammonia is aoxidized with oxidant (sodium hypochlorite) to synthesize, ketazine hydrolyzes under high pressure generates hydrazine hydrate and ketone, hydrolyzes generation
Ketone is recycled for producing ketazine；Although ketazine process only needs to consume 2 moles of caustic soda, and ammonia therein etc. is recycled profit
With, reduce raw materials consumption, but due to the needs of its hydrolysis, the concentration of hydrazine hydrate of preparation also 10%~12% or so,
It is follow-up to also need to carry out concentration and evaporation, it is also desirable to consume a large amount of steam；Importantly, though ketazine process yield is high, produce
Raw saliferous waste residue, and waste water containing COD is generated, environmental protection pressure is big, and limit is received in the use of part medicine, electronics, space flight etc.
System.
Peroxide passivation (PUCK methods) is the technique of France's invention, similar to ketazine process technique, and only oxidant is with height
The hydrogen peroxide of concentration, the methyl ethyl ketone that ketone is mainly.Peroxide passivation (PUCK methods) is although environmental protection, and yield is high, in China
Industrialized production or blank out.Domestic literature report will use high concentration hydrogen peroxide to the research of this method, and it is hidden to there is safety
Suffer from, low with low concentration hydrogen peroxide synthesis yield, production cost is high, and industrial applications value is little.
Invention content
To solve above-mentioned existing problem, the present invention provides a kind of method that peroxide regenerates oxo-synthesis of hydrazine hydrate, the party
The hydrazine hydrate of method production is to use controlled syntheses intermediate raw material, and by intermediate raw material oxo-synthesis of hydrazine hydrate, and intermediate raw material is repeatable
Regeneration, not only high income, does not equally generate environment pollution.
The technical solution adopted by the present invention is as follows：A kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate, including walk as follows
Suddenly：
(I) it is catalyst with organic amine or derivatives thereof, ketone and amide first carry out addition cyclization, generate 2-R3Hydroxyl-
3R1R2Azepine propylene oxide intermediate；Its reaction equation is as follows：
(II) 2-R generated3Hydroxyl -3R1R2Azepine propylene oxide intermediate, then be condensed with renewable peroxide
Reaction generates a pair of horses going side by side 2-R3Hydroxyl -3R1R2Azepine propylene oxide intermediate raw material；Its reaction equation is as follows：
(III) it is quantitatively passed through liquefied ammonia again and carries out cracking acid-base neutralization reaction, generates among ketazine intermediate and ammonium carboxylate salt
Body；Its reaction equation is as follows：
(IV) the ketazine intermediate hydrolysis in step (III) generates hydrazine hydrate and ketone, regenerates ketone Returning utilization；It is reacted
Equation is as follows：
(V) the ammonium carboxylate salt intermediate dehydrating condensation in step (III) regenerates amide Returning utilization；Its reactional equation
Formula is as follows：
(VI) it is renewable dose to have recycled the bottom material after amide 98%, with industrial hydrogen peroxide reaction regeneration at peroxide
Returning utilization, the peroxide are homemade SODIUM PERCARBONATE or peroxide urea；Its reaction equation is：
2Na2CO3+3H2O2→2Na2CO3·3H2O2
Or CO (NH2)2+H2O2→CO(NH2)2·H2O2。
Further, the molar ratio of the addition of the ketone described in step (I) and catalyst is 1：(0.002~0.1).
Further, the ketone that is added in above-mentioned (I) (II) (III) step, amide, peroxide, liquefied ammonia molar ratio be (1
~4)：(1~4)：(0.5~3)：(0.5~4), reaction temperature are preferably 28~68 DEG C, and reaction pressure is normal pressure or is less than
It is carried out under the micro-positive pressure of 0.2MPa.Liquefied ammonia is quantitative in step (III), and liquefied ammonia participates in reacting completely, so in whole process not
Need to recycle liquefied ammonia, and other ketazine technique ammonia be it is a large amount of excessive, the recycling problem of liquefied ammonia be other techniques without
The problem that method is avoided, including research technique of the country to hydrogen peroxide legal system hydrazine hydrate (PUCK).
Further, step (IV) obtains the target product hydrazine hydrate of this programme, in addition generates that raw ketone is also renewable follows
Ring utilizes, and step (IV) is carried out in tower, and tower can be packed tower, can also be column plate tower, the water described in step (IV)
Molar ratio with the inventory of ketazine intermediate is (3~12)：1, reaction temperature is controlled at 110~185 DEG C, in step (IV)
In reaction process plus nitrogen protection, nitrogen keep system pressure in 0.1~1MPa.There are two the main functions for adding nitrogen, when
Oxygen in displaced air reduces impurity and generates, second is that system pressure is maintained to ensure that hydrolysis is complete.
Further, step (V) is to regenerate the ammonium carboxylate salt intermediate that reaction generates to react required original as us
Material, it is therefore an objective to which economize on resources cost, while also reducing the influence caused by environment.Whole process is carried out in tower and kettle, step
Suddenly (V) is intermittent dehydration, and steam, oil bath or fused salt heat supply, dehydration Optimal Temperature is used to select 60~220 DEG C in reaction process,
Pressure is completed in the case where taking out negative pressure condition, and vacuum, which takes out to bear, to be ensured to carry out at 0.01~0.1MPa；The segments of product that tower top steams
Trapping：What early period, dehydration trapped is process water, return to step (IV), later stage trapping amide return course (I)；If used
Sodium carbonate or peroxide urea do [O] raw material, and bottom material, which returns, uses dioxygen water reuse (treatment, wherein when doing bottom material with peroxide urea, urea exists
A small amount of decomposition is had when high temperature dehydration or polymerization, this mixture have no effect on this technological reaction, polymerize the dicyandiamide of generation instead
Or melamine can make catalyst use, it is beneficial to reacting.
Preferably, organic amine described in step (I) or derivatives thereof is one in cyanamide, dicyandiamide or melamine
Kind is a variety of.Catalyst organic amine or derivatives thereof can be one of which or several mixing, preferred catalyst in process (I)
It is melamine.R described in step (I)1And R2For the straight chained alkyl or cyclic alkyl of 1-10 carbon atom, R3It is hydrogen or tool
There is the alkyl of 1-6 carbon atom.
Preferably, the ketone described in step (I) is acetone, 2- butanone or cyclohexanone.
Preferably, the amide described in step (I) is formamide, acetamide or propionamide.
It is a discovery of the invention that when ketone is reacted with amide equimolar ratio, a period of time is reacted at 0~100 DEG C, when normal
When pressure is heated to the boiling point of ketone, no apparent boiling phenomenon occurs, this is because largely generating new substance 2-R3Hydroxyl-
3R1R2The boiling point of the reason of azepine propylene oxide, novel substance are more significantly raised than the boiling point of ketone.
Further, the hydrogen peroxide described in step (VI) is 25%~30% regular industrial hydrogen peroxide, wherein superfluous
Water is handled by Conventional concentration can reach first discharge standard, and concentrate is recyclable to be applied mechanically.25%~30% dioxygen in this step
There is excessive water in water, but can reach discharge by simple and regular processing.The aqueous solution that the reaction was complete in step (VI), using normal
Recycled after rule decompression dehydration.The water deviate from the process completely can be with qualified discharge.So entire technique need not be another
Build wastewater treatment equipment.
Raw material peroxide [O] almost covers all peroxide in step (II), but preferably, in step (II)
The peroxide is homemade SODIUM PERCARBONATE or peroxide urea, can be any one or more mixing therein, this is anti-
It should be environmentally friendly operation.Preferred purpose：Mainly SODIUM PERCARBONATE or peroxide urea sodium carbonate or urea that the reaction was complete generates afterwards
Recyclable, the sodium carbonate or urea of recycling reduce the ginseng of water again with hydrogen peroxide reaction regeneration at SODIUM PERCARBONATE or peroxide urea
With, reducing the generation of side reaction, improves product quality, the water for reacting generation is supplied to step (IV) hydrolysis to apply mechanically completely,
It emits no waste water.
Preferably, ketazine intermediate described in step (III) will be obviously layered with unclassified stores.Process (III) is anti-
After answering completely, it is with the significantly different point of other techniques：No matter which kind of raw ketone, the product ketazine that is generated and other objects are used
Material can be obviously layered, and compared with other techniques, this substantial saved manufacture energy consumption.The main reason is that raw material amide passes through
(I) ammonium carboxylate salt is generated after (II) (III) step reaction, and ammonium carboxylate salt does not dissolve in ketone, is equally also insoluble among ketazine
Product, so there is apparent layering.
The present invention is obtained and is had the beneficial effect that using the above scheme：The side of peroxide regeneration oxo-synthesis of hydrazine hydrate of the present invention
Method, the method for the present invention produce hydrazine hydrate whole process in addition to consumption hydrogen peroxide is for regenerating peroxide, consumption liquefied ammonia generation carboxylic
Outside sour ammonium regeneration amide, intermediate raw material is renewable to be recycled.Whole process does not have any waste to generate, and synthesis yield is high,
It is most rationally most environmentally friendly hydrazine hydrate production technique.
Figure of description
Fig. 1 is present invention process flow chart.
Specific implementation mode
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
All other embodiment that technical staff is obtained without making creative work belongs to the model that the present invention protects
It encloses.Acetone, acetamide, liquefied ammonia, hydrogen peroxide are technical grade in following embodiments.
Comparative example 1
In tetra- mouthfuls of reaction flasks of 1000ml, 280 grams of acetone is added, 285 grams of acetamide, acetamide is lived in comparative example 1
Property catalyst use, stirring is warming up to 45~50 DEG C, and liquefied ammonia is passed through by 25 ls/h of speed, be added hydrogen peroxide (hydrogen peroxide
Mass percent is 27.5%) 300 grams, controls 8 hours reaction time, stops reaction, and entirely reaction liquefied ammonia is excessive, as a result
Do not occur lamination, feed liquid turns yellow, analysis wherein ketazine, ketazine yield only 38.68% in terms of hydrogen peroxide.
Embodiment 1
In tetra- mouthfuls of reaction flasks of 1000ml, 280 grams of acetone is added, 285 grams of acetamide, acetamide is made anti-in embodiment 1
It answers raw material to use, 10 grams of catalyst melamine is added, stirring is warming up to 45~50 DEG C, and after reacting 45 minutes, hydrogen peroxide (mistake is added
The mass percent of hydrogen oxide is 27.5%) 300 grams, and 100 liters of quantitative liquefied ammonia, control reaction are passed through by 25 ls/h of speed
8 hours time stopped reaction, and was as a result obviously layered, the equal water white transparency of levels separates upper oil phase and weighs, analyzes it
Middle ketazine, ketazine yield is 91.82% in terms of hydrogen peroxide.
Embodiment 2
In tetra- mouthfuls of reaction flasks of 1000ml, 280 grams of acetone is added, 285 grams of acetamide, acetamide is made anti-in embodiment 2
It answers raw material to use, 10 grams of catalyst melamine is added, stirring is warming up to 50 DEG C, after reacting 45 minutes, SODIUM PERCARBONATE is added and (contains
The mass percent for imitating oxygen is about 13%) 295 grams, is passed through 100 liters of quantitative liquefied ammonia by 25 ls/h of same speed, control is anti-
8 hours between seasonable, stop reaction, be as a result obviously layered, the equal water white transparency of levels separates upper oil phase and weighs, analysis
Wherein ketazine, ketazine yield is 95.36% in terms of effective oxygen.By wherein reacted SODIUM PERCARBONATE carrier, hydrogen peroxide is used
Repeated reproducibility SODIUM PERCARBONATE repeats experiment 50 times, and ketazine yield is 95.25% in terms of effective oxygen, to result without apparent shadow
It rings.
Embodiment 3
In 50L stainless steel reactors, 14 kilograms of acetone is added, 14.25 kilograms of acetamide, acetamide is made in embodiment 3
Reaction raw materials are used, and 0.5 kilogram of catalyst melamine is added, and stirring is warming up to 45~50 DEG C, and after reacting 45 minutes, carbon was added
Sour 14.75 kilograms of sodium (mass percent containing effective oxygen is about 13%), by 1.25m3The speed of/hour is passed through quantitative liquefied ammonia 5m3
8 hours reaction time is controlled, stops reaction, is as a result obviously layered, the equal water white transparency of levels separates upper oil phase and claims
Weight, analysis wherein ketazine, ketazine yield is 96.12% in terms of the effective oxygen of SODIUM PERCARBONATE.
Embodiment 4
According to embodiment 3 at the middle and upper levels ketazine as a result, press water：Mole charge ratio 10.5 of ketazine：1, it calculates
Technique water yield should be added, be put into the reboiler of designed 50 liters of hydrolysis towers, closed good equipment, heat up, nitrogen tune is used in combination
Pressure ensures pressure in 0.6MPa, and system temperature controls flow at 170~175 DEG C, gradually with nitrogen by upper layer ketazine pressure
Enter in tower and be hydrolyzed, hydrolysis time 2 hours, hydrolysis finishes, and it is 98.5% that yield is hydrolyzed in terms of ketazine, and bottom of tower hydrazine hydrate is dense
Degree is 30.5%, and by this dilute concentration hydrazine hydrate concentrate to 80%, yield 97.8%.
Embodiment 5
It is put into subnatant in embodiment 3 in designed concentration kettle, with heat-conducting oil heating, first controls temperature at 60 DEG C,
Pressure is controlled in 0.1MPa, controls dewatering speed, temperature is made slowly to increase, collection process water, is hydrolyzed and is used for ketazine.It is de-
Water is complete, and conversion collecting tank then increases temperature to amide regenerating tank, control pressure in -0.09MPa, temperature control 175~
180 DEG C, collect amide, the amide rate of recovery 98.5%.The bottom material sodium carbonate rate of recovery has 95% simultaneously.
Embodiment 6
It by 5 bottom material of embodiment and needs additive amount oxide spinel sodium together, is put into SODIUM PERCARBONATE reaction kettle processed, make percarbonic acid
Sodium repeats 3 step of embodiment, analyzes ketazine, and ketazine yield is 96.01% in terms of the effective oxygen of SODIUM PERCARBONATE.
Embodiment 7
In 50L stainless steel reactors, 14 kilograms of acetone is added, acetamide (14.25 kilograms, make in embodiment 7 by acetamide
Reaction raw materials are used, and 0.5 kilogram of catalyst melamine is added, and stirring is warming up to 45~50 DEG C, and after reacting 45 minutes, peroxide is added
12.4 kilograms of urea (mass percent containing effective oxygen is about 15.8%), by 1.25m3The speed of/hour is passed through quantitative liquefied ammonia
5m38 hours reaction time is controlled, stops reaction, is as a result obviously layered, the equal water white transparency of levels separates upper oil phase
It weighs, analysis wherein ketazine, ketazine yield is 97.50% in terms of the effective oxygen of peroxide urea.
Embodiment 8
The mother liquor of SODIUM PERCARBONATE will have been extracted in embodiment 6, taken 2000 grams in 2000ml glass concentration kettles, opened true
Sky keeps vacuum in -0.08MPa hereinafter, electric chuck heating, slowly heats up, and guarantee temperature in the kettle is no more than 70 DEG C of dehydrations, is protecting
Vacuum is held under -0.08MPa negative pressure, when temperature in the kettle is more than 70 DEG C, concentrated mother liquor is pressed 6 recycled of example by stopping dehydration
SODIUM PERCARBONATE is made, each index, wherein COD in water are deviate from analysis：15mg/l, BOD:5mg/l, total nitrogen：11mg/l, ammonia nitrogen：
0.8mg/l.Reach first discharge standard.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (10)
1. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate, which is characterized in that include the following steps：
(I) it is catalyst with organic amine or derivatives thereof, ketone and amide first carry out addition cyclization, generate 2-R3Hydroxyl -3R1R2Nitrogen
Heterocycle Ethylene Oxide intermediate；Its reaction equation is as follows：
(II) 2-R generated3Hydroxyl -3R1R2Azepine propylene oxide intermediate, then with renewable peroxide be condensed instead
It answers, generates a pair of horses going side by side 2-R3Hydroxyl -3R1R2Azepine propylene oxide intermediate raw material；Its reaction equation is as follows：
(III) it is quantitatively passed through liquefied ammonia again and carries out cracking acid-base neutralization reaction, generates ketazine intermediate and ammonium carboxylate salt intermediate；
Its reaction equation is as follows：
(IV) the ketazine intermediate hydrolysis in step (III) generates hydrazine hydrate and ketone, regenerates ketone Returning utilization；Its reactional equation
Formula is as follows：
(V) the ammonium carboxylate salt intermediate dehydrating condensation in step (III) regenerates amide Returning utilization；Its reaction equation is such as
Under：
(VI) it is renewable dose to have recycled the bottom material after amide 98%, is returned at peroxide with industrial hydrogen peroxide reaction regeneration
It utilizes, the peroxide is homemade SODIUM PERCARBONATE or peroxide urea；Its reaction equation is：
2Na2CO3+3H2O2→2Na2CO3·3H2O2
Or CO (NH2)2+H2O2→CO(NH2)2·H2O2。
2. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step (I)
Described in ketone and catalyst addition molar ratio be 1：(0.002~0.1).
3. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that above-mentioned (I)
(II) ketone that is added in (III) step, amide, peroxide, liquefied ammonia molar ratio be (1~4)：(1~4)：(0.5~3)：
(0.5~4), reaction temperature are 28~68 DEG C, and reaction pressure carries out under the micro-positive pressure for normal pressure or less than 0.2MPa.
4. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step (IV)
Described in water and ketazine intermediate inventory molar ratio be (3~12)：1, reaction temperature is controlled at 110~185 DEG C,
In step (IV) reaction process plus nitrogen protection, nitrogen keep system pressure in 0.1~1MPa.
5. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step (V)
For intermittent dehydration, steam, oil bath or fused salt heat supply, dehydration Optimal Temperature is used to select 60~220 DEG C in reaction process, pressure is
It is completed in the case where taking out negative pressure condition, vacuum, which takes out to bear, to be ensured to carry out at 0.01~0.1MPa；The segments of product trapping that tower top steams：Before
What phase dehydration trapped is process water, return to step (IV), later stage trapping amide return to step (I)；If using SODIUM PERCARBONATE
Or peroxide urea does [O] raw material, bottom material, which returns, uses dioxygen water reuse (treatment, wherein when doing bottom material with peroxide urea, urea is de- in high temperature
A small amount of decomposition is had when water or polymerization, this mixture have no effect on this technological reaction, polymerize the dicyandiamide or trimerization of generation instead
Cyanamide can make catalyst use, beneficial to reacting.
6. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step (I)
Described in organic amine or derivatives thereof be one or more in cyanamide, dicyandiamide or melamine.
7. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step (I)
Described in ketone be acetone, 2- butanone or cyclohexanone.
8. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step (I)
Described in amide be formamide, acetamide or propionamide.
9. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step (VI)
Described in hydrogen peroxide be 25%~30% regular industrial hydrogen peroxide, can reach wherein superfluous water is handled by Conventional concentration
First discharge standard, concentrate is recyclable to be applied mechanically.
10. a kind of method of peroxide regeneration oxo-synthesis of hydrazine hydrate according to claim 1, which is characterized in that step
(III) ketazine intermediate described in will be obviously layered with unclassified stores.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380708A (en) * | 2022-01-26 | 2022-04-22 | 中国天辰工程有限公司 | Method for recovering catalyst for synthesizing hydrazine hydrate intermediate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933910A (en) * | 1973-05-19 | 1976-01-20 | Bayer Aktiengesellschaft | Process for the production of ketazines |
| US3972878A (en) * | 1974-02-08 | 1976-08-03 | Produits Chimiques Ugine Kuhlmann | Method for preparing azines and hydrazones |
| CN1149578A (en) * | 1995-10-27 | 1997-05-14 | 化学工业部西南化工研究院 | Method for synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process |
| CN104555953A (en) * | 2014-10-11 | 2015-04-29 | 重庆锦杉科技有限公司 | Preparation method of hydrazine hydrate |
-
2018
- 2018-05-31 CN CN201810544523.0A patent/CN108569681A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933910A (en) * | 1973-05-19 | 1976-01-20 | Bayer Aktiengesellschaft | Process for the production of ketazines |
| US3972878A (en) * | 1974-02-08 | 1976-08-03 | Produits Chimiques Ugine Kuhlmann | Method for preparing azines and hydrazones |
| CN1149578A (en) * | 1995-10-27 | 1997-05-14 | 化学工业部西南化工研究院 | Method for synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process |
| CN104555953A (en) * | 2014-10-11 | 2015-04-29 | 重庆锦杉科技有限公司 | Preparation method of hydrazine hydrate |
Non-Patent Citations (1)
| Title |
|---|
| 顾春思等: "过氧化氢法合成丁酮连氮的工艺研究", 《化学试剂》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380708A (en) * | 2022-01-26 | 2022-04-22 | 中国天辰工程有限公司 | Method for recovering catalyst for synthesizing hydrazine hydrate intermediate |
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