CN1053656C - Method for synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process - Google Patents
Method for synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process Download PDFInfo
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- CN1053656C CN1053656C CN95113048A CN95113048A CN1053656C CN 1053656 C CN1053656 C CN 1053656C CN 95113048 A CN95113048 A CN 95113048A CN 95113048 A CN95113048 A CN 95113048A CN 1053656 C CN1053656 C CN 1053656C
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- hydrazine hydrate
- methylethylketone
- ammonia
- hydrogen peroxide
- azine
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Abstract
The present invention provides a method for synthesizing hydrazine hydrate by an ammonia-hydrogen peroxide liquid-phase catalysis oxygenation method. Rare earth-silica gel-phosphate are used as catalysts, hydrogen peroxide is used as an oxidizing agent and methyl ethyl ketone is used as a reaction medium and the catalysts, the oxidizing agent and the reaction medium react to synthesize water-insoluble methyl ethyl ketone azine intermediate bodies; the methyl ethyl ketone azine is separated from the methyl ethyl ketone azine intermediate bodies by a phase separator, and hydrazine hydrate is obtained through the hydrolysis. The present invention has the advantages of less investment, low energy consumption, no chloride by-product, high product yield, etc.; the catalysts and amide can be recovered circularly for reuse, and the present invention is favorable for environment protection.
Description
The present invention is a kind of method of synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process.
Hydrazine hydrate is an important chemical material, has purposes widely, owing to contain two nucleophilic nitrogen and four replaceable hydrogen in the hydrazine hydrate molecule, therefore, is that the fine chemical product of raw material almost relates to all areas with the hydrazine hydrate.Because the application of hydrazine hydrate constantly enlarges, so production technique is updated, the method for oxo-synthesis of hydrazine hydrate has four kinds: oxidation proceses of ammonia, Wyler's process, ketazine process and dioxygen water law.
As everyone knows, United States Patent (USP) 910858 (La Xifa) hypochlorous sodium is the oxygenant oxo-synthesis of hydrazine hydrate, and this method needs excessive ammonia, and ammonia: the mol ratio of clorox is 30: 1, and hydrazine hydrate concentration has only 1--2% in the reaction solution; United States Patent (USP) 3494737 (Bayer ketazine process) is a reaction medium with acetone, has avoided the decomposition of hydrazine hydrate, but ammonia: the mol ratio of clorox is 20: 1, thereby produces the energy consumption height of hydrazine hydrate; 3442612 couples of La Xifa of United States Patent (USP) improve, and replace ammonia to make nitrogenous source with urea, though easy and simple to handle, less investment, the concentration of hydrazine hydrate has only about 3% in reaction solution, has shortcomings such as energy consumption height and by product are many.The Bayer ketazine process is the technology of the development seventies, has to replace the traditional oxidation proceses of ammonia and the trend of Wyler's process.Though Bayer ketazine method has a series of advantage, be raw material but still need chlorine and sodium hydroxide.Because the production of these two kinds of products all will consume a large amount of electric energy, so the development of Bayer ketazine process still can be subjected to the restriction of raw material and environmental protection.
United States Patent (USP) 3972878 (PCUK method) is oxygenant with the hydrogen peroxide, and acid amides is the carrier of oxygen, and phosphoric acid salt is the catalyzer oxo-synthesis of hydrazine hydrate.The technological process of dioxygen water law oxo-synthesis of hydrazine hydrate comprises the synthetic of methylethylketone azine, the pressurized hydrolysis of methylethylketone azine and rare hydrazine hydrate carry three process such as dense.Though the PCUK method has no chlorinated secondary product, help advantages such as environment protection and energy consumption be relatively low, adopt the yield low (having only 78%) of the synthetic methylethylketone azine of single phosphate as catalyst and cause energy consumption and material consumption height in hydrogen peroxide.
Purpose of the present invention just is to overcome the aforesaid method weak point, and a kind of less investment is provided, low, the first chlorinated secondary product of energy consumption, and what the product yield was high in the presence of--silica gel--phosphate catalyst, is combined to the method for hydrazine hydrate at rare earth with the hydrogen peroxide oxidation ammoniacal liquor.
The object of the present invention is achieved like this:
Adopting rare earth--silica gel--phosphate as catalyst, is oxygenant with the hydrogen peroxide, is reaction medium with the methylethylketone, synthesizes water-fast intermediate methylethylketone azine, and tells the methylethylketone azine through phase separator, obtains hydrazine hydrate through hydrolysis again.
Wherein each substance weight per-cent is in the catalyzer:
Rare earth oxide 10--20%
Silica gel 10--40%
Phosphoric acid hydrogen two is received 5--40%
EDTA and an alkali metal salt 5--40% thereof
Methylethylketone: hydrogen peroxide=1.5--4.0 (mol ratio)
The reaction formula of ammonia hydrogen peroxide liquid phase catalytic oxidation oxo-synthesis of hydrazine hydrate is as follows:
Accompanying drawing is the process flow sheet of oxo-synthesis of hydrazine hydrate of the present invention.
Raw material hydrogen peroxide concentrate to 70% with 27.5%. Again with 70% hydrogen peroxide, help Catalyst, catalyst and MEK add in the reactor together, and logical ammonia also stirs intensification To 35--70 ℃ (pressure is normal pressure 0.5MPa), to react 3--12 hour, product is MEK azine and water. Reactant enters the phase separator phase-splitting, and the upper strata is oil phase, and is lower Layer is water. Oil phase and water enter the hydrolysis tower hydrolysis by a certain percentage. The first that is hydrolyzed out The ethyl ketone Returning reactor recycles. Rare hydrazine hydrate that hydrolysis obtains enters hydrazine hydrate and carries Dense tower is with the hydrazine hydrate product of rare hydrazine hydrate concentrate to 80%.
The reaction water reclaims catalyst through centrifugal filtration. Through the water behind the centrifuge Replenish a certain amount of acetic acid, enter the acetamide destilling tower, reclaim acetamide, make Acetamide process spray crystallization again Returning reactor recycles.
The method of ammonia hydrogen peroxide liquid phase catalytic oxidation oxo-synthesis of hydrazine hydrate provided by the invention, Its major advantage is as follows; (1) compares with Bayer process with La Xifa, because no a large amount of The concentration of hydrazine hydrate is higher in ammonia circulation and the hydrolysate, thereby small investment, and energy consumption is low (2) the hydrazine hydrate production cost hangs down 1/4 approximately than said method; (3) catalyst and acid amides, Ammonia, MEK all can be recycled; (4) no chlorinated secondary product is conducive to environment Protection; (5) reactor is easy to amplify. Compare synthetic MEK azine with the PCUK method Yield reaches more than 92%, and the synthetic MEK azine yield of PCUK method only 78%; With dioxygen The whole process yield of the oxo-synthesis of hydrazine hydrate of water meter reaches 85%, and the PCUK method only has 75%.
The invention will be further described with example below: in the present invention, the synthesis yield of methylethylketone azine serves as to calculate benchmark with the hydrogen peroxide that adds.No matter the present invention is with fresh methylethylketone or reclaims methylethylketone and react as raw material that gained methylethylketone azine yield all can reach more than 92%, and the oxo-synthesis of hydrazine hydrate total recovery reaches 85%.
Example one:
In Wolff bottle, add hydrogen peroxide (74%) 1.4mol, methylethylketone 2.2mol, ethanamide 1.3mol, phosphate catalyst 0.8 gram, logical ammonia stirs and is warming up to 35--70 ℃, reacts after 3--12 hour stopped reaction.Reaction solution being moved into phase separator, behind the question response liquid standing demix, tell upper oil phase and weigh, and analyze wherein methylethylketone azine content, is 78.75% in the methylethylketone azine yield of hydrogen peroxide.
Example two:
In Wolff bottle, add hydrogen peroxide (74%) 1.1mol, methylethylketone 1.5mol, catalyzer 5 grams, ethanamide 0.9mol, according to the facts the condition and the working method of example one are carried out for other.After reaction finishes, tell upper oil phase and weigh, analyze wherein methylethylketone azine content, in the methylethylketone azine yield 92% of hydrogen peroxide.
Example three:
In Wolff bottle, add hydrogen peroxide (73%) 1.6mol, reclaim methylethylketone 2.3mol, reclaim ethanamide 1.3mol, catalyzer 5 grams, other according to the facts the condition and the working method of example one carry out, gained methylethylketone azine yield is 93.94%.
Example four:
With the methylethylketone azine of above-mentioned reaction gained, in 2 liters of hydrolysis kettles, carry out pressurized hydrolysis: 130 ℃ of hydrolysis temperatures by following condition--190 ℃; Hydrolysis pressure 0.1MPa--1.2MPa; Water: the methylethylketone azine is 3--15 (mol ratio); Hydrolysis time 2--12 hour.Hydrolysis finishes, and is 99.19% in the hydrolysis yield of methylethylketone azine, hydrazine hydrate concentration 20.09% in the hydrolysis kettle.This rare hydrazine hydrate is carried dense to 80% hydrazine hydrate, its yield is 98%.
Claims (4)
1, a kind of method of synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process, it is characterized in that: adopt rare earth--silica gel--phosphate as catalyst, with the hydrogen peroxide is oxygenant, with the methylethylketone is reaction medium, synthetic water-fast intermediate methylethylketone azine, and tell the methylethylketone azine through phase separator, obtain hydrazine hydrate through hydrolysis again.
2, method according to claim 1 is characterized in that: each substance weight per-cent is in the catalyzer:
Rare earth oxide 10--20%
Silica gel 10--40%
Phosphoric acid hydrogen two is received 5--40%
EDTA and an alkali metal salt 5--40% thereof
3, method according to claim 1 and 2 is characterized in that: methylethylketone: hydrogen peroxide=1.5--4.0 (mol ratio).
4, method according to claim 1 is characterized in that: all recyclable utilization of catalyzer, ethanamide, ammonia, methylethylketone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113048A CN1053656C (en) | 1995-10-27 | 1995-10-27 | Method for synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113048A CN1053656C (en) | 1995-10-27 | 1995-10-27 | Method for synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1149578A CN1149578A (en) | 1997-05-14 |
| CN1053656C true CN1053656C (en) | 2000-06-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95113048A Expired - Fee Related CN1053656C (en) | 1995-10-27 | 1995-10-27 | Method for synthetic hydrazine hydrate by ammonia oxyful liquid phase catalytic oxidation process |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105130844A (en) * | 2015-07-29 | 2015-12-09 | 重庆锦杉科技有限公司 | Methyl ethyl ketazine preparation method |
| 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 |
| 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 |
| CN116554051A (en) * | 2023-05-12 | 2023-08-08 | 洛阳理工学院 | Method for rapidly synthesizing salicylaldehyde azine with assistance of ultrasonic waves |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3494737A (en) * | 1966-12-17 | 1970-02-10 | Bayer Ag | Process for the preparation of hydrazine by tray column fractionation |
| US3972878A (en) * | 1974-02-08 | 1976-08-03 | Produits Chimiques Ugine Kuhlmann | Method for preparing azines and hydrazones |
-
1995
- 1995-10-27 CN CN95113048A patent/CN1053656C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3494737A (en) * | 1966-12-17 | 1970-02-10 | Bayer Ag | Process for the preparation of hydrazine by tray column fractionation |
| US3972878A (en) * | 1974-02-08 | 1976-08-03 | Produits Chimiques Ugine Kuhlmann | Method for preparing azines and hydrazones |
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| CN1149578A (en) | 1997-05-14 |
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