CN106865513B - A kind of preparation method of hydrazine hydrate - Google Patents
A kind of preparation method of hydrazine hydrate Download PDFInfo
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- CN106865513B CN106865513B CN201710078020.4A CN201710078020A CN106865513B CN 106865513 B CN106865513 B CN 106865513B CN 201710078020 A CN201710078020 A CN 201710078020A CN 106865513 B CN106865513 B CN 106865513B
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- hydrolysis
- hydrazine hydrate
- ketazine
- hydrazine
- catalyst
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to chemosynthesis technical fields, and in particular to a kind of preparation method of hydrazine hydrate, this method include the steps that hydrolyzing ketazine in a distillation column to obtain hydrazine hydrate, it is characterised in that：Suitable catalyst is added in the hydrolyzate that hydrazine hydrate is produced in ketazine hydrolysis, the catalyst refers to the mixture of one or both of hydrazine hydrochloride, hydrazine sulfate.This method can effectively promote the progress of hydrolysis, the hydrolysis of ketazine is set to carry out under normal pressure, reduce the temperature and pressure of hydrolysis, shorten hydrolysis time, the yield for improving hydrazine hydrate, reduces steam consumption, requires hydrolysis device low, hydrolytic process danger is small, has the characteristics that the simple and economical remarkable benefit of industrial implementation.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of preparation method of hydrazine hydrate.
Background technology
Hydrazine hydrate is a kind of important industrial chemicals and widely used chemical products, can be hydrolyzed and is refining to obtain by ketazine
Arrive, 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.
Currently, there are mainly three types of the production methods of domestic hydrazine hydrate：La Xifa, urea method and ketazine process.Wherein, ketone connects
The yield highest of nitrogen method, the method are quickly grown at home in recent years.Ketazine is typically oxidant in the presence of acetone（It is secondary
Sodium chlorate or hydrogen peroxide）The ketazine for aoxidizing ammonia to synthesize.Ketazine hydrolyzes under high pressure generates hydrazine hydrate and acetone,
The acetone that hydrolysis generates is recycled for producing ketazine.Reaction equation is as follows：
2NH3 + NaClO + 2(CH3)2C=O → (CH3)2C=N-N=C(CH3)2 + NaCl + 3H2O
(CH3)2C=N-N=C(CH3)2 + 3H2O → 2(CH3)2C=O + N2H4•••••••H2O
In general, what the hydrolysis of ketazine was performed such：Ketazine and water is allowed to be continuously fed into certain proportion
Then reaction is hydrolyzed in destilling tower under elevated pressure, obtain the azeotropic mixture and vinasse of the acetone and water of distillate form
The hydrazine hydrate solution of form.It is a reversible endothermic reaction that ketazine, which hydrolyzes hydrazine hydrate processed, in order to promote the progress of hydrolysis,
Hydrolysis temperature is generally at 150 ~ 200 DEG C, and pressure is in 0.8 ~ 1MPa, and for hydrolysis time at 8 ~ 10 hours, yield was 80% ~ 90%.Therefore,
That there are hydrolysis temperatures is high for the prior art, pressure is big, and hydrolysis time is long, and yield is low, and steam consumption is big（1 ton of hydrazine hydrate of production need to disappear
Consume about 16 tons of steam）, high, the problems such as hydrolytic process is dangerous big, is required hydrolysis device.
Invention content
To solve the above-mentioned problems, the present inventor conducts in-depth research ketazine hydrolysis process, as a result, it has been found that,
Proper catalyst is added in ketazine hydrolyzate can effectively facilitate the progress of hydrolysis, can reduce the temperature and pressure of hydrolysis
Power shortens hydrolysis time, improves the yield of hydrazine hydrate.The present invention is namely based on this discovery to complete.
The object of the present invention is to provide a kind of preparation method of hydrazine hydrate, this method can reduce ketazine hydrolysis
Temperature and pressure shortens hydrolysis time, improves the yield of hydrazine hydrate, reduces steam consumption, low to hydrolysis device requirement, hydrolyzed
Journey danger is small, and it also has the characteristics that the simple and economical remarkable benefit of industrial implementation.
To achieve the above object, the technical solution adopted by the present invention is：The hydrolyzate of hydrazine hydrate is produced in ketazine hydrolysis
Middle that suitable catalyst is added, the catalyst refers to the mixture of one or both of hydrazine hydrochloride, hydrazine sulfate, catalyst
Addition is the 5% ~ 30% of ketazine quality.Specifically processing step is：Ketazine and water are added with molar ratio 1: 5 ~ 1: 20
Enter into destilling tower, then the catalyst of ketazine quality 5% ~ 30% is added into destilling tower, then in column bottom temperature 120 ~ 130
DEG C and 60 ~ 100 DEG C of tower top temperature at distilled with reflux ratio R=5 ~ 20, hydrolysis time be 4 ~ 6 hours, the azeotropic of acetone and water
Object is steamed from tower top and is recycled in the form of distillate, after the completion of hydrolysis, continues to distill, and collects tower top temperature at 110 ~ 120 DEG C
Distillate be hydrazine hydrate（A concentration of 80 ~ 90%）；The vinasse that catalyst is contained in bottom of tower is circularly used for hydrolysis.
Beneficial effects of the present invention are as follows：The present invention is effectively facilitated by the way that catalyst is added into ketazine hydrolyzate
The progress of hydrolysis, enables the hydrolysis of ketazine to carry out under normal pressure, reduces the temperature and pressure of hydrolysis,
Hydrolysis time is shortened, the yield of hydrazine hydrate is improved（The yield of hydrazine hydrate is increased to 90 ~ 95% from 80 ~ 90%）, reduce
Steam consumption（1 ton of hydrazine hydrate of production need to only consume about 8 tons of steam）, low to hydrolysis device requirement, hydrolytic process danger is small, tool
There is the features such as industrial implementation simple and economical remarkable benefit.
Specific implementation mode
Embodiment 1
224kg ketazines and 180kg water are added to destilling tower（Interior diameter=360mm, height=15000mm, 45 towers
The bubble column of disk）In, then 25kg hydrazine hydrochlorides are added into destilling tower, then 120 ~ 130 DEG C of column bottom temperature and tower top temperature 60 ~
It is distilled with reflux ratio R=10 at 100 DEG C, hydrolysis time is 6 hours, and the azeotropic mixture of acetone and water is steamed from tower top to distillate
The form of liquid recycles, and after the completion of hydrolysis, continues to distill, and collects distillate 109.6kg of the tower top temperature at 110 ~ 120 DEG C, water
It is 83% to close hydrazine content.
Embodiment 2
224kg ketazines and 250kg water are added to destilling tower（Interior diameter=360mm, height=15000mm, 45 towers
The bubble column of disk）In, then 45kg hydrazine sulfates are added into destilling tower, then 120 ~ 130 DEG C of column bottom temperature and tower top temperature 60 ~
It is distilled with reflux ratio R=15 at 100 DEG C, hydrolysis time is 5 hours, and the azeotropic mixture of acetone and water is steamed from tower top to distillate
The form of liquid recycles, and after the completion of hydrolysis, continues to distill, and collects distillate 105.7kg of the tower top temperature at 110 ~ 120 DEG C, water
It is 88% to close hydrazine content.
Embodiment 3
224kg ketazines and 320kg water are added to destilling tower（Interior diameter=360mm, height=15000mm, 45 towers
The bubble column of disk）In, then 35kg hydrazine hydrochlorides and 28kg hydrazine sulfates are added into destilling tower, then in 120 ~ 130 DEG C of column bottom temperature
It is distilled with reflux ratio R=12 at 60 ~ 100 DEG C of tower top temperature, hydrolysis time is 4 hours, and the azeotropic mixture of acetone and water is from tower
Top is steamed is recycled in the form of distillate, after the completion of hydrolysis, is continued to distill, is collected tower top temperature distillating at 110 ~ 120 DEG C
Liquid 110.6kg, hydrazine hydrate content are 85%.
Embodiment 4
224kg ketazines and 220kg water are added in embodiment 3 in the destilling tower with vinasse, then existed
It is distilled with reflux ratio R=8 at 60 ~ 100 DEG C of 120 ~ 130 DEG C of column bottom temperature and tower top temperature, hydrolysis time is 5 hours, acetone
It steams from tower top with the azeotropic mixture of water and is recycled in the form of distillate, after the completion of hydrolysis, continue to distill, collect tower top temperature and exist
Distillate 113.4kg at 110 ~ 120 DEG C, hydrazine hydrate content are 82%.
Claims (1)
1. a kind of preparation method of hydrazine hydrate, it is characterised in that include the following steps：By ketazine and water with molar ratio 1: 5~
Be added in destilling tower at 1: 20, then catalyst is added into destilling tower, then in 120~130 DEG C of column bottom temperature and tower top temperature
It is distilled with reflux ratio R=5~20 at 60~100 DEG C, hydrolysis time is 4~6 hours, and the azeotropic mixture of acetone and water is from tower top
It steams and is recycled in the form of distillate, after the completion of hydrolysis, continue to distill, collect distillate of the tower top temperature at 110~120 DEG C
As hydrazine hydrate；The vinasse that catalyst is contained in bottom of tower is circularly used for hydrolysis；The catalyst refer to hydrazine hydrochloride,
The mixture of one or both of hydrazine sulfate, the addition of catalyst are the 5%~30% of ketazine quality.
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| CN201710078020.4A CN106865513B (en) | 2017-02-14 | 2017-02-14 | A kind of preparation method of hydrazine hydrate |
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| CN201710078020.4A CN106865513B (en) | 2017-02-14 | 2017-02-14 | A kind of preparation method of hydrazine hydrate |
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| CN106865513B true CN106865513B (en) | 2018-11-02 |
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| CN108191708B (en) * | 2018-01-30 | 2021-04-06 | 江苏凌云药业股份有限公司 | Synthesis method of adipic acid dihydrazide |
| CN109437133A (en) * | 2018-12-25 | 2019-03-08 | 浙江工业大学 | A kind of method that butanone azine hydrolysis prepares hydrazine hydrate |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1049886C (en) * | 1992-04-24 | 2000-03-01 | 中国科学院福建物质结构研究所 | Preparation of hydrazine hydrate by calcium-ammonia method |
| CN1081180A (en) * | 1992-07-10 | 1994-01-26 | 化学工业部西南化工研究院 | Catalytic oxo-synthesis of hydrazine hydrate with ammonia and sodium hypochlorite |
| JP3962872B2 (en) * | 1995-08-14 | 2007-08-22 | 三菱瓦斯化学株式会社 | Method for synthesizing ketazine |
| CN1053656C (en) * | 1995-10-27 | 2000-06-21 | 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 |
| CN105130844A (en) * | 2015-07-29 | 2015-12-09 | 重庆锦杉科技有限公司 | Methyl ethyl ketazine preparation method |
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Effective date of registration: 20180919 Address after: 362000 Fujian Huian Quanzhou County Taiwan Investment Zone Dongyuan group Green Village seeking industrial area Applicant after: Fujian Quanzhou South flying bird shoe industry Co., Ltd. Address before: 408099 Chongqing city Fuling District Xinghua Middle Road 48, elegant garden apartment 12-5 Applicant before: Li Yashan |
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Effective date of registration: 20200413 Address after: 408000 Youfang village, Baitao Town, Fuling District, Chongqing (Jianfeng plant) Patentee after: Chongqing tengze Chemical Co., Ltd Address before: 362000 Qingcun Headhunting Industrial Zone, Dongyuan Group, Taiwanese Business Investment Zone, Huian County, Quanzhou City, Fujian Province Patentee before: FUJIAN QUANZHOU SOUTH FEINIAO FOOTWEAR INDUSTRY Co.,Ltd. |
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