CN105384655B - A kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system - Google Patents
A kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system Download PDFInfo
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- CN105384655B CN105384655B CN201510700258.7A CN201510700258A CN105384655B CN 105384655 B CN105384655 B CN 105384655B CN 201510700258 A CN201510700258 A CN 201510700258A CN 105384655 B CN105384655 B CN 105384655B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C241/00—Preparation of compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C241/02—Preparation of hydrazines
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/42—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrolysis
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system, it includes the steps such as pressurized hydrolysis, separation.This method is that the ketazine solution containing impurity isopropyl hydrazine in hydrazine hydrate hydrolysis system is introduced into two-stage pressurizing hydrolysis tower, it is hydrazine hydrate and acetone to make ketazine complete hydrolysis, one-level separation tower is returned in vapour form containing acetone and isopropyl hydrazine to be separated, acetone is isolated in one-level separation column overhead according to boiling point substance difference, acetone returns to acetone recovery system and recycled, and bottom of towe obtains aqueous isopropyl hydrazine.The present invention is recycled by two-stage separator to impurity isopropyl hydrazine, both separates harmful constituent, useful constituent has been reclaimed again, not only increase the percent hydrolysis of ketazine, while also reducing production cost.
Description
Technical field
The present invention relates to a kind of processing method of impurity, and in particular to one kind is removed in ketazine process hydrazine hydrate production system
The method of impurity.
Background technology
Hydrazine hydrate, also known as：Hydrazine hydrate, chemical formula is N2H4·H2O, is strong reductant, is important industrial chemicals,
It is the raw material of medicine, agricultural chemicals, dyestuff, foaming agent, developer, antioxidant；Produce, have for boiler water deoxidation, high pure metal
Machine compound synthesis and reduction, rare element separation, also serve as the manufacture of rocket fuel and explosive, with advances in technology, society
Can development, in recent years the application field of hydrazine hydrate also constantly widening.
The production method of hydrazine hydrate mainly has Raschig process, urea method, ketazine process, peroxide passivation and air oxidation process
Deng.The present invention mentions hydrazine hydrate production method for ketazine process, and it is using in the middle of acetone, sodium hypochlorite and ammonia reaction production
Body-ketazine, ketazine hydrolyzes the process of production hydrazine hydrate again.Its main chemical reactions equation is：
2NaOH+Cl2→ NaCl+NaClO+H2O
NH3+NaClO→NH2Cl+NaOH
CH3COCH3+NH3+NH2Cl+NaOH→(CH3)2C=N-NH2+H2O+NaCl
(CH3)2C=N-NH2+H2O+CH3COCH3→(CH3)2C=N-N=C(CH3)2Synthetic reaction
(CH3)2C=N-N=C(CH3)2+3H2O→N2H4·H2O+2CH3COCH3Hydrolysis
Ketazine hydrolysis is the process that hydrazine hydrate and acetone are generated in hydrolysis system, and this reaction is reversible reaction, in water
Solution top of tower obtains acetone recycling use after overhead condenser；Hydrolysis tower bottom of towe obtains the hydration containing a small amount of ketazine
Hydrazine, feeding ketazine rectifying column makes ketazine and hydrazine hydrate further separate, and unhydrolysed ketazine returns to water by gas phase pipe
Xie Ta continues to hydrolyze, hydrazine hydrate feeding rectifying column concentrate.
In hydrolysis reaction, it is also possible to occur following side reaction and form impurity：
CH3COCH3+H →CH3COHCH3（Isopropanol）
CH3COHCH3+ N2H4·H2O→（CH3）2CHNHNH2（Isopropyl hydrazine）
Isopropanol also known as 2- propyl alcohol, English 2-Propanol or Isopropanol are a kind of colourless liquid, boiling point 82.4
℃.Isopropyl hydrazine, colourless transparent liquid, l06 DEG C-l08 DEG C/750mmHg of boiling point is dissolved in ether, chloroform, water insoluble, hydrolysis
The isopropanol of generation enters acetone recovery system with acetone, and the processing of isopropanol is not in scope.
Inventor has found the presence of impurity isopropanol and isopropyl hydrazine in the chromatography to hydrating solution, by above-mentioned anti-
It should learn, be due to that the acetone of hydrolysis generation is reduced and obtains isopropanol, isopropanol generates isopropyl hydrazine with hydrazine hydrate again,
This material can not hydrolyze generation hydrazine hydrate, consume raw material, decline hydrazine hydrate yield；In the system, acetone boiling point is
58 DEG C, ketazine boiling point is 95 DEG C, and isopropyl hydrazine is l06 DEG C ~ l08 DEG C/750mmHg, and hydrazine hydrate boiling point is 118.5 DEG C.By upper
Stating each boiling point substance can be drawn, impurity isopropyl hydrazine is close with ketazine boiling point, and hydrazine hydrate boiling point is less than higher than acetone,
In practical operation, hydrolysis column overhead temperatures control is 65 ~ 68 DEG C, and ketazine tower bottom of rectifying tower temperature is 125 DEG C or so, so
Isopropyl hydrazine will not be taken out of in hydrolysis system with acetone or hydrazine hydrate, but content is built up in hydrolysis system, and concentration is delayed
Slow to rise, consumption of raw material takes effective reaction space, declines production capacity, steam consumption increase so that ketazine percent hydrolysis drops
It is low.
Be not documented in isopropyl hydrazine in hydrazine hydrate production in current patent influences on hydrazine hydrate ketazine percent hydrolysis
The problem of and treating method.In hydrazine hydrate actual production, in order to avoid isopropyl hydrazine content accumulates too high, hydrazine hydrate ketone is influenceed
Azine percent hydrolysis, solution has following two：One be when Iproniazid content height to influence hydrolysis system can not be normally carried out when,
Hydrolysis system material is all released, line replacement is entered to system；Two be periodically by a hydrolysis tower discharge of materials part, above method
Isopropyl hydrazine can be discharged from system, but useful component acetone and ketazine are also drawn off as liquid waste processing simultaneously,
Cause loss of material.
The content of the invention
In order to solve the above technical problems, the present invention provides a kind of side for removing impurity in ketazine process hydrazine hydrate hydrolysis system
Ketazine solution containing impurity isopropyl hydrazine in hydrazine hydrate hydrolysis system is introduced impurity treatment system-two-stage by method, the present invention
Series pressurized hydrolyzes knockout tower, and by using two-stage pressurized hydrolysis, the mode of separation, ketazine is hydrolyzed into acetone and hydration
Hydrazine, acetone is recycled, and the isopropyl hydrazine waste liquid isolated individually is handled.
The percent hydrolysis comparative study that inventor passes through to the isopropyl hydrazine content in hydrating solution and ketazine is found, works as water
When isopropyl hydrazine content is more than 10% in solution system, ketazine percent hydrolysis is down to 80% or so by 95%, while yield declines, steam
Consumption increase, so must be by the control of isopropyl hydrazine in certain content.Actual production shows, when isopropyl hydrazine mass percent
When content is below 6%, ketazine percent hydrolysis may remain in more than 90%, in order to which production cost considers, when isopropyl hydrazine
When mass percentage content reaches 6% ~ 10%, the ketazine solution containing impurity isopropyl hydrazine is just sent into impurity treatment system by us
System carries out separating treatment.
To achieve these goals, the technical solution adopted by the present invention is as follows：
A kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system, comprises the following steps：
（1）, will be different containing impurity when the isopropyl hydrazine mass percentage content of hydrazine hydrate hydrolysis system reaches 6% ~ 10%
The ketazine solution feeding two-stage pressurizing hydrolysis tower of propyl group hydrazine, and it is passed through nitrogen protection；
（2）Pressurized hydrolysis：Ketazine solution feeding two-stage pressurizing hydrolysis tower containing impurity isopropyl hydrazine is pressurizeed
Hydrolysis, control tower pressure is 0.25 ~ 0.3MPa, ketazine is hydrolyzed to hydrazine hydrate and acetone, in 108 DEG C~110 DEG C tower top temperatures,
Rectifying obtains isopropyl hydrazine and acetone, and in 115 DEG C~117 DEG C bottom temperatures, rectifying obtains hydrazine hydrate kettle material；
（3）Separation：Step（2）Middle isopropyl hydrazine and acetone enter one-level separation tower, control in the form of gas phase
Tower processed pressure is 0.18 ~ 0.25 MPa, and in 100 DEG C~102 DEG C tower top temperatures, rectifying obtains acetone and water vapour, 108 DEG C~
110 DEG C of bottom temperatures, rectifying obtains isopropyl hydrazine；
（4）When can't detect acetone in one-level separation column overhead condensate liquid, illustrating ketazine complete hydrolysis, stopping
Only react, each material is reclaimed in discharge.
Further, step（1）When middle isopropyl hydrazine mass percentage content reaches 9.5%, impurity isopropyl hydrazine will be contained
Ketazine solution sends into two-stage pressurizing hydrolysis tower.
Wherein, step（1）Middle nitrogen addition is 2 ~ 5 m3/h；Step（2）Middle two-stage pressurizing hydrolysis tower tower pressure is
0.28MPa, it is 109 DEG C to control tower top temperature, and bottom temperature is 116 DEG C；Step（2）What middle two-stage pressurizing hydrolysis tower tower reactor was obtained
Hydrazine hydrate returns to hydrazine hydrate hydrolysis system；Step（3）One-level separation tower tower pressure is 0.20MPa, and it is 101 to control tower top temperature
DEG C, bottom temperature is 109 DEG C.
Beneficial effect
The present invention is using two-stage separator to the ketazine solution containing impurity isopropyl hydrazine in hydrazine hydrate hydrolysis system
Separated, by controlling the temperature and pressure of two-stage pressurizing hydrolysis tower, ketazine is hydrolyzed to hydrazine hydrate and acetone, rectifying is obtained
To hydrazine hydrate kettle material, one-level separation tower is returned in vapour form containing acetone and isopropyl hydrazine and is separated, according to
Boiling point is different to separate acetone return acetone recovery system in one-level separation column overhead, and the isopropyl hydrazine that bottom of towe is isolated is independent
Handled；Eliminate the impurity isopropyl hydrazine of hydrazine hydrate hydrolysis system in time by the inventive method, make the isopropyl in system
Base hydrazine content is reduced to less than the 0.05 of original content, improves ketazine system percent hydrolysis, while having reclaimed utility, drops
Low production cost.
Brief description of the drawings
Fig. 1 is the inventive method process chart.
Embodiment
In order to be more clearly understood from the purpose of the present invention, technical scheme and beneficial effect, with reference to specific embodiment
The present invention is described further, but protection scope of the present invention is not limited in the examples below.
Embodiment 1：
（1）It is 20% hydrolyzate 500ml containing ketazine in 1L three-necked flasks, and adds the isopropyl hydrazine of different content,
Use the rectifier unit progress ordinary-pressure hydrolysis experiment that length is 500mm thorn types distillation column, ball condenser, composition, bottom-heated
Using electric jacket, it is 58 DEG C ~ 60 DEG C to control thorn type distillation column gas phase temperature, almost without stopping heating when distillating, hydrolyzes and completes
Add pure water to supply because acetone distillates reduced volume, hydrazine hydrate content and ketazine content, contrast in solution after analysis hydrolysis
The percent hydrolysis of ketazine is studied, percent hydrolysis refers to remaining ketazine and input ketazine ratio in hydrolyzate.
Data list is as follows：
（2）Will experiment（1）Hydrolyzate after hydrolysis carries out heating distillation again, controls the thorn type distillation column gas phase temperature to be
95 DEG C -100 DEG C, ketazine is distillated, almost without stopping heating when distillating, analyze hydrazine hydrate content, calculated yield in flask.
Embodiment 2：
（1）Contain ketazine, hydrazine hydrate and isopropyl hydrazine component such as following table in hydrolyzate.
It is listed as follows
（1）Hydrolyzate 5m need to be handled3Two-stage pressurizing hydrolysis tower is added, 5m is added3Pure water, and it is passed through nitrogen protection, nitrogen
Addition is 3 m3/h；
（2）Pressurized hydrolysis：The ketazine solution of impure isopropyl hydrazine is sent into two-stage pressurizing hydrolysis tower, pressure (hydraulic) water is carried out
Solution, control tower pressure is 0.3MPa, ketazine is hydrolyzed to hydrazine hydrate and acetone, and it is 110 DEG C to control tower top temperature, and rectifying obtains different
Propyl group hydrazine and acetone, bottom temperature are 115 DEG C, and rectifying obtains hydrazine hydrate kettle material；
（3）Separation：Step（2）Middle isopropyl hydrazine and acetone enter one-level separation tower, control in the form of gas phase
Tower processed pressure is 0.2MPa, and tower top temperature is 102 DEG C, and acetone and water vapour are obtained in tower top, 110 DEG C of bottom temperature, and tower reactor is obtained
Isopropyl hydrazine；
（4）When there is no acetone to distillate in one-level separation column overhead condensate liquid, illustrate ketazine complete hydrolysis, this
When one-level pressurized hydrolysis tower tower reactor in isopropyl hydrazine reach maximum concentration, can now stop processing, each material is reclaimed in discharge.
One-level separation tower bottom batch ingredients, are listed as follows：
Two-stage pressurizing hydrolysis tower bottoms material component, it is listed as follows：
| Component | Hydrazine hydrate (%) | Isopropyl hydrazine (%) | Ketazine (%) |
| Content | 10.52 | 0.22 | 0.10 |
By the processing method of the present invention, the impurity isopropyl hydrazine impacted to hydrolysis system can be effectively removed,
Ensure being normally carried out for hydrolysis, improve the percent hydrolysis of ketazine.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent by other or with similar purpose
Alternative features are replaced.The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all at this
Any modifications, equivalent substitutions and improvements made within the spirit and principle of invention etc., should be included in the protection model of the present invention
Within enclosing.
Claims (6)
1. a kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system, comprises the following steps：
（1）When the isopropyl hydrazine mass percentage content of hydrazine hydrate hydrolysis system reaches 6% ~ 10%, impurity isopropyl will be contained
The ketazine solution feeding two-stage pressurizing hydrolysis tower of hydrazine, and it is passed through nitrogen protection；
（2）Pressurized hydrolysis：Ketazine solution feeding two-stage pressurizing hydrolysis tower containing impurity isopropyl hydrazine is subjected to pressurized hydrolysis,
Control tower pressure is 0.25 ~ 0.3MPa, ketazine is hydrolyzed to hydrazine hydrate and acetone, in 108 DEG C~110 DEG C tower top temperatures, rectifying
Isopropyl hydrazine and acetone are obtained, in 115 DEG C~117 DEG C bottom temperatures, rectifying obtains hydrazine hydrate kettle material；
（3）Separation：Step（2）Middle isopropyl hydrazine and acetone enter one-level separation tower, control tower in the form of gas phase
Press as 0.18 ~ 0.25 MPa, in 100 DEG C~102 DEG C tower top temperatures, rectifying obtains acetone and water vapour, at 108 DEG C~110 DEG C
Bottom temperature, rectifying obtains isopropyl hydrazine；
（4）When can't detect acetone in one-level separation column overhead condensate liquid, illustrating ketazine complete hydrolysis, stopping anti-
Should, each material is reclaimed in discharge.
2. a kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system according to claim 1, its feature exists
In：Work as step（1）When middle isopropyl hydrazine mass percentage content reaches 9.5%, by the ketazine solution containing impurity isopropyl hydrazine
Send into two-stage pressurizing hydrolysis tower.
3. a kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system according to claim 1, its feature exists
In：Step（1）Middle nitrogen addition is 2 ~ 5 m3/h。
4. a kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system according to claim 1, its feature exists
In：Step（2）Middle two-stage pressurizing hydrolysis tower tower pressure is 0.28MPa, and it is 109 DEG C to control tower top temperature, and bottom temperature is 116 DEG C.
5. a kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system according to claim 1, its feature exists
In：Step（2）The hydrazine hydrate that middle two-stage pressurizing hydrolysis tower tower reactor is obtained returns to hydrazine hydrate hydrolysis system.
6. a kind of method for removing impurity in ketazine process hydrazine hydrate hydrolysis system according to claim 1, its feature exists
In：Step（3）One-level separation tower tower pressure is 0.20MPa, and it is 101 DEG C to control tower top temperature, and bottom temperature is 109 DEG C.
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| GB1118744A (en) * | 1965-07-07 | 1968-07-03 | Bayer Ag | Preparation of hydrazine hydrate |
| SU1004358A2 (en) * | 1981-12-03 | 1983-03-15 | Предприятие П/Я В-8469 | Process for preparing ketoazines |
| FR2655336B1 (en) * | 1989-12-04 | 1993-05-21 | Atochem | PROCESS FOR VAPORIZING A HYDRAZINE HYDRATE SOLUTION. |
| JP3755543B2 (en) * | 1995-08-14 | 2006-03-15 | 三菱瓦斯化学株式会社 | Method for producing hydrated hydrazine |
| CN104086362A (en) * | 2014-07-08 | 2014-10-08 | 潍坊蓝海环境保护有限公司 | Method for recycling organic solvents of wastewater generated in synthesis of hydrazine hydrate by ketazine method |
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Address after: 644200 Yangchun dam Industrial Zone, Jiang'an County, Yibin, Sichuan Patentee after: Yibin Haifeng Herui Co., Ltd. Address before: 644004 No. 1 Zhongyuan Road, lower Jiangbei, Yibin, Sichuan Patentee before: Yibin Haifeng Herui Co., Ltd. |