CN1745914A - Recovering method of acetone and ammonia in hydrated hydrazine waste salt water by ketone azine method - Google Patents
Recovering method of acetone and ammonia in hydrated hydrazine waste salt water by ketone azine method Download PDFInfo
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- CN1745914A CN1745914A CN 200510021860 CN200510021860A CN1745914A CN 1745914 A CN1745914 A CN 1745914A CN 200510021860 CN200510021860 CN 200510021860 CN 200510021860 A CN200510021860 A CN 200510021860A CN 1745914 A CN1745914 A CN 1745914A
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Abstract
A process for reclaiming the acetone and ammonia from the rejected saline generated in preparing hydrazine hydrate from ammonia, sodium hypochlorite and ketone by oxidizing method includes bubble evaporating, flash evaporating, and returning the recovered acetone and ammonia back to production system of hydrazine hydrate.
Description
Technical Field
The invention relates to a method for recovering acetone and ammonia carried away by waste brine in a hydrazine hydrate production process by using an ammonia, sodium hypochlorite and ketone oxidation method, in particular to a method for recovering and utilizing the acetone and ammonia carried away by the waste brine in a distillation process.
Background
Hydrazine hydrate, also known as: hydrazine hydrate, formula: n is a radical of2H4·H2O, molecular weight: 50.07, belonging to fine chemical products. Hydrazine hydrate is used as a chemical intermediate, has wide potential application and application fields, and is mainly divided into three aspects: firstly, producing a plastic foaming agent; secondly, in the steam cycle of the power industry, the device is used for preventing pipelines from rusting and aging in advance, so that the safety and reliability of a power station are greatly improved; hydrazine hydrate is also an important raw material for pharmaceuticals and agricultural chemicals. Various methods for producing hydrazine hydrate, such as Rashig method, Bayer method or hydrogen peroxide method. The production method of hydrazine hydrate related to the patent application adopts an ammonia, sodium hypochlorite and acetone oxidation method (ketone method for short), and the process flow mainly comprises the following steps: adding sodium hypochlorite, acetone and 20% ammonia water according to a certain proportion, allowing the mixture to enter a reactor for reaction at 35 ℃ and 0.2Mpa, allowing excessive unreacted ammonia to pass through a stripping tower, condensing the obtained ammonia water, returning the condensed ammonia water to the reactor, separating out the ketazine solution containing unreacted acetone, sodium chloride and other organic impurities, hydrolyzing the ketazine solution obtained by distillation under the pressure of 0.8-1.2 Mpa, returning the obtained acetone to the reactor for circulation, and gradually concentrating the hydrazine hydrate solution to obtain the concentration required by the process, such as 60%.
The main reaction formula is as follows:
the chemical composition of the waste brine continuously fed into the distillation column is as follows:
sodium chloride: 5-7% ketazine: less than or equal to 0.5 percent of ammonia: less than or equal to 0.5 percent, less than or equal to 0.5 percent of acetone
It can be seen that such a production method has the following disadvantages: during the reaction, a large amount of excessive ammonia and acetone exist, the content of ammonia and acetone in the distilled waste brine is too high, and if the distilled waste brine containing ketone and ammonia discharged during the distillation process is directly discharged, a large amount of acetone and ammonia in raw materials are lost from the waste brine, so that the yield of hydrazine hydrate prepared by the ketone method is low.
Disclosure of Invention
The invention aims to solve the problems and provide a method for recovering acetone and ammonia in the waste brine as a byproduct of hydrazine hydrate produced by the ketazine process.
In consideration of the volatility of acetone, ammonia and ketazine and the non-volatility of sodium chloride, the invention designs the followingtechnical scheme to recover acetone, ammonia and sodium chloride in distilled wastewater brine, and the recovered substances are respectively used in the processes of producing hydrazine hydrate by a ketazine method and producing hydrazine hydrate by a urea method:
the invention is carried out according to the following steps:
(a) continuously feeding waste salt water which is a byproduct in the production process of hydrazine hydrate by the ketazine method into a distillation tower, continuously and directly feeding steam with the temperature of 140-180 ℃ into a tower kettle of the distillation tower to bubble the waste salt water, controlling the top temperature of the distillation tower to be between 90 and 98 ℃ through steam flow, separating ketazine, acetone and ammonia in the waste salt water from liquid, recovering the liquid from the tower top, using the liquid as a raw material for producing hydrazine hydrate by the ketazine method, and returning the raw material to a hydrazine hydrate production system for use;
(b) and (c) feeding the residual waste brine with the temperature of 119 ℃ or above after evaporation in the step (a) into a flash tank for flash evaporation, namely, suddenly reducing the flow velocity of the material, rapidly expanding the volume of the material, depositing heavy components sodium chloride and water in the waste brine downwards to the bottom of the tank, volatilizing light components acetone and ammonia upwards, and recovering the light components acetone and ammonia through the top of the tank.
Wherein, the acetone and ammonia recovered from the tank top can be used as raw materials for producing hydrazine hydrate by the ketazine process and returned to a production system of hydrazine hydrate by the ketazine process for use;
in order to improve the concentration of the recovered acetone and ammonia, the acetone and ammonia recovered after flash evaporation in the step (b) can be used as heat sources to enter a distillation tower in the step (a) for rectification recovery, and the acetone and ammonia recovered by rectification are used as raw materials for producing hydrazine hydrate in the ketazine process and are returned to a production system of the hydrazine hydrate in the ketazine process for use.
Compared with the prior art, the invention has the following advantages:
the invention utilizes the volatility of acetone, ammonia and ketazine and the non-volatility of sodium chloride, adopts two organically combined physical treatment procedures of steam bubbling evaporation and flash evaporation, and can maximally recover acetone and ammonia without damaging acetone and ammonia, thereby improving the yield of hydrazine hydrate by the ketazine method.
Drawings
FIG. 1 is a block diagram of a process flow of the present invention.
Detailed Description
The invention will be described in more detail below with reference to the following figures and examples, but the invention is not limited to these examples only:
firstly, preparing hydrazine hydrate according to the conventional steps, reacting sodium hypochlorite, acetone and ammonia to generate ketazine, sodium chloride and water, and synthesizing a chemical reaction formula:
and hydrolyzing the ketazine solution to obtain hydrazine hydrate.
Thehydrolysis reaction formula is as follows:
the chemical composition of the waste brine continuously fed into the distillation column is as follows:
sodium chloride: 6% ketazine: 0.5% ammonia: 0.5 percent and acetone 0.5 percent
Example 1:
(a) continuously feeding waste salt water in the production process of ketazine process hydrazine hydrate into a distillation tower, continuously and directly introducing steam at 150 ℃ into a tower kettle of the distillation tower to bubble the waste salt water, controlling the top temperature of the distillation tower at 90 ℃ by utilizing the steam flow, controlling the temperature of the waste salt water to reach 119 ℃, evaporating acetone and ammonia in the waste salt water at the tower kettle, recovering ketazine, acetone and ammonia separated from the waste salt water through the tower top to be used as raw materials for ketazine process hydrazine hydrate production, and returning the raw materials to a ketazine process hydrazine hydrate production system for use; the remaining spent brine was sampled and analyzed, containing sodium chloride: 6%, ketazine: 0.1%, ammonia: 0.1%, acetone: 0.1 percent; therefore, a large amount of ketazine, acetone and ammonia are recovered;
(b) and (b) feeding the residual waste brine with the temperature of 119 ℃ evaporated in the step (a) into a flash tank for flash evaporation, namely, suddenly reducing the flow rate of the material, rapidly expanding the volume of the material, downwards depositing heavy sodium chloride and water in the waste brine to the bottom of the tank, upwards volatilizing light acetone and ammonia, recovering the heavy sodium chloride and water from the top of the tank, directly using the heavy sodium chloride and water as raw materials for producing hydrazine hydrate by the ketazine method, reacting the heavy sodium chloride and water with sodium hypochlorite to obtain ketazine, and hydrolyzing the ketazine to obtain hydrazine hydrate.
Example 2:
the method for recovering acetone and ammonia in ketazine process hydrazine hydrate waste brine is as in example 1, wherein the temperature of steam introduced in the step (a) is changed to 180 ℃, the temperature of residual waste brine entering a flash tank is 122 ℃, acetone and ammonia recovered after flash evaporation in the step (b) are not directly returned to a ketazine process hydrazine hydrate production system for use, but are used as heat sources to enter a distillation tower in the step (a) for rectification and recovery, the acetone and ammonia are concentrated to be used as ketazine process hydrazine hydrate production raw materials, and are reacted with sodium hypochlorite to obtain ketazine, and the ketazine is hydrolyzed to obtain hydrazine hydrate. Finally, the residual brine can be prepared into qualified brine to be used as a raw material.
Claims (4)
1. A method for recovering acetone and ammonia in ketazine process hydrazine hydrate waste brine is characterized by comprising the following steps:
(a) continuously feeding waste salt water which is a byproduct in the production process of hydrazine hydrate by the ketazine method into a distillation tower, continuously and directly feeding steam with the temperature of 140-180 ℃ into a tower kettle of the distillation tower to bubble the waste salt water, controlling the top temperature of the distillation tower to be between 90 and 98 ℃ through steam flow, separating ketazine, acetone and ammonia in the waste salt water from liquid, recovering the liquid from the tower top, using the liquid as a raw material for producing hydrazine hydrate by the ketazine method, and returning the raw material to a hydrazine hydrate production system for use;
(b) and (c) feeding the residual waste brine with the temperature of 119 ℃ or above after evaporation in the step (a) into a flash tank for flash evaporation, namely, suddenly reducing the flow velocity of the material, rapidly expanding the volume of the material, depositing heavy components sodium chloride and water in the waste brine downwards to the bottom of the tank, volatilizing light components acetone and ammonia upwards, and recovering the light components acetone and ammonia through the top of the tank.
2. The method for recovering acetone and ammonia in the waste brine of ketazine process hydrazine hydrate as recited in claim 1, wherein the acetone and ammonia recovered after flash evaporation in step (b) are used as raw materials for ketazine process hydrazine hydrate production and returned to the ketazine process hydrazine hydrate production system for use.
3. The method for recovering acetone and ammonia in ketazine process hydrazine hydrate waste brine according to claim 1, wherein the acetone and ammonia recovered after flash evaporation in step (b) are used as heat sources to enter the distillation tower in step (a) for rectification and recovery.
4. The method for recovering acetone and ammonia from waste salt water of ketazine process hydrazine hydrate as claimed in claim 3, wherein the acetone and ammonia recovered by distillation in the distillation column are used as raw material for ketazine process hydrazine hydrate production and returned to the ketazine process hydrazine hydrate production system for use.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100218604A CN100389893C (en) | 2005-10-13 | 2005-10-13 | Recovering method of acetone and ammonia in hydrated hydrazine waste salt water by ketone azine method |
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| CNB2005100218604A CN100389893C (en) | 2005-10-13 | 2005-10-13 | Recovering method of acetone and ammonia in hydrated hydrazine waste salt water by ketone azine method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425553C (en) * | 2006-12-22 | 2008-10-15 | 昆明锦洋化学工业有限公司 | Hydrazine hydrate byproduct 5% salt water processing and reclamation method |
| CN101311107B (en) * | 2007-05-21 | 2011-11-02 | 华东理工大学 | Method for gas stripping and separating hydrazine from hydrazine-containing solution using acetone and use thereof |
| CN102531862A (en) * | 2010-12-27 | 2012-07-04 | 青岛高晶化学有限公司 | Comprehensive utilization method for organic waste liquor generated in hydrazine hydrate production process |
| CN103613237A (en) * | 2013-11-28 | 2014-03-05 | 天津普莱化工技术有限公司 | Technique for processing high-salinity wastewater in preparation of hydrazine hydrate by use of ketazine process |
| CN104529049A (en) * | 2014-11-19 | 2015-04-22 | 宜宾天原集团股份有限公司 | Treatment method for using ketazine process hydrazine hydrate brine waste in ion exchange membrane electrolysis |
| CN114684798A (en) * | 2022-05-23 | 2022-07-01 | 北京化工大学 | System and process for producing hydrazine hydrate by ketazine method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| FR2655336B1 (en) * | 1989-12-04 | 1993-05-21 | Atochem | PROCESS FOR VAPORIZING A HYDRAZINE HYDRATE SOLUTION. |
| CN1309085A (en) * | 2000-12-18 | 2001-08-22 | 张庆陆 | Process for separating alkaline-contg. hydrazine hydrate salt mud |
| CN1322684A (en) * | 2001-06-15 | 2001-11-21 | 赖中胜 | Method of eliminating nitrogenous matters from hydrazine hydrate saline-alkali mud |
| CN1159237C (en) * | 2001-07-16 | 2004-07-28 | 巨化集团公司 | Process and gas-film air tower for treating hydrazine contained sewage generated in production of azodimethylamide |
| CN1381400A (en) * | 2002-01-04 | 2002-11-27 | 张庆陆 | Process for recovering alkali-contained salt mud of hydrazine hydrate by carbonizing and drying |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425553C (en) * | 2006-12-22 | 2008-10-15 | 昆明锦洋化学工业有限公司 | Hydrazine hydrate byproduct 5% salt water processing and reclamation method |
| CN101311107B (en) * | 2007-05-21 | 2011-11-02 | 华东理工大学 | Method for gas stripping and separating hydrazine from hydrazine-containing solution using acetone and use thereof |
| CN102531862A (en) * | 2010-12-27 | 2012-07-04 | 青岛高晶化学有限公司 | Comprehensive utilization method for organic waste liquor generated in hydrazine hydrate production process |
| CN103613237A (en) * | 2013-11-28 | 2014-03-05 | 天津普莱化工技术有限公司 | Technique for processing high-salinity wastewater in preparation of hydrazine hydrate by use of ketazine process |
| CN104529049A (en) * | 2014-11-19 | 2015-04-22 | 宜宾天原集团股份有限公司 | Treatment method for using ketazine process hydrazine hydrate brine waste in ion exchange membrane electrolysis |
| CN114684798A (en) * | 2022-05-23 | 2022-07-01 | 北京化工大学 | System and process for producing hydrazine hydrate by ketazine method |
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