CN104230080A - Technique for producing caustic soda from spent brine generated in hydrazine hydrate production process - Google Patents
Technique for producing caustic soda from spent brine generated in hydrazine hydrate production process Download PDFInfo
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- CN104230080A CN104230080A CN201310245634.9A CN201310245634A CN104230080A CN 104230080 A CN104230080 A CN 104230080A CN 201310245634 A CN201310245634 A CN 201310245634A CN 104230080 A CN104230080 A CN 104230080A
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- hydrazine hydrate
- effluent brine
- caustic soda
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Abstract
The invention discloses a technique for producing caustic soda from spent brine generated in a hydrazine hydrate production process, which comprises the following steps: carrying out distillation treatment on spent brine generated in the hydrazine hydrate production process to remove organic matters in the spent brine, adding an oxidizer to carry out oxidation reaction to remove residual ammonia and hydrazine hydrate in the spent brine, adding sodium sulfite to remove free chlorine in the spent brine, adding a precipitant to carry out precipitation reaction to remove sulfate ions and metal impurity ions in the spent brine, and carrying out electrolytic treatment on the spent brine to obtain a caustic soda solution and chlorine gas. The technique can effectively implement treatment on the spent brine, and the prepared caustic soda can be used for other purposes or used as a production raw material of hydrazine hydrate, thereby saving the production cost of the caustic soda and implementing clean production of the hydrazine hydrate.
Description
Technical field
The present invention relates to production of caustic soda field, be specifically related to the technique that caustic soda produced by a kind of effluent brine utilizing hydrazine hydrate production to produce.
Background technology
Hydrazine hydrate, also known as hydrazine hydrate, be a kind of important industrial chemicals, be mainly used in feedwater deoxidation, high pure metal is produced, and organic compound synthesizes, the fields such as rare elements separation and rocket assist raw material.
The production method of hydrazine hydrate mainly contains Raschig process, Wyler's process, ketazine process, peroxide passivation and air oxidation process etc.Wherein, Raschig process due to environmental pollution serious, facility investment is large, and product yield is low, at present eliminate by home and abroad.Hydrazine hydrate production domestic at present mainly applies ketazine process, and ketazine process adopts acetone, oxygenant or clorox and ammonia to react generation intermediate-ketazine.Synthesis liquid sloughs unreacted ammonia through pressurization deammoniation tower, ketazine reactor is returned again after ammonia is only absorbed by the water, deammoniation tower kettle base solution is sent into ketazine tower and is distilled, the ketazine steamed from tower top and the azeotrope of water in the hydrolyzed under pressure of 1MPa, generate acetone and hydrazine hydrate in pressurized hydrolysis tower.Concrete reaction principle is as follows:
2NH
3+NaClO+2(CH
3)
2C＝O-→
(CH
3)
2＝N-N＝(CH
3)2+NaCl+H
2O
(CH
3)
2＝N-N＝(CH
3)
2+2H
2O-→
2(CH
3)
2CO+N
2H
2
Although above-mentioned ketazine process effectively can be produced and obtain hydrazine hydrate, it can produce a large amount of effluent brines in production process, and difficulty or ease process, contaminate environment.Therefore be necessary to provide a kind of method effectively to process the effluent brine produced in hydrazine hydrate production process.
Summary of the invention
The object of the present invention is to provide a kind of effluent brine utilizing hydrazine hydrate production to produce to produce the method for caustic soda, it effectively can process the effluent brine produced in hydrazine hydrate production and process, and treatment cycle is short, and cost is low.
For achieving the above object, the technical solution used in the present invention is: the technique of caustic soda produced by a kind of effluent brine utilizing hydrazine hydrate production to produce, concrete operations are: carry out distilling the organism processing and remove in effluent brine to the effluent brine that hydrazine hydrate production produces, add in effluent brine after removing organism oxygenant carry out oxidizing reaction removing effluent brine in residual ammonia and hydrazine hydrate, the free chlorine in S-WAT removing effluent brine is added after oxidizing reaction, and then add precipitation agent carry out precipitin reaction removing effluent brine in sulfate ion and metallic impurity ion, precipitin reaction terminates to carry out electrolysis treatment to effluent brine and can produce and obtain caustic soda soln and chlorine afterwards.
By first removing organism to the effluent brine produced in hydrazine hydrate production in this programme, then the remaining ammonia of oxygenant removing and hydrazine hydrate is added, and add precipitation agent removing sulfate ion and metallic impurity ion, effluent brine after such process just can carry out electrolysis treatment for the preparation of caustic soda, thus the process realized effluent brine, simultaneously obtained caustic soda may be used for his use or the raw materials for production as hydrazine hydrate, saves the production cost of caustic soda and realizes the cleaner production of hydrazine hydrate.
Further scheme is:
The caustic soda soln produced and chlorine are for the production of the raw materials for production of clorox as hydrazine hydrate.
After oxidizing reaction, the content of the free chlorine in effluent brine is detected, before precipitin reaction, the content of the sulfate ion in effluent brine, metallic impurity ion is detected.
Described precipitation agent is barium chloride solution and sodium carbonate solution, first in effluent brine, adds barium chloride solution, and then adds excessive sodium carbonate solution.
Add hydrochloric acid after precipitin reaction terminates and carry out adjustment PH, in effluent brine, add sodium-chlor after regulating PH and be configured to saturated effluent brine solution, and then carry out electrolysis treatment.
The oxygenant added in oxidationization reaction process is chlorine and clorox, adopts the methyl chloride that pressurized air stripping generates after oxide treatment.
The temperature of distillation process is 50 ~ 60 DEG C, and pressure is 0.02 ~ 0.04MPa.
Distillation processes the raw materials for production of organism as hydrazine hydrate of recovery.
Resin is adopted to carry out adsorption treatment to effluent brine before electrolysis treatment.
On the basis realizing the object of the invention, implemented further by above-mentioned concrete scheme, it can better process effluent brine, produces and obtains caustic soda.Meanwhile, the raw materials such as the chlorine chosen in the application, clorox, barium chloride solution, sodium carbonate solution are easy to obtain or directly obtain from treating processes.Therefore can effectively process the effluent brine produced in hydrazine hydrate production, treatment cycle is short, and cost is low.
Embodiment
Below by way of embodiment, the invention will be further described, but it should not be construed as limiting the scope of the invention.
Embodiment 1
Get effluent brine that hydrazine hydrate production produces be placed in distillation tower 60 DEG C, carry out under 0.04MPa condition distilling the low-boiling-point organic compound such as hydrazine hydrate, acetone that process removes effluent brine, the organism that reclaims of distillation process is as the raw materials for production of hydrazine hydrate.Pass into chlorine and add chlorine bleach liquor in the backward effluent brine of distillation process and carry out oxidizing reaction, to remove residual ammonia in effluent brine and hydrazine hydrate, oxidizing reaction terminates the methyl chloride that generates in rear pressurized air stripping effluent brine and online to the free chlorine (ClO in effluent brine
-) content carry out on-line monitoring, the amount of the S-WAT added required for calculating, again on-line monitoring is carried out to the sulfate ion in effluent brine and metallic impurity ion after adding S-WAT reaction, first in effluent brine, barium chloride solution is added to remove sulfate ion according to detected result, and then add excessive sodium carbonate solution removing metallic impurity ion, the completely rear collecting by filtration effluent brine solution of precipitation.
In above-mentioned effluent brine solution, add hydrochloric acid regulate about PH to 7, in effluent brine, add sodium-chlor after regulating PH and be configured to saturated effluent brine solution, then adopt resin to carry out adsorption treatment to effluent brine, carry out electrolysis treatment after adsorption treatment and can produce and obtain caustic soda soln and chlorine.The caustic soda soln produced and chlorine can be used for producing the raw materials for production of clorox as hydrazine hydrate.
Embodiment 2
Get effluent brine that hydrazine hydrate production produces be placed in distillation tower 50 DEG C, carry out under 0.02MPa condition distilling the low-boiling-point organic compound such as hydrazine hydrate, acetone that process removes effluent brine, the organism that reclaims of distillation process is as the raw materials for production of hydrazine hydrate.Pass into chlorine and add chlorine bleach liquor in the backward effluent brine of distillation process and carry out oxidizing reaction, to remove residual ammonia in effluent brine and hydrazine hydrate, oxidizing reaction terminates the methyl chloride that generates in rear pressurized air stripping effluent brine and online to the free chlorine (ClO in effluent brine
-) content carry out on-line monitoring, the amount of the S-WAT added required for calculating, again on-line monitoring is carried out to the sulfate ion in effluent brine and metallic impurity ion after adding S-WAT reaction, first in effluent brine, barium chloride solution is added to remove sulfate ion according to detected result, and then add excessive sodium carbonate solution removing metallic impurity ion, the completely rear collecting by filtration effluent brine solution of precipitation.
In above-mentioned effluent brine solution, add hydrochloric acid regulate about PH to 7, in effluent brine, add sodium-chlor after regulating PH and be configured to saturated effluent brine solution, then adopt resin to carry out adsorption treatment to effluent brine, carry out electrolysis treatment after adsorption treatment and can produce and obtain caustic soda soln and chlorine.The caustic soda soln produced and chlorine can be used for producing the raw materials for production of clorox as hydrazine hydrate.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. the technique of the effluent brine production caustic soda utilizing hydrazine hydrate production to produce, concrete operations are: carry out distilling the organism processing and remove in effluent brine to the effluent brine that hydrazine hydrate production produces, add in effluent brine after removing organism oxygenant carry out oxidizing reaction removing effluent brine in residual ammonia and hydrazine hydrate, the free chlorine in S-WAT removing effluent brine is added after oxidizing reaction, and then add precipitation agent carry out precipitin reaction removing effluent brine in sulfate ion and metallic impurity ion, precipitin reaction terminates to carry out electrolysis treatment to effluent brine and can produce and obtain caustic soda soln and chlorine afterwards.
2. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as claimed in claim 1, it is characterized in that: the caustic soda soln produced and chlorine are for the production of the raw materials for production of clorox as hydrazine hydrate.
3. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as claimed in claim 1, it is characterized in that: after oxidizing reaction, the content of the free chlorine in effluent brine is detected, before precipitin reaction, the content of the sulfate ion in effluent brine, metallic impurity ion is detected.
4. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as claimed in claim 1, it is characterized in that: described precipitation agent is barium chloride solution and sodium carbonate solution, first in effluent brine, add barium chloride solution, and then add excessive sodium carbonate solution.
5. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as claimed in claim 1, it is characterized in that: add hydrochloric acid after precipitin reaction terminates and carry out adjustment PH, in effluent brine, add sodium-chlor after regulating PH and be configured to saturated effluent brine solution, and then carry out electrolysis treatment.
6. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as claimed in claim 1, it is characterized in that: the oxygenant added in oxidationization reaction process is chlorine and clorox, adopt the methyl chloride that pressurized air stripping generates after oxide treatment.
7. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as claimed in claim 1, it is characterized in that: the temperature of distillation process is 50 ~ 60 DEG C, and pressure is 0.02 ~ 0.04MPa.
8. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as described in claim 1 or 7, it is characterized in that: distillation processes the raw materials for production of organism as hydrazine hydrate of recovery.
9. the technique of caustic soda produced by the effluent brine utilizing hydrazine hydrate production to produce as claimed in claim 1, it is characterized in that: adopt resin to carry out adsorption treatment to effluent brine before electrolysis treatment.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104724871A (en) * | 2015-03-20 | 2015-06-24 | 苏州聚智同创环保科技有限公司 | Technique for recycling ketazine-process hydrazine hydrate high-salt wastewater |
| CN105884090A (en) * | 2016-05-10 | 2016-08-24 | 浙江钛合工程技术有限公司 | Method for recycling chlor-alkali industrial tail gas absorption wastewater |
| CN105836930B (en) * | 2016-06-01 | 2019-04-23 | 江苏索普（集团）有限公司 | Membrane integrated treatment process for high-salt-content wastewater generated in preparation of hydrazine hydrate by ketazine method |
| CN109930169A (en) * | 2017-12-15 | 2019-06-25 | 江苏久吾高科技股份有限公司 | A kind of purification process and device of abraum salt |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58189093A (en) * | 1982-04-30 | 1983-11-04 | Toshiba Corp | Treatment of aqueous hydrazine |
| CN1792825A (en) * | 2005-11-22 | 2006-06-28 | 宜宾天原股份有限公司 | Process for treating hydrazine hydrate waste salt water by ketone linking nitrogen method |
| CN102491559A (en) * | 2011-12-13 | 2012-06-13 | 宜宾天原集团股份有限公司 | Treatment method for urea-method hydrazine hydrate recovered saline water |
| CN202482153U (en) * | 2011-12-14 | 2012-10-10 | 空军南京航空四站制备修理厂 | Device for degrading hydrazine wastewater by virtue of catalytic oxidation of static bed |
-
2013
- 2013-06-20 CN CN201310245634.9A patent/CN104230080A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58189093A (en) * | 1982-04-30 | 1983-11-04 | Toshiba Corp | Treatment of aqueous hydrazine |
| CN1792825A (en) * | 2005-11-22 | 2006-06-28 | 宜宾天原股份有限公司 | Process for treating hydrazine hydrate waste salt water by ketone linking nitrogen method |
| CN102491559A (en) * | 2011-12-13 | 2012-06-13 | 宜宾天原集团股份有限公司 | Treatment method for urea-method hydrazine hydrate recovered saline water |
| CN202482153U (en) * | 2011-12-14 | 2012-10-10 | 空军南京航空四站制备修理厂 | Device for degrading hydrazine wastewater by virtue of catalytic oxidation of static bed |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104724871A (en) * | 2015-03-20 | 2015-06-24 | 苏州聚智同创环保科技有限公司 | Technique for recycling ketazine-process hydrazine hydrate high-salt wastewater |
| CN105884090A (en) * | 2016-05-10 | 2016-08-24 | 浙江钛合工程技术有限公司 | Method for recycling chlor-alkali industrial tail gas absorption wastewater |
| CN105836930B (en) * | 2016-06-01 | 2019-04-23 | 江苏索普（集团）有限公司 | Membrane integrated treatment process for high-salt-content wastewater generated in preparation of hydrazine hydrate by ketazine method |
| CN109930169A (en) * | 2017-12-15 | 2019-06-25 | 江苏久吾高科技股份有限公司 | A kind of purification process and device of abraum salt |
| CN109930169B (en) * | 2017-12-15 | 2023-10-20 | 江苏久吾高科技股份有限公司 | Purification method and device for waste salt |
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Application publication date: 20141224 |