CN100347100C - Method of treating wastewater containing salt for producing hydrazine hydrate by carbamide method - Google Patents
Method of treating wastewater containing salt for producing hydrazine hydrate by carbamide method Download PDFInfo
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- CN100347100C CN100347100C CNB2005100207718A CN200510020771A CN100347100C CN 100347100 C CN100347100 C CN 100347100C CN B2005100207718 A CNB2005100207718 A CN B2005100207718A CN 200510020771 A CN200510020771 A CN 200510020771A CN 100347100 C CN100347100 C CN 100347100C
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- saturated brine
- hydrazine hydrate
- ammonia
- hydrochloric acid
- sodium
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Abstract
The present invention discloses a method for processing saturated brine prepared in the course of the reclamation and classification of salt and alkali in the preparation of hydrazine hydrate by a carbamide method. Oxidation substances at least equivalent to hydrazine hydrate and ammonia which exist in waste water are added to the saturated brine, so that the hydrazine hydrate and the ammonia react with the oxidation substances to be converted into nitrogen gas and water; hydrochloric acid equivalent to sodium hydroxide existing in the saturated brine is added, so that the hydrochloric acid react with the sodium hydroxide to be converted into sodium chloride; then, the sodium chloride is recovered; the nitrogen gas can be directly discharged into atmosphere. The sodium hydroxide in the saturated brine is processed by adding the hydrochloric acid, the ammonia nitrogen index in the processed saturated brine is greatly reduced, and the value of the index is less than 15 mg/l; the processed saturated brine can be sent to a system converting chlorine and alkali into salt for preparing the sodium hydroxide by electrolysis; the resource is utilized fully, and the waste is avoided.
Description
Technical field
The present invention relates to a kind of treatment process of producing the by product in the hydrazine hydrate process with urea, clorox, sodium hydroxide oxidation style, more particularly, is the treatment process to the saturated brine that makes in the saline and alkaline recovery classification process.
Background technology
Hydrazine hydrate has another name called: hydrazine hydrate, chemical formula: N
2H
4H
2O, molecular weight: 50.07, belong to fine chemical product.Hydrazine hydrate is as a kind of chemical intermediate, and its potential use and Application Areas are very extensive, mainly is divided into three aspects: one, produce plastics blowing agent; Its two, in the steam cycle of power industry, it is used as and prevents that pipeline from getting rusty and aging in advance, thereby improves the safe reliability in power station greatly; In addition, hydrazine hydrate also is important medicine and pesticide material.The various production methods of hydrazine hydrate, as draw west (Rashig) method, Bel's (Bayer) method or hydrogen peroxide method, Chinese patent discloses " method for preparing concentrated solution of hydrazine hydrate " of being applied for by the applicant with the patent No. 02113375.1, it is to adopt urea, clorox, sodium hydroxide oxidation style (abbreviation Wyler's process), technical process is mainly as follows: with caustic soda, water, chlorine is the preparation of raw material chlorine bleach liquor, close the thick solution of hydrazine with the urea soln water generation reaction, wherein contain yellow soda ash, sodium-chlor, sodium hydroxide and water, the thick solution of hydrazine hydrate is through crystallisation by cooling, reclaim Sodium carbonate decahydrate wherein, again solution is evaporated, water that evaporates and hydrazine hydrate steam carry out rectifying again and obtain high-load hydrazine hydrate, a large amount of sodium-chlor that contain that vapo(u)rization system is discharged carry out saline and alkaline the separation with the sodium carbonate salt alkaline residue, and isolated sodium-chlor turns to salt solution.Its main chemical reactions equation is:
NaClO+N
2H
4CO+2NaOH＝N
2H
4·H
2O+Na
2CO
3+NaCl
Wherein, the Chemical Composition of the saturated brine that makes in the saline and alkaline recovery classification process is as follows:
NaCl：280-300g/l NaOH：2-4g/l Na
2CO
3：10-22g/l
NH
3：60-100mg/l N
2H
4·H
2O：120-380mg/l
As seen, there is following shortcoming in production method like this: in the saturated brine that in saline and alkaline recovery classification process, makes owing to contain hydrazine hydrate and ammonia and caustic soda, directly discharging on the one hand, not only cause the wasting of resources, and since the ammonia nitrogen index of waste water exceed standard greatly and reach (discharged wastewater met the national standard ammonia nitrogen index is 15mg/l), even more serious to the pollution of environment; On the other hand, use if this saturated brine is delivered to the chlor-alkali system, ammonia and hydrazine hydrate will be converted into nitrogen trichloride in the chlorine system chlor-alkali production will be buried the major hidden danger source; On the one hand the too high caustic soda content of this saturated brine is delivered to the chlor-alkali system chlor-alkali system salt solution can't be used again.Regrettably, also find so far how to handle the saturated brine that makes in the saline and alkaline recovery classification process and it is handled after useful matter be used for the document that the chlor-alkali production process is used.
Summary of the invention
The present invention at first purpose is for addressing the above problem when providing a kind of Wyler's process to produce hydrazine hydrate the treatment process of its brine waste, using the salt solution ammonia nitrogen index after this method is handled to reach the national environmental protection emission request; A further object of the present invention is the saturated brine that saline and alkaline recovery produces to be handled the back recycle.
The object of the present invention is achieved like this:
Adopt Wyler's process to produce to add in the saturated brine that hydrazine hydrate makes in saline and alkaline recovery classification process at least and be present in that hydrazine hydrate and ammonia mate normal oxidizing substance in the waste water, make the reaction of hydrazine hydrate and ammonia and oxidizing substance be converted into the nitrogen G﹠W, the caustic soda that adds and be present in the salt solution mates normal hydrochloric acid, makes the reaction of hydrochloric acid and caustic soda be converted into sodium-chlor.
Wherein, described oxidizing substance is any in hydrogen peroxide, chlorine or the clorox, is most preferred scheme with hydrogen peroxide.
When adopting hydrogen peroxide to handle above-mentioned waste water, following reaction takes place:
N
2H
4·H
2O+2H
2O
2＝N
2↑+5H
2O
2NH
3+3H
2O
2＝N
2↑+6H
2O
When adopting the above-mentioned waste water of chlorine treatment, following reaction takes place:
N
2H
4·H
2O+2Cl
2＝N
2↑+2HCl+H
2O
2NH
3+3Cl
2＝6HCl+N
2↑
And then adding hydrochloric acid is converted into sodium-chlor to the sodium hydroxide in the gained solution in gained solution, sodium chloride solution is delivered to the chlor-alkali system again and is used.
When adopting clorox to handle above-mentioned waste water, following reaction takes place:
N
2H
4·H
2O+2NaClO＝2NaCl+N
2↑+2H
2O
2NH
3+3NaClO＝3NaCl+N
2↑+3H
2O
In gained solution, add hydrochloric acid then the sodium hydroxide in the gained solution is converted into sodium-chlor, again sodium chloride solution is delivered to the chlor-alkali system and used.
The present invention has following advantage than prior art:
The present invention is because of hydrazine hydrate and ammonia react in the saturated brine that has adopted oxidizing substance and Wyler's process production hydrazine hydrate to make, make them be converted into the nitrogen G﹠W, nitrogen can directly be thrown in the atmosphere, and sodium hydroxide in the adding salt acid treatment saturated brine, the ammonia nitrogen index of the saturated brine after the processing reduces greatly, reaches＜15mg/l, and this saturated brine after the processing can be delivered to the chlor-alkali salt system and be used for electrolysis and produce caustic soda, make full use of resource, avoid waste.
Description of drawings
Fig. 1 is a technological process block-diagram of the present invention.
Embodiment
Step at first routinely prepares hydrazine hydrate, at first 30% caustic soda is put into the diluted alkaline Preparation tank, add certain amount of industrial water and with pump constantly circulation to mix content stand-by after being 285-290g/l; Again service water is put into urea liquid Preparation tank, under agitation added solid urea and catalyzer, treat that it is solution for later use behind the 295-300g/l that solid urea dissolves content; Then diluted alkaline is sent in the sodium hypochlorite reaction device continuously by certain flow, fed chlorine, with 0-5 ℃ of chilled brine cooling, control reaction temperature contains the chlorine bleach liquor that available chlorine is 8-12% making below 15 ℃.Chemical equation:
2NaOH+Cl
2＝NaClO+NaCl+H
2O
With pump clorox and urea liquid are mixed the back by a certain percentage then and contain the thick solution of hydrazine hydrate, chemical equation to 106-108 ℃ of reaction generation with steam-heated cal(l)andria:
NaClO+N
2H
4CO+2NaOH＝N
2H
4·H
2O+Na
2CO
3+NaCl
The thick solution of hydrazine hydrate is cooled to＜sends in the crystallization kettle after 35 ℃ with pump then, with＜-5 ℃ chilled brine (or liquefied ammonia) cooling, after temperature is reduced to-2 ℃, go out 70% about yellow soda ash in the thick hydrazine hydrate solution with centrifugation.Send in the pump feed evaporator and evaporate removing the thick solution of hydrazine hydrate behind the yellow soda ash, water that evaporates and hydrazine hydrate steam enter again constantly carry in the rectifying tower dense to 40%.At centrifugal its composition of salt and alkali slag that goes out of evaporation is NaCl:50-60%Na2CO3:20-30%, NaOH:6-8%, N2H4.H2O:0.3-0.6%, this salt and alkali slag is made pulpous state to be delivered to saline and alkaline recovery and carries out separating of sodium-chlor and yellow soda ash, isolated monohydrated sodium carbonate is sold as product, and isolated solid sodium chloride is a saturated brine with industrial water dissolution.
Wherein, the Chemical Composition of the saturated brine that makes in the saline and alkaline recovery classification process is as follows:
NaCl：280-300g/l NaOH：2-4g/l Na
2CO
3：10-22g/l
NH
3：60-100mg/l N
2H
4·H
2O：120-380mg/l
Embodiment 1: adopt hydrogen peroxide as oxidizer treatment Wyler's process brine waste.
The isolated solid sodium chloride of saline and alkaline recovery is added in the salt dissolving tank, control certain salt layer height, the 280-300g/l salt solution that the adding service water makes is sent in the salt solution basin, according to contained NH in the salt solution
3With N
2H
4H
2The amount of O, add the normal hydrogen peroxide of coupling and use the pump circulating reaction to the inside, treat behind ammonia-nitrogen content＜15mg/l again amount according to contained NaOH in the salt solution, add the normal hydrochloric acid of coupling to the inside and carry out circulating reaction, after treating NaOH content＜0.1g/l, make raw material salt solution usefulness with being pumped to the production of caustic soda system.Wherein, following reaction takes place in the solution:
N
2H
4·H
2O+2H
2O
2＝N
2↑+5H
2O
2NH
3+3H
2O
2＝N
2↑+6H
2O
HCl+NaOH＝NaCl+H
2O
Embodiment 2: adopt chlorine as oxidizer treatment Wyler's process brine waste.
The isolated solid sodium chloride of saline and alkaline recovery is added in the salt dissolving tank, control certain salt layer height, the 280-300g/l salt solution that the adding service water makes is sent in the salt solution basin, according to contained NH in the salt solution
3With N
2H
4H
2The amount of O, feed the normal chlorine of coupling and use the pump circulating reaction to the inside, treat behind ammonia-nitrogen content＜15mg/l again amount according to contained NaOH in the salt solution, add the normal hydrochloric acid of coupling to the inside and carry out circulating reaction, after treating NaOH content＜0.1g/l, make raw material salt solution usefulness with being pumped to the production of caustic soda system.Wherein, following reaction takes place in the solution:
N
2H
4·H
2O+2Cl
2＝N
2↑+2HCl+H
2O
2NH
3+3Cl
2＝6HCl+N
2↑
HCl+NaOH＝NaCl+H
2O
Embodiment 3: adopt clorox as oxidizer treatment Wyler's process brine waste.
The isolated solid sodium chloride of saline and alkaline recovery is added in the salt dissolving tank, control certain salt layer height, the 280-300g/l salt solution that the adding service water makes is sent in the salt solution basin, according to contained NH in the salt solution
3With N
2H
4H
2The amount of O, add the normal clorox of coupling and use the pump circulating reaction to the inside, treat behind ammonia-nitrogen content＜15mg/l again amount according to contained NaOH in the salt solution, add the normal hydrochloric acid of coupling to the inside and carry out circulating reaction, after treating NaOH content＜0.1g/l, make raw material salt solution usefulness with being pumped to the production of caustic soda system.Wherein, following reaction takes place in the solution:
N
2H
4·H
2O+2NaClO＝2NaCl+N
2↑+2H
2O
2NH
3+3NaClO＝3NaCl+N
2↑+3H
2O
HCl+NaOH＝NaCl+H
2O。
Claims (4)
1, the treatment process of Wyler's process hydrazine hydrate brine waste, add in the saturated brine that it is characterized in that in saline and alkaline recovery classification process, making and mate normal hydrogen peroxide or chlorine or clorox with the hydrazine hydrate and the ammonia that are present in the saturated brine at least, make hydrazine hydrate and ammonia and hydrogen peroxide or chlorine or sodium hypochlorite reaction be converted into the nitrogen G﹠W, add at least and be present in that caustic soda mates normal hydrochloric acid in the saturated brine, make caustic soda be converted into sodium-chlor and water.
2, the treatment process of Wyler's process hydrazine hydrate brine waste according to claim 1, its feature at normal temperatures will be present in hydrazine hydrate in the saturated brine and ammonia and mate normal hydrogen peroxide and add in the saturated brine that makes in the saline and alkaline recovery classification process, make the reaction of hydrazine hydrate in the saturated brine and ammonia and hydrogen peroxide be converted into the nitrogen G﹠W, till ammonia-nitrogen content＜15mg/l in salt solution, in gained solution, add then at least with saturated brine in caustic soda mate normal hydrochloric acid and make caustic soda and hydrochloric acid reaction in the gained solution be converted into sodium chloride solution, in sodium chloride solution, behind sodium hydrate content＜0.1g/l, sodium chloride solution is delivered in the chlor-alkali production process used again.
3, the treatment process of Wyler's process hydrazine hydrate brine waste according to claim 1, it is characterized in that at normal temperatures will be present in hydrazine hydrate in the saturated brine and ammonia and mate normal chlorine and add in the saturated brine that makes in the saline and alkaline recovery classification process, make hydrazine hydrate in the saturated brine and ammonia and chlorine reaction be converted into the nitrogen G﹠W, hydrogenchloride, behind ammonia-nitrogen content＜15mg/l in salt solution, and then in gained solution, add at least with saturated brine in caustic soda mate normal hydrochloric acid and make caustic soda and hydrochloric acid reaction in the gained solution be converted into sodium chloride solution, in sodium chloride solution, behind sodium hydrate content＜0.1g/l, sodium chloride solution is delivered in the chlor-alkali production process used again.
4, the treatment process of Wyler's process hydrazine hydrate brine waste according to claim 1, it is characterized in that at normal temperatures will be present in hydrazine hydrate in the saturated brine and ammonia and mate normal clorox and add in the saturated brine that makes in the saline and alkaline recovery classification process, make hydrazine hydrate in the saturated brine and ammonia and sodium hypochlorite reaction be converted into the nitrogen G﹠W, sodium-chlor, till ammonia-nitrogen content＜15mg/l in salt solution, and then in gained solution, add at least with saturated brine in caustic soda mate normal hydrochloric acid and make caustic soda and hydrochloric acid reaction in the salt solution be converted into sodium chloride solution, in sodium chloride solution, behind sodium hydrate content＜0.1g/l, sodium chloride solution is delivered in the chlor-alkali production process used again.
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|---|---|---|---|
| CNB2005100207718A CN100347100C (en) | 2005-04-22 | 2005-04-22 | Method of treating wastewater containing salt for producing hydrazine hydrate by carbamide method |
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| CNB2005100207718A CN100347100C (en) | 2005-04-22 | 2005-04-22 | Method of treating wastewater containing salt for producing hydrazine hydrate by carbamide method |
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Families Citing this family (10)
| 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 |
| CN101219973B (en) * | 2008-01-22 | 2010-06-02 | 浙江海虹控股集团有限公司 | A kind of preparation method of biurea |
| CN102040197B (en) * | 2010-11-17 | 2012-10-31 | 株洲化工集团诚信有限公司 | Method for removing ammonia nitrogen in hydrazine hydrate evaporation byproduct residues containing alkali salt by utilizing urea method |
| CN102557164B (en) * | 2010-12-15 | 2013-12-11 | 益海嘉里(连云港)化工有限公司 | Recycling method of high-salt industrial wastewater containing glycerin |
| 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 |
| 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 |
| CN103386305B (en) * | 2013-07-31 | 2015-09-09 | 南京威安新材料科技有限公司 | For the preparation of hydrazine and ammonia nitrogen waste water process catalyst and technique for applying thereof and device |
| CN108840425A (en) * | 2018-07-09 | 2018-11-20 | 郭秦 | A kind of thiocarbohydrazide wastewater treatment method |
| CN112209410B (en) * | 2020-09-30 | 2022-09-16 | 宜宾海丰和锐有限公司 | Method for treating hydrazine hydrate byproduct sodium chloride brine |
| CN112326874A (en) * | 2020-11-30 | 2021-02-05 | 宁夏日盛高新产业股份有限公司 | Method for analyzing mixed alkali in hydrazine hydrate by hydrogen peroxide oxidation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU791628A1 (en) * | 1978-04-10 | 1980-12-30 | Предприятие П/Я В-8469 | Method of rendering harmless waste water by oxidation in hydrazine hydrate production |
| US4849114A (en) * | 1988-02-18 | 1989-07-18 | Ultrox International | Oxidation of toxic compounds in water |
| CN1686857A (en) * | 2005-04-22 | 2005-10-26 | 宜宾天原股份有限公司 | Method for treating wastewater of rectification for producing hydrazine hydrate by carbamide method |
-
2005
- 2005-04-22 CN CNB2005100207718A patent/CN100347100C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU791628A1 (en) * | 1978-04-10 | 1980-12-30 | Предприятие П/Я В-8469 | Method of rendering harmless waste water by oxidation in hydrazine hydrate production |
| US4849114A (en) * | 1988-02-18 | 1989-07-18 | Ultrox International | Oxidation of toxic compounds in water |
| CN1686857A (en) * | 2005-04-22 | 2005-10-26 | 宜宾天原股份有限公司 | Method for treating wastewater of rectification for producing hydrazine hydrate by carbamide method |
Non-Patent Citations (2)
| Title |
|---|
| 水合肼生产技术进展 沈韧虎.氯碱工业，第1期 2001 * |
| 水合肼粗合成液蒸发脱碱盐工艺的研究 冯涛，刘治文.化工设计，第4卷 1999 * |
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