CN102775330A - Recycling method of byproduct saline during preparation of hydrazine hydrate by using urea method - Google Patents
Recycling method of byproduct saline during preparation of hydrazine hydrate by using urea method Download PDFInfo
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- CN102775330A CN102775330A CN2012102584484A CN201210258448A CN102775330A CN 102775330 A CN102775330 A CN 102775330A CN 2012102584484 A CN2012102584484 A CN 2012102584484A CN 201210258448 A CN201210258448 A CN 201210258448A CN 102775330 A CN102775330 A CN 102775330A
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Abstract
The invention discloses a recycling method of a byproduct saline during preparation of hydrazine hydrate by using a urea method. The method includes adding excess CO2 into a coarse hydrazine solution, and keeping the negative pressure of a steel cylinder containing the CO2 to be 100pa to 150pa and the flow to be 0.5-0.8mol/L; stirring the mixture continuously for 0.5 hour when the negative pressure in the steel cylinder is zero; freezing and crystallizing the solution through general freezing brine, and controlling the temperature in a range from 2 DEG C to 6 DEG C and the freezing time to be 2 hours; performing cold filtering to obtain filter residues, drying the filter residues in a vacuum drying oven for 4 hours, and keeping the temperature of the drying oven to be 35 DEG C to 45 DEG C; adding urea into the filtrate obtained through cold filtering, adding sulfuric acids to regulate the pH to be 3 to 4, controlling the temperature to be 106 DEG C to 120 DEG C, and reacting the mixture for 2 hours; and feeding chlorine into a biurea reaction still to perform oxidation to obtain the resultant ADC foaming agents, wherein the filtrate is sent to an electrolytic tank. The recycling method of byproduct saline during preparation of hydrazine hydrate by using the urea method has the advantages that the byproduct sodium salt of the hydrazine hydrate is fully recycled, the cost is reduced, and the method is a green chemical process.
Description
Technical field
The present invention relates to a kind of treatment process that adopts Wyler's process to produce by-product in the Hydrazine Hydrate 80 process, more particularly, is that Wyler's process is produced the saline and alkaline recovery and treatment methods such as sodium-chlor, yellow soda ash and sodium hydroxide that contain in the thick hydrazine of by-product in the Hydrazine Hydrate 80 process.
Background technology
Hydrazine Hydrate 80 has another name called hydrazine hydrate, is the monohydrate (N of hydrazine
2H
4H
2O), outward appearance is a colourless transparent liquid, can mix arbitrarily with water, alcohol, is insoluble to EC.Hydrazine Hydrate 80 is a kind of important fine-chemical intermediate, is widely used in synthetic pesticide, medicine, water treatment, whipping agent, initiator and solidifying agent etc., and exploitation prospect is wide.
The working method of Hydrazine Hydrate 80 has Raschig process, Wyler's process, ketazine process, dioxygen water law, air oxidation process.
It is the most general method of domestic employing that Wyler's process is produced Hydrazine Hydrate 80, and the process of this method is following:
4NaOH+Cl
2→NaClO+NaCl+2NaOH
NaClO+NaCl+2NaOH+NH
2CONH
2→NH
2.NH
2.H
2O+2NaCl+Na
2CO
3
The present invention produces in the Hydrazine Hydrate 80 process according to Wyler's process; Contain impurity such as a large amount of sodium-chlor, yellow soda ash and sodium hydroxide in the thick hydrazine that obtains; Thick hydrazine solution carries out the freezing and crystallizing recovery and obtains Sodium carbonate decahydrate; Again solution is evaporated; Evaporate the water that and Hydrazine Hydrate 80 steam and carry out rectifying again and obtain high-load Hydrazine Hydrate 80, the yellow soda ash of by-product, sodium-chlor and the saline and alkaline mixtures such as a small amount of Hydrazine Hydrate 80, sodium hydroxide and water that are entrained with in the evaporative process, the chemical ingredients of this saline and alkaline mixture is following:
Sodium-chlor: 20%-60% yellow soda ash: 10%-35% caustic soda: 2%-15%
N
2H
4H
2All the other 10%-25% of O:0.2-1.0% are water and other trace impurities.
Above-mentioned Wyler's process is produced in the Hydrazine Hydrate 80 process; The Sodium carbonate decahydrate that obtains is the emphasis problem how present domestic research uses; And remaining sodium-chlor and sodium hydroxide and Hydrazine Hydrate 80 are carried and are directly carried out the condensation still after dense and carry out condensation and produce hydrazo-dicarbonamide; Hydrazo-dicarbonamide obtains the ADC whipping agent through peroxo-, mainly comprises sodium-chlor and filter the filtrating that obtains, and sodium sulfate etc. directly discharge.This causes sodium-chlor a large amount of in the solution and sodium sulfate all to be not used, and is so long-term, certainly will cause local soil to become the saltings, wasting space and resource.
Summary of the invention
The objective of the invention is to produce the recovery and treatment method of by-product saline-alkali in the Hydrazine Hydrate 80 process for a kind of Wyler's process that addresses the above problem proposition; This method is with the logical excessive carbon dioxide of the thick hydrazine solution that obtains, and makes wherein yellow soda ash and sodium hydroxide change into sodium hydrogencarbonate, and Hydrazine Hydrate 80 changes into the heavy carbonic hydrazine; Carry out freezing and crystallizing then; The crystallized product that obtains is a sodium hydrogencarbonate, filters rear filtrate and mainly consists of heavy carbonic hydrazine and sodium-chlor, directly heat then carry dense; Obtain the heavy carbonic hydrazine solution of high density; The heavy carbonic hydrazine solution gets into next workshop section and finally obtains the ADC whipping agent, and the filtrating that the filtration of ADC whipping agent obtains is mainly sodium-chlor, can be sent to the power station and carry out electrolysis production sodium hydroxide.Use the advantage after this method is handled by-product saline-alkali to be: with the whole recycles of the sodium salt of Hydrazine Hydrate 80 by-product, cost reduces, and is a kind of green chemical industry technology.
The object of the invention can be realized through following technical scheme: a kind of Wyler's process is produced the recovery and treatment method of by-product saline-alkali in the Hydrazine Hydrate 80 process, and this treatment process comprises the steps:
A. in the reaction kettle that thick hydrazine solution is housed, feed excessive CO
2Gas keeps being equipped with CO
2The negative pressure of the steel cylinder dress of gas is 100-150pa, and flow is 0.5-0.8mol/L;
B. CO ought be housed
2After negative pressure in the steel cylinder dress of gas is 0, continue to feed in the stirred autoclave excessive CO
2The thick hydrazine solution 0.5h of gas;
C. adopt logical chilled brine to carry out freezing and crystallizing above-mentioned solution, temperature is controlled at 2-6 ° of C, and freezing time is 2h;
D. the solution after the filter freezing crystallization, the filter residue that obtains are placed on the dry 4h of vacuum drying oven, and the temperature of the case that keeps dry is at 35-45 ° of C;
E. the filtrating that obtains of the solution after the filter freezing crystallization adds urea, adds sulfuric acid and regulates pH to 3-4, and controlled temperature is to react 2h under the condition of 106-120 ° of C;
F. be that logical chlorine carries out oxidation in the reaction kettle of hydrazo-dicarbonamide to the product that above-mentioned reaction obtains, the product that obtains is the ADC whipping agent, and the filtrating that wherein obtains after the reaction is sent to electrolyzer.
The invention has the advantages that: 1. feed CO
2Yellow soda ash and a spot of free alkali with by-product in the thick hydrazine solution behind the gas change into sodium hydrogencarbonate, and sodium hydrogencarbonate can be used as inorganic foaming agent, and foodstuff additive also can be used as fire-fighting medium, are a kind of high value-added products; 2. behind the sodium hydrogencarbonate freezing and crystallizing, filtrating can directly be carried out condensation reaction and produced hydrazo-dicarbonamide, and then produces the ADC whipping agent, and the yield of the finished product ADC whipping agent is improved, and purity improves; 3. produce the main sodium chloride-containing of filtrating that the ADC whipping agent obtains, can get into electrolyzer and carry out the electrolysis production caustic soda soln.
Description of drawings
Fig. 1 is a technological process block-diagram of the present invention.
The practical implementation method
Following examples are used to explain the present invention, and are not used in restriction the present invention.
Embodiment 1
Get the thick hydrazine solution of 500g,, wherein contain Hydrazine Hydrate 80 50g/L, sodium-chlor 220g/L, yellow soda ash 150g/L, sodium hydroxide 15g/L through detecting.Thick hydrazine solution is added in the 1L reaction kettle, and in reaction kettle, feed dioxide gas, regulating the steel cylinder negative pressure that dioxide gas is housed is 100pa, flow 0.8mol/L, and the steel cylinder negative pressure of waiting to be equipped with dioxide gas is 0 o'clock, continues to stir 0.5h.The logical circulating frozen salt solution in back carries out freezing and crystallizing, maintains the temperature at 6 ° of C, behind the freezing 2h, and cold filtration, filter residue is put into 35 ° of dry 4h of C vacuum drying oven.Filtrating adds urea, and adding sulfuric acid, to regulate pH be 3, and controlled temperature is to stir 2h under the condition of 106 ° of C, filters and obtains hydrazo-dicarbonamide, and logical chlorine oxidation obtains the ADC whipping agent in the reaction kettle of hydrazo-dicarbonamide, and the filtrating that wherein obtains after the reaction is sent to electrolyzer.Calculating can know that the yield of sodium hydrogencarbonate is 88%, and the yield of calculating the ADC whipping agent with Hydrazine Hydrate 80 is 95%.
Embodiment 2
Get the thick hydrazine solution of 500g, through detecting, composition is the same; Thick hydrazine solution is added in the 1L reaction kettle; And in reaction kettle, feed dioxide gas, regulating the steel cylinder negative pressure that dioxide gas is housed is 150pa, flow 0.5mol/L; The steel cylinder negative pressure of waiting to be equipped with dioxide gas is 0 o'clock, continues to stir 0.5h.The logical circulating frozen salt solution in back carries out freezing and crystallizing, maintains the temperature at 2 ° of C, behind the freezing 2h, and cold filtration, filter residue is put into 45 ° of dry 4h of C vacuum drying oven.Filtrating adds urea, and adding sulfuric acid, to regulate pH be 4, and controlled temperature is to stir 2h under the condition of 120 ° of C, filters and obtains hydrazo-dicarbonamide, and logical chlorine oxidation obtains the ADC whipping agent in the hydrazo-dicarbonamide reaction kettle, and the filtrating that wherein obtains after the reaction is sent to electrolyzer.Calculating can know that the yield of sodium hydrogencarbonate is 90%, and the yield of calculating the ADC whipping agent with Hydrazine Hydrate 80 is 98%.
Claims (1)
1. a Wyler's process is produced the recovery and treatment method of by-product saline-alkali in the Hydrazine Hydrate 80 process, it is characterized in that this art treatment comprises the steps:
A. in the reaction kettle that thick hydrazine solution is housed, feed excessive CO
2Gas keeps being equipped with CO
2The negative pressure of the steel cylinder dress of gas is 100-150pa, and flow is 0.5-0.8mol/L;
B. CO ought be housed
2After negative pressure in the steel cylinder dress of gas is 0, continue to feed in the stirred autoclave excessive CO
2The thick hydrazine solution 0.5h of gas;
C. adopt chilled brine to carry out freezing and crystallizing above-mentioned solution, temperature is controlled at 2-6 ° of C, and freezing time is 2h;
D. the solution after the filter freezing crystallization, the filter residue that obtains are placed on the dry 4h of vacuum drying oven, and the temperature of the case that keeps dry is at 35-45 ° of C;
E. the filtrating that obtains of the solution after the filter freezing crystallization adds urea, adds sulfuric acid and regulates pH to 3-4, and controlled temperature is to react 2h under the condition of 106-120 ° of C;
F. be that logical chlorine carries out oxidation in the reaction kettle of hydrazo-dicarbonamide to the product that above-mentioned reaction obtains, the product that obtains is the ADC whipping agent, and the filtrating that wherein obtains after the reaction is sent to electrolyzer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102584484A CN102775330A (en) | 2012-07-24 | 2012-07-24 | Recycling method of byproduct saline during preparation of hydrazine hydrate by using urea method |
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|---|---|---|---|
| CN2012102584484A CN102775330A (en) | 2012-07-24 | 2012-07-24 | Recycling method of byproduct saline during preparation of hydrazine hydrate by using urea method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058891A (en) * | 2013-01-06 | 2013-04-24 | 杭州海虹精细化工有限公司 | Method for producing biruea and urotropine |
| CN106349119A (en) * | 2016-08-26 | 2017-01-25 | 衡阳市锦轩化工有限公司 | Method for co-production of biurea and sodium fluoride |
| CN108715453A (en) * | 2018-07-05 | 2018-10-30 | 河南元亨精细化工有限公司 | A kind of process for cleanly preparing of saline and alkaline mixed liquor production sodium pyrosulfite and sodium chloride |
| CN114853638A (en) * | 2022-05-13 | 2022-08-05 | 宁夏日盛高新产业股份有限公司 | Production method and system of biurea |
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2012
- 2012-07-24 CN CN2012102584484A patent/CN102775330A/en active Pending
Patent Citations (5)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058891A (en) * | 2013-01-06 | 2013-04-24 | 杭州海虹精细化工有限公司 | Method for producing biruea and urotropine |
| CN103058891B (en) * | 2013-01-06 | 2014-07-16 | 杭州海虹精细化工有限公司 | Method for producing biruea and urotropine |
| CN106349119A (en) * | 2016-08-26 | 2017-01-25 | 衡阳市锦轩化工有限公司 | Method for co-production of biurea and sodium fluoride |
| CN106349119B (en) * | 2016-08-26 | 2018-08-03 | 衡阳市锦轩化工有限公司 | The method of coproduction biruea and sodium fluoride |
| CN108715453A (en) * | 2018-07-05 | 2018-10-30 | 河南元亨精细化工有限公司 | A kind of process for cleanly preparing of saline and alkaline mixed liquor production sodium pyrosulfite and sodium chloride |
| CN114853638A (en) * | 2022-05-13 | 2022-08-05 | 宁夏日盛高新产业股份有限公司 | Production method and system of biurea |
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Application publication date: 20121114 |