CN103043636B - Method for increasing concentration of hydrazine hydrate - Google Patents
Method for increasing concentration of hydrazine hydrate Download PDFInfo
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- CN103043636B CN103043636B CN201310004518.8A CN201310004518A CN103043636B CN 103043636 B CN103043636 B CN 103043636B CN 201310004518 A CN201310004518 A CN 201310004518A CN 103043636 B CN103043636 B CN 103043636B
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- hydrazine hydrate
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Abstract
The invention provides a method for increasing the concentration of hydrazine hydrate. The method comprises the steps that inorganic salt capable of forming crystal water is added into a hydrazine hydrate solution, and a large amount of water is taken away in an inorganic salt hydration crystallization form; sufficient inorganic salt containing no crystal water or low-content crystal water is added into the hydrazine hydrate solution, crystallized out in a high-content hydration inorganic salt form on a certain condition, and subjected to centrifugal separation; a mother solution is hydrazine hydrate with the increased concentration; a crystalline portion through the centrifugal separation is subjected to dehydration treatment; and dehydrated inorganic salt is added into the hydrazine hydrate solution for recycling. The method has the benefits that the water is taken away through the combination with the crystal water, and then the dehydration is conducted with relatively lower energy consumption, so that hydrazine hydrate with higher concentration can be obtained with less energy consumption on the condition that the quality of hydrazine hydrate is unaffected; the repeatability of added inorganic salt is considered fully in the process; and the operating cost is lowered.
Description
Technical field
The present invention relates to hydrazine hydrate field, be specifically related to a kind of method improving concentration of hydrazine hydrate.
Background technology
Hydrazine hydrate has another name called hydrazine hydrate, is the monohydrate (N of hydrazine
2h
4h
2o), outward appearance is colourless transparent liquid, can mix arbitrarily, be insoluble to EC with water, alcohol.Hydrazine hydrate is a kind of important fine-chemical intermediate, and be widely used in synthetic pesticide, medicine, water treatment, whipping agent, initiator and solidifying agent etc., exploitation prospect is wide.
The method of current domestic production hydrazine hydrate mainly contains Wyler's process and ketazine process, in the thick hydrazine of Wyler's process hydrazine hydrate, hydrazine hydrate content is 4 ~ 6%, in ketazine process hydrazine hydrate, concentration of hydrazine hydrate is 10 ~ 12%, the hydrazine hydrate hydrazine content of hydrazine hydrate prepared by additive method or recovery is all lower, be prepared into 40%, the hydrazine hydrate of the high density such as 80%, all need through pervaporation, rectifying is concentrated waits processing step, need to consume a large amount of steam, 80% hydrazine hydrate per ton about consumes 25 ~ 35t steam, the production cost of hydrazine hydrate is improved greatly, cut the relevant policies not meeting national energy-saving and reduce discharging.
The present invention by adding not containing crystal water or the inorganic salt containing low crystal water in hydrazine hydrate solution, inorganic salt and moisture is utilized to form the feature of crystalline hydrate, inorganic salt are regarded as water entrainer, and by the crystallization to inorganic salt, separation, dehydration, inorganic salt can reuse.And in crystallisation process, it needs a small amount of cold of consumption or additive method just can obtain, and in dehydration, according to the difference of inorganics, required heat is not high yet, and the dehydration of such as sal glauberi, sodium sulfate per ton only consumes the heat of 0.03t standard coal.Remove the moisture of identical amount, its energy consumption can reduce greatly, and the cost of enriching stage can reduce half.Because the inorganic salt added are relatively stable, all do not react with compositions such as the hydrazine hydrates in original solution, do not affect the use of hydrazine hydrate, hydrazine hydrate after concentrated directly can carry out having sour condensation reaction to prepare hydrazo-dicarbonamide, also directly can be obtained the hydrazine hydrate of high density by evaporation, not need carrying out rectifying concentrate.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art existence, and provide a kind of method improving concentration of hydrazine hydrate, by conjunction with the inorganic salt of crystal water through being separated in conjunction with crystal water, moisture can be removed to crystallization, recycle, improve the novel process of concentration of hydrazine hydrate with lower energy consumption.
The object of the invention is to have come by following technical solution.The method of this raising concentration of hydrazine hydrate, the method comprises following step:
A. the hydrazine hydrate solution of 100-1000ml is got;
B. in hydrazine hydrate solution, 30g-200g is added not containing crystal water or the inorganic salt containing low crystal water;
C. carrying out crystallization to adding the hydrazine hydrate solution after inorganic salt, determining its optimum condition index for different Inorganic Salts, be i.e. crystallization as far as possible completely under the condition in conjunction with maximum crystal water;
D. centrifuging is carried out to the hydrazine hydrate solution after crystallization, the hydrazine hydrate after mother liquor and concentrate;
E. the hydrated inorganic salt after centrifugal, dewaters, obtains anhydrous or that crystal water content is less inorganic salt, use as feedstock circulation.
Described hydrazine hydrate solution can be hydrazine hydrate prepared by hydrazine hydrate, ketazine process prepared by Wyler's process, lower concentration hydrazine hydrate solution that is prepared by additive method, that reclaim.The hydrazine hydrate solution that Wyler's process hydrazine hydrate can be through preliminary treatment also can be the hydrazine hydrate solution without any process.
Do not have not containing the feature of crystal water, crystal water containing different quantities with crystal water or containing the inorganic salt of low crystal water.
These moisture inorganic salt can be that sodium sulfate, sodium hydrogen phosphate, magnesium sulfate, sodium carbonate, Potassium monofluoride, copper sulfate, magnesium chloride etc. have a compounds that can contain crystal water, also can be wherein one or more.
The selection of this inorganics should be deferred in hydrazine hydrate solution stable, react with hydrazine hydrate, easy crystallization, crystalline particle easily filters, crystal water content is higher, crystal water easily removes, etc. feature.Present method preferably sulfuric acid sodium.
Different types of crystallization such as the crystallisation process of this hydrate can be freezing and crystallizing, evaporative crystallization, ted.
The dehydration of this hydrated inorganic salt-pepper noise, can be heating, evaporation, dry etc. one or more.
These inorganic salt add with crystallisation process can be once complete also can complete step by step, mainly to determine according to the size of required concentrated concentration and solid content, to ensure that material can normally be carried, normally produce.
These inorganic salt, after processed, can recycle.
Beneficial effect of the present invention is: by the form in conjunction with crystal water, a large amount of moisture is taken away, then use relatively low power consuming dehydration, when not affecting hydrazine hydrate quality, by less energy consumption, can obtain the hydrazine hydrate of greater concn.In the process, also taken into full account add the repeatability of inorganic salt, reduce operation cost.
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention;
Embodiment
Below by embodiment, the present invention is further elaborated, and help is understood the present invention by embodiment better, but the present invention is not limited only to following embodiment.
This technical process shown in Fig. 1 using Wyler's process hydrazine hydrate (neutralizing caustic soda wherein and sodium carbonate in advance by the vitriol oil), adopt anhydrous sodium sulphate as water entrainer, reinforced concentrate is example at twice.
Embodiment 1
Get smart hydrazine solution 1000ml, the concentration of hydrazine hydrate measured wherein is 59.46g/l, and carbonate content is 55.42g/l, caustic soda content is 12.28g/l, drips the industrial vitriol oil of 98% first wherein, regulates hydrazine solution PH=7, make sodium carbonate wherein, sodium hydroxide etc. all be converted into sodium sulfate, adding 200g anhydrous sodium sulphate wherein, after fully stirring, be cooled to 0 DEG C, crystallization, centrifugation, obtains filter cake 583g, mother liquor is 667ml, and the hydrazine hydrate content wherein of survey is 88.25g/l.Concentration of hydrazine hydrate improves 48.42%.The filter cake obtained, through drying and dehydrating, obtains solid matter 268.5g.
Embodiment 2
Continue to add dried filter cake 200g in the mother liquor in example 1, after abundant stirring, be cooled to 0 DEG C, crystallization, centrifugation, obtains filter cake 613g, mother liquor is 346ml, the hydrazine hydrate content recorded wherein is 168.4g/l, and concentration of hydrazine hydrate improves filter cake that 90.8%. obtains through drying and dehydrating, obtains solid matter 280.7g.
Added by twice, make concentration of hydrazine hydrate bring up to 168.4g/l from 59.46g/l, improve 2.8 times, Chlorine in Solution sodium etc. also partial crystallization are separated out, and decrease the salinity in hydrazine hydrate solution, reuse after sodium sulfate, when normal production, do not increase material cost.Through calculating, the comprehensive yield of hydrazine hydrate, more than 98%, can also improve yield further, therefore the loss of hydrazine hydrate also belongs to comparatively low degree in centrifuging link aborning by a small amount of water washing.
Embodiment 3
Get the commodity hydrazine hydrate 100ml of 40%, add anhydrous sodium sulphate 30g wherein, after fully stirring, be cooled to 0 DEG C of crystallization, centrifugation, obtain filter cake 59.8g sal glauberi, the content recording hydrazine hydrate in centrifuge mother liquor is 56.2%, and concentration improves 40.5%.
Finally, it should be pointed out that above example is only the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to above-mentioned example, can also have many distortion, all distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, and all should think protection scope of the present invention.
Claims (3)
1. improve a method for concentration of hydrazine hydrate, it is characterized in that: the method comprises following step:
A. the hydrazine hydrate solution of 100-1000ml is got;
B. in hydrazine hydrate solution, 30g-200g is added not containing crystal water or the inorganic salt containing low crystal water;
C. crystallization is carried out to adding the hydrazine hydrate solution after inorganic salt, crystallization as far as possible completely under the condition in conjunction with maximum crystal water;
D. centrifuging is carried out to the hydrazine hydrate solution after crystallization, the hydrazine hydrate after mother liquor and concentrate;
E. the hydrated inorganic salt after centrifugal, dewaters, obtains anhydrous or that crystal water content is less inorganic salt, use as feedstock circulation.
The crystallisation process of this hydrate is freezing and crystallizing or teds crystallization.
2. the method for raising concentration of hydrazine hydrate according to claim 1, is characterized in that: described inorganic salt be sodium sulfate, sodium hydrogen phosphate, magnesium sulfate, sodium carbonate, Potassium monofluoride, copper sulfate or magnesium chloride one or more.
3. the method for raising concentration of hydrazine hydrate according to claim 1, is characterized in that: the dehydration of this hydrated inorganic salt-pepper noise, is heating, evaporation or one or more of drying.
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| CN201310004518.8A CN103043636B (en) | 2013-01-06 | 2013-01-06 | Method for increasing concentration of hydrazine hydrate |
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| CN103043636B true CN103043636B (en) | 2015-07-08 |
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| CN110325260A (en) * | 2016-11-08 | 2019-10-11 | 曼瑟森三汽油公司 | The method for removing moisture from hydrazine |
| CN110606609B (en) * | 2019-08-01 | 2022-06-14 | 中石化宁波工程有限公司 | Method for recovering organic matters in F-T synthesis reaction water |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963232A (en) * | 1987-05-28 | 1990-10-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a purified hydrazine hydrate |
| CN1927702A (en) * | 2006-08-16 | 2007-03-14 | 赖中胜 | Energy-saving process of producing hydrazine hydrate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3838274B2 (en) * | 1995-07-05 | 2006-10-25 | 三菱瓦斯化学株式会社 | How to deodorize hydrazine |
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2013
- 2013-01-06 CN CN201310004518.8A patent/CN103043636B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4963232A (en) * | 1987-05-28 | 1990-10-16 | Mitsubishi Gas Chemical Company, Inc. | Process for producing a purified hydrazine hydrate |
| CN1927702A (en) * | 2006-08-16 | 2007-03-14 | 赖中胜 | Energy-saving process of producing hydrazine hydrate |
Non-Patent Citations (1)
| Title |
|---|
| 国外水合肼、无水肼制备及提纯方法研发进展;胡长诚;《化学推进剂与高分子材料》;20050825;第3卷(第4期);第1-5页 * |
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Effective date of registration: 20191226 Address after: 314000 401, building 32, Hangzhou bay new economic Park, Jiaxing Port Area, Zhejiang Province Patentee after: Zhejiang Haiti New Material Technology Co., Ltd Address before: Science and Technology Industrial Park, seven village Haihong Yuhang District Liangzhu town of Hangzhou city in 311113 in Zhejiang Province Patentee before: Hangzhou Hi-Tech Fine Chemical Co., Ltd |
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