CN105712463B - A kind of method of hydrazine hydrate in conversion waste water - Google Patents
A kind of method of hydrazine hydrate in conversion waste water Download PDFInfo
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- CN105712463B CN105712463B CN201610180185.8A CN201610180185A CN105712463B CN 105712463 B CN105712463 B CN 105712463B CN 201610180185 A CN201610180185 A CN 201610180185A CN 105712463 B CN105712463 B CN 105712463B
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- hydrazine hydrate
- waste water
- transistion metal
- metal compound
- alcoholic solvent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of method for converting hydrazine hydrate in waste water, including：Transistion metal compound and alcoholic solvent are added in the waste water containing hydrazine hydrate, again with NaOH or ammoniacal liquor regulation pH to 9~14, then reacted at a temperature of 50~200rpm mixing speed and 10~40 DEG C, reaction time is 18~24h, wherein transistion metal compound is Fe, Co, Ni, Ru, Pd or Pt chloride or nitrate compound, and the mol ratio of transistion metal compound and hydrazine hydrate is 1:400~500, alcoholic solvent is 20~40 with protectant mass ratio:1.Instant invention overcomes equipment volume in traditional Ammonia-nitrogen wastewater treatment technology is huge, power consumption is big, cost high energy consumption, floor space is big, water quality requirement is strict a series of problems, such as.
Description
Technical field
The invention belongs to technical field for the treatment of of organic waste, and in particular to a kind of method for converting hydrazine hydrate in waste water.
Background technology
Hydrazine hydrate is important Minute Organic Synthesis raw material, and tool has been widely used.Mainly have 35%, 40%, 55%,
64%th, 80%, 85% and 100% plurality of specifications, its purposes is very extensive, and 1/3 above is make boiler water in the purposes distribution of hydrazine
Deoxidant, the hydrazine (including hydrazine hydrate and hydrazine sulfate) of foaming agent accounts for 30%, 10% accounted for for pharmacy.Due to hydrazine hydrate point
Containing two nitrogen and four active hydrogen that can be replaced with nucleophilicity in son, therefore, using hydrazine hydrate as the fine of raw material
Chemical products are almost related to all spectra.Hydrazine hydrate is strong reductant, has strong a reproducibility and corrosivity, can etching glass,
Rubber, leather, cork etc..Have strong basicity, dehydration hydrazine, be a kind of very important chemical raw material.It is main in consumer goods industry
It is used to produce foaming agent；It is the key component for producing various medicines in pharmaceutical industry；It is another can be also used for producing insecticide,
The tens of kinds of agricultural chemicals such as bactericide；In industrial circle, antioxidant can be used as.Due to the strong reducing property of hydrazine hydrate, and and oxygen
Reaction product is nontoxic, free from corrosion feature, while is also widely used in the deoxidation treatment of large-scale electricity generation boiler water or as electricity
Plate the cleaning agent of industry.
Ammonia nitrogen class material in water body is a main contamination index in China's waste water, the ammonia nitrogen class material meeting in water body
The eutrophication of water body is caused, reduces the ornamental value of water body, the existence of the mankind and biology are even endangered when serious.So in life
During production, waste water containing hydrazine hydrate can not be directly emitted, it is necessary to which, by wastewater treatment, its industrial production cost necessarily increases
Add.The method of domestic more common ammonia nitrogen waste water of the processing containing hydrazine hydrate mainly has physico-chemical process, chemical oxidization method, ion exchange
Method, chemical precipitation method and biological treatment etc..Physico-chemical process mainly includes blow-off method and vaporizing extract process, and both approaches are by waste water
Contacted with gas, ammonia nitrogen substances is transferred to gas phase from liquid phase, treatment mechanism is mass transport process, is now used to ammonia nitrogen in high density and gives up
The processing of water.But the equipment volume needed for physico-chemical process is huge, and power consumption is big, and removal effect is limited.Chemical oxidization method processing
The preferable technology of ammonia nitrogen waste water practicality is exactly chloridising.Chloridising is that the chlorine of sufficient amount or sodium hypochlorite are put into waste water
In, the ammonia nitrogen in waste water is oxidized to nitrogen and is divested.This method can produce the accessory substances such as chloramines and chlorinatedorganic and cause
Secondary pollution, after-treatment must be passed through, consider cost and Energy Consumption Factors, be unsuitable for the processing of big yield high-concentration ammonia nitrogenous wastewater.
Ion-exchange is to swap reaction by the ammonium ion in the ion and waste water on ion-exchanger in ion exchange column,
So as to reach the purpose of denitrogenation of waste water, the ammonia nitrogen waste water that this method is applied to middle low concentration is handled.Chemical precipitation method is to ammonia nitrogen
The magnesium salts and phosphate of solubility are added in waste water, it is MgNH to make the mineralized nitrogen in waste water4PO4·6H2O is precipitated, so as to remove
Ammonia nitrogen in waste water.This method dosing is big, and cost is higher, the after-treatment of caused a large amount of sludge in processing procedure, and
The chlorion and phosphatic pollution that adding of agent introduces are still to need to solve the problems, such as.Biological treatment treatment effect is by biology
The limitation of activity, the technology is stricter to entering water water quality requirement, and floor space is big, and low temperature aging rate is low, cycle length, is not appropriate for
It is widely applied.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of method for converting hydrazine hydrate in waste water.
The principle of the present invention is as follows：
The present invention be using waste water of the transistion metal compound processing containing hydrazine hydrate, wherein add protective agent, hydrazine hydrate and
Redox reaction generation nitrogen, the mistake generated in being reacted when hydrazine hydrate excess occur under normal circumstances for transistion metal compound
Crossing metal powder has certain autocatalysis, and its presence accelerates the decomposition of hydrazine hydrate itself to a certain extent, so as to reach
To the purpose of degraded hydrazine hydrate.By taking nickel based compound as an example, specific reaction is as follows：
When hydrazine hydrate is a small amount of：2Ni2++N2H4+4OH-→2Ni↓+N2↑+4H2O
During hydrazine hydrate excess：N2H4·H2O→N2H4+H2O
In above-mentioned reaction, alcoholic solvent makes hydrazine hydrate, protective agent and transition metal ions scattered evenly, does not join directly
With reaction；Protectant addition has no effect on reaction and carried out, it might even be possible to is not added with.The reaction need to be carried out in the basic conditions,
PH value of solution need to be adjusted into alkalescence；Reaction temperature major control reaction rate, but from the point of view of cost for wastewater treatment, temperature is not easy
Too high, normal temperature is just.
The concrete technical scheme of the present invention is as follows：
A kind of method of hydrazine hydrate in conversion waste water, including：Transition metal compound is added in the waste water containing hydrazine hydrate
Thing and alcoholic solvent, then pH to 9~14 is adjusted with NaOH or ammoniacal liquor, then in 50~200rpm mixing speed and 10~40 DEG C
At a temperature of reacted, the reaction time is 18~24h, wherein transistion metal compound be Fe, Co, Ni, Ru, Pd or Pt chlorination
The mol ratio of thing or nitrate compound, transistion metal compound and hydrazine hydrate is 1:400~500, alcoholic solvent and protectant matter
Amount is than being 20~40:1.
In a preferred embodiment of the invention, before with NaOH or ammoniacal liquor regulation pH to 9~14, also to add
The mass ratio of protective agent, protective agent and transistion metal compound is 1~1.5:1.It is further preferred that the protective agent be PVP,
PVA or PEG.
In a preferred embodiment of the invention, the alcoholic solvent is methanol or ethanol.It is it is further preferred that described
Ethanol is 95% ethanol.
In a preferred embodiment of the invention, the mixing speed is 80rpm.
In a preferred embodiment of the invention, the reaction time is 24h.
The beneficial effects of the invention are as follows：
1st, method of the invention is directed to the transition problem of the hydrazine reaction liquid containing hydration, it is proposed that a kind of new catalysis oxidation drop
Solve ammonia nitrogen waste water in hydrazine hydrate method, the method overcome equipment volume in traditional Ammonia-nitrogen wastewater treatment technology it is huge,
Power consumption is big, cost high energy consumption, a series of problems, such as floor space is big, water quality requirement is strict.
2nd, in method of the invention, hydrazine hydrate transforming degree is controllable, subsequent treatment process is simple, and reaction condition is gentle, has
It is widely applied promotion prospect.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
The solution that 1300ml contains 0.1% hydrazine hydrate is added in 5L reactors, adds 0.03g transistion metal compounds
H2PtCl6·6H2O, 0.04g protective agents PVP powder, 1.6ml 95% alcohol solvent, the pH to 9 of solution, control are adjusted with ammoniacal liquor
10 DEG C of reaction temperature processed, 80 turns/min of stir speed (S.S.), react 24 hours.
Hydrazine hydrate content is 0.1% before being reacted in the present embodiment, and hydrazine hydrate content is 0.07% after reaction.
Embodiment 2
The solution that 1300ml contains 1% hydrazine hydrate is added in 5L reactors, adds 0.12g transistion metal compounds
RuCl3·3H2O, 0.16g protective agents PVA powder, 6.4ml 95% alcohol solvent, the pH to 10 of solution, control are adjusted with ammoniacal liquor
20 DEG C of reaction temperature processed, 80 turns/min of stir speed (S.S.), react 24 hours.
Hydrazine hydrate content is 1% before being reacted in the present embodiment, and hydrazine hydrate content is 0.54% after reaction.
Embodiment 3
The solution that 1300ml contains 5% hydrazine hydrate is added in 5L reactors, adds 0.6g transistion metal compounds FeCl2·
4H2O, 0.8g protective agents PVP powder, 32ml 95% alcohol solvent, the pH to 11 of solution, control reaction temperature are adjusted with NaOH
30 DEG C, 80 turns/min of stir speed (S.S.) of degree, react 24 hours.
Hydrazine hydrate content is 5% before being reacted in the present embodiment, and hydrazine hydrate content is 1.4% after reaction.
Embodiment 4
The solution that 1300ml contains 10% hydrazine hydrate is added in 5L reactors, adds 1.33g transistion metal compounds
CoCl2·6H2O, 1.88g protective agents PEG powder, 75ml 95% alcohol solvent, the pH to 12 of solution, control are adjusted with NaOH
40 DEG C of reaction temperature, 80 turns/min of stir speed (S.S.), react 24 hours.
Hydrazine hydrate content is 10% before being reacted in the present embodiment, and hydrazine hydrate content is 3.2% after reaction
Embodiment 5
The solution that 1300ml contains 10% hydrazine hydrate is added in 5L reactors, adds 1.33g transistion metal compounds
NiCl2·6H2O, 2g protective agents PVP powder, 80ml 95% alcohol solvent, the pH to 10 of solution is adjusted with ammoniacal liquor, and control is anti-
10 DEG C of temperature is answered, 80 turns/min of stir speed (S.S.), is reacted 24 hours.
Hydrazine hydrate content is 10% before being reacted in the present embodiment, and hydrazine hydrate content is 4.6% after reaction.
Embodiment 6
The waste water solution that 1300ml contains 20% hydrazine hydrate is added in 5L reactors, adds 3.2g transistion metal compounds Ni
(NO3)2·6H2O, 4.8g protective agents PVA powder, 190ml 95% ethylene glycol solvent, the pH to 13 of solution is adjusted with NaOH,
30 DEG C of controlling reaction temperature, 80 turns/min of stir speed (S.S.), react 24 hours.
Hydrazine hydrate content is 20% before being reacted in the present embodiment, and hydrazine hydrate content is 5.0% after reaction.
Embodiment 7
The solution that 1300ml contains 10% hydrazine hydrate is added in 5L reactors, adds 1g transistion metal compounds PdCl2、
1.33g protective agent PVP powder, 50ml 95% alcohol solvent, the pH to 10 of solution, controlling reaction temperature 10 are adjusted with ammoniacal liquor
DEG C, 80 turns/min of stir speed (S.S.), react 24 hours.
Hydrazine hydrate content is 10% before being reacted in the present embodiment, and hydrazine hydrate content is 4.4% after reaction.
Embodiment 8
The solution that 1300ml contains 20% hydrazine hydrate is added in 5L reactors, adds 2g transistion metal compounds PdCl2、3g
Protective agent PEG powder, 120ml 95% ethylene glycol solvent, with NaOH adjust solution pH to 14,30 DEG C of controlling reaction temperature,
80 turns/min of stir speed (S.S.), react 24 hours.
Hydrazine hydrate content is 20% before being reacted in the present embodiment, and hydrazine hydrate content is 4.4% after reaction.
Those of ordinary skill in the art understand, when technical scheme changes in following ranges, remain able to
To same as the previously described embodiments or similar technique effect：
A kind of method of hydrazine hydrate in conversion waste water, including：Transition metal compound is added in the waste water containing hydrazine hydrate
Thing and alcoholic solvent, then pH to 9~14 is adjusted with NaOH or ammoniacal liquor, then in 50~200rpm mixing speed and 10~40 DEG C
At a temperature of reacted, the reaction time is 18~24h, wherein transistion metal compound be Fe, Co, Ni, Ru, Pd or Pt chlorination
The mol ratio of thing or nitrate compound, transistion metal compound and hydrazine hydrate is 1:400~500, alcoholic solvent and protectant matter
Amount is than being 20~40:1.
Preferably, before with NaOH or ammoniacal liquor regulation pH to 9~14, protective agent, protective agent and transition gold also to be added
The mass ratio for belonging to compound is 1~1.5:1, the protective agent is PVP, PVA or PEG.The alcoholic solvent is methanol or ethanol.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still it belong in the range of the present invention covers.
Claims (7)
- A kind of 1. method for converting hydrazine hydrate in waste water, it is characterised in that：Including：Transition is added in the waste water containing hydrazine hydrate Metallic compound and alcoholic solvent, then pH to 9~14 is adjusted with NaOH or ammoniacal liquor, then in 50~200rpm mixing speed and 10 Reacted at a temperature of~40 DEG C, the reaction time is 18~24h, wherein transistion metal compound be Fe, Co, Ni, Ru, Pd or The mol ratio of Pt chloride or nitrate compound, transistion metal compound and hydrazine hydrate is 1:400~500, alcoholic solvent is with protecting The mass ratio for protecting agent is 20~40:1.
- 2. the method as described in claim 1, it is characterised in that：Before with NaOH or ammoniacal liquor regulation pH to 9~14, also to add Enter protective agent, the mass ratio of protective agent and transistion metal compound is 1~1.5:1.
- 3. method as claimed in claim 2, it is characterised in that：The protective agent is PVP, PVA or PEG.
- 4. the method as described in claim 1, it is characterised in that：The alcoholic solvent is methanol or ethanol.
- 5. method as claimed in claim 4, it is characterised in that：The ethanol is 95% ethanol.
- 6. the method as described in any claim in claim 1 to 5, it is characterised in that：The mixing speed is 80rpm.
- 7. the method as described in any claim in claim 1 to 5, it is characterised in that：The reaction time is 24h.
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| CN201610180185.8A CN105712463B (en) | 2016-03-25 | 2016-03-25 | A kind of method of hydrazine hydrate in conversion waste water |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134120A (en) * | 2011-02-25 | 2011-07-27 | 深圳市科之泉水处理科技有限公司 | Method for recovering precious metals in acidic waste liquid |
| CN103386305A (en) * | 2013-07-31 | 2013-11-13 | 南京威安新材料科技有限公司 | Preparation method, application process and application device of catalyst for treatment of hydrazine and ammonia-nitrogen wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134120A (en) * | 2011-02-25 | 2011-07-27 | 深圳市科之泉水处理科技有限公司 | Method for recovering precious metals in acidic waste liquid |
| CN103386305A (en) * | 2013-07-31 | 2013-11-13 | 南京威安新材料科技有限公司 | Preparation method, application process and application device of catalyst for treatment of hydrazine and ammonia-nitrogen wastewater |
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