CN107531523A - The processing method and ammonium-nitrogen distintegrant of the waste water containing ammonium-nitrogen - Google Patents
The processing method and ammonium-nitrogen distintegrant of the waste water containing ammonium-nitrogen Download PDFInfo
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- CN107531523A CN107531523A CN201680025926.3A CN201680025926A CN107531523A CN 107531523 A CN107531523 A CN 107531523A CN 201680025926 A CN201680025926 A CN 201680025926A CN 107531523 A CN107531523 A CN 107531523A
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- nitrogen
- ammonium
- waste water
- bromine
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/586—Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing ammoniacal nitrogen
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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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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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
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
Abstract
There is provided：The processing method for the waste water containing ammonium-nitrogen that can be handled in easy method waste water containing ammonium-nitrogen.A kind of processing method of waste water containing ammonium-nitrogen, the reactant and sulfamic acid compound for making bromine system oxidant or bromine compounds and chlorine system oxidant are present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen；Make the reactant of bromine system oxidant or bromine compounds and chlorine system oxidant, be present in the mixture of sulfamic acid compound or reaction product in the waste water containing ammonium-nitrogen containing ammonium-nitrogen；Or the mixture of bromine and sulfamic acid compound or the reaction product of bromine and sulfamic acid compound is set to be present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen.
Description
Technical field
The present invention relates to the processing method and ammonia of the waste water containing ammonium-nitrogen for handling the waste water such as the sewage comprising ammonium-nitrogen
Property nitrogen distintegrant.
Background technology
When enterprise's plant chimney stalk comprising plant chimney stalk, recycled treated water etc. are emitted into commons waters, these discharges
Water is applicable according to water quality dirt method is prevented by waste water benchmark.In addition, for Tokyo Bay, Yi Shiwan, Seto Island Sea this 3
Marine site, it turns into the object of the total amount limitation based on COD, nitrogen, phosphorus.
In waste water, such as sewage, the waste water etc. of aquatic products processing factory, in order to tackle waste water benchmark and total amount limitation,
It must carry out disinfection before discharging so that coli-group number turns into 3000/below mL, in addition, also it is desirable to reduce ammonia as far as possible
Property the content as the composition of the object of waste water limitation such as nitrogen.
As the disinfectant of sewage etc., general use has the chlorine such as hypochlorite system oxidant, but ammonia is included in processed water
During property nitrogen, chlorine system oxidant can react with ammonium-nitrogen and generate chloramines, and accordingly, there exist Disinfection Effect to become insufficient class
Topic.Therefore, it is recently proposed, disinfectant composition is used as using bromine system oxidant.If using has contained by Decomposition Wastewater
The composition of the effect of ammonium-nitrogen then causes the load reduction of the biological treatments such as nitrification denitrogenation of back segment as disinfectant composition, from
From the viewpoint of wastewater treatment, favourable processing can also be carried out.
In patent document 1, as the waste water disinfectant of sewage etc., the disinfectant comprising hypobromous acid or its salt is shown.
In addition, in patent document 2, as the sterilization method comprising ammonia or the sewage effluent of ammonium ion, show that use includes the bromo- 3- of 1-
The sterilization method of the solid disinfecting agent of chloro- 5,5- dimethyl hydantoins, for this method, sewage when can also tackle the rainy day
Processing.
However, for the method described in patent document 1, it is necessary to for obtain hypobromous acid or its salt bromide salt and time
The storage facilities of this 2 kinds of medicaments of chlorate and the reaction unit for reacting them, equipment become huge.For in patent document 2
The method of record, because disinfectant is solid, it is therefore desirable to dissolver, similarly equipment become huge.In addition, for patent
Method described in document 1,2, not on ammonium-nitrogen contained in waste water, sewage etc. minimizing effect any record.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2003-012425 publications
Patent document 2：No. 4628132 publications of Japanese Patent No.
The content of the invention
Problems to be solved by the invention
It is an object of the present invention to provide：What waste water containing ammonium-nitrogen can be handled in easy method contains ammonia
The processing method and ammonium-nitrogen distintegrant of nitrogen waste water.
The solution used to solve the problem
The present invention is a kind of processing method of waste water containing ammonium-nitrogen, bromine system oxidant or bromine compounds is aoxidized with chlorine system
The reactant and sulfamic acid compound of agent are present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen.
The present invention is a kind of processing method of waste water containing ammonium-nitrogen, makes bromine system oxidant or bromine compounds and chlorine system oxygen
The mixture or reaction product of the reactant of agent and sulfamic acid compound are present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen
In.
The present invention is a kind of processing method of waste water containing ammonium-nitrogen, is present in the mixture of bromine and sulfamic acid compound
In waste water containing ammonium-nitrogen containing ammonium-nitrogen；Or the reaction product of bromine and sulfamic acid compound is set to be present in containing ammonia
In the waste water containing ammonium-nitrogen of nitrogen.
In the processing method of the foregoing waste water containing ammonium-nitrogen, it is preferred that make foregoing bromine system oxidant or foregoing bromine compounds
It is present in the reactant of chlorine system oxidant and foregoing sulfamic acid compound in foregoing waste water containing ammonium-nitrogen, then further
The processing water reduced with reverse osmosis membrane to ammonium-nitrogen is handled.
In the processing method of the foregoing waste water containing ammonium-nitrogen, it is preferred that close foregoing bromine system oxidant or foregoing bromination
The reactant of thing and chlorine system oxidant, it is present in the mixture of foregoing sulfamic acid compound or reaction product and foregoing contains ammonia
In nitrogen waste water, the processing water then further reduced with reverse osmosis membrane to ammonium-nitrogen is handled.
In the processing method of the foregoing waste water containing ammonium-nitrogen, it is preferred that make the mixing of foregoing bromine and sulfamic acid compound
After thing is present in foregoing waste water containing ammonium-nitrogen or the reaction product of foregoing bromine and sulfamic acid compound is set to be present in foregoing contain
After in ammonium-nitrogen waste water, the processing water further reduced with reverse osmosis membrane to ammonium-nitrogen is handled.
In the processing method of the foregoing waste water containing ammonium-nitrogen, it is preferred that the equivalent of sulfamic acid compound is relative to bromine
The ratio between equivalent is 0.5~1.5 scope.
In the processing method of the foregoing waste water containing ammonium-nitrogen, it is preferred that the effective chlorine density in foregoing waste water containing ammonium-nitrogen
The molar concentration of effective halogen of conversion is more than 1.6 relative to the ratio between molar concentration of ammonium-nitrogen.
In the processing method of the foregoing waste water containing ammonium-nitrogen, it is preferred that ammonium-nitrogen in foregoing waste water containing ammonium-nitrogen it is dense
Spend for more than 5mg/L.
The present invention is a kind of ammonium-nitrogen distintegrant, and it is for decomposing the ammonium-nitrogen of the ammonium-nitrogen in waste water containing ammonium-nitrogen point
Agent is solved, comprising：The reactant and sulfamic acid compound of bromine system oxidant or bromine compounds and chlorine system oxidant.
The present invention is a kind of ammonium-nitrogen distintegrant, and it is for decomposing the ammonium-nitrogen of the ammonium-nitrogen in waste water containing ammonium-nitrogen point
Agent is solved, comprising：The reactant of bromine system oxidant or bromine compounds with chlorine system oxidant, the mixing with sulfamic acid compound
Thing or reaction product.
The present invention is a kind of ammonium-nitrogen distintegrant, and it is for decomposing the ammonium-nitrogen of the ammonium-nitrogen in waste water containing ammonium-nitrogen point
Agent is solved, comprising：The mixture or bromine of bromine and sulfamic acid compound and the reaction product of sulfamic acid compound.
In foregoing ammonium-nitrogen distintegrant, it is preferred that the equivalent of sulfamic acid compound is relative to the ratio between equivalent of bromine
0.5~1.5 scope.
In foregoing ammonium-nitrogen distintegrant, it is preferred that the concentration of the ammonium-nitrogen in foregoing waste water containing ammonium-nitrogen be 5mg/L with
On.
The effect of invention
In the present invention, waste water containing ammonium-nitrogen can be handled in easy method.
Embodiment
Hereinafter, illustrated for embodiments of the present invention.Present embodiment is only to implement of the invention one, this hair
It is bright to be not limited to present embodiment.
The processing method ＞ of ＜ waste water containing ammonium-nitrogen
The processing method of the waste water containing ammonium-nitrogen of embodiments of the present invention is following method：Make " bromine system oxidant " and
The method that " sulfamic acid compound " is present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen；Or, make " bromine compounds and chlorine system oxygen
The method that the reactant of agent " and " sulfamic acid compound " are present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen.Thus recognize
For in waste water containing ammonium-nitrogen, generation stabilizes hypobromous acid composition.
The processing method of the waste water containing ammonium-nitrogen of embodiments of the present invention is following method：Make " bromine system oxidant and ammonia
The mixture of base sulfoacid compound " or " reaction product of bromine system oxidant and sulfamic acid compound " stabilize hypobromous acid
The method that composition is present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen；Or, make the " reaction of bromine compounds and chlorine system oxidant
Thing, the mixture with sulfamic acid compound " or " reactant and sulfamic acid chemical combination of bromine compounds and chlorine system oxidant
The reaction product of thing " stabilizes the method that hypobromous acid composition is present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen.
Specifically, the processing method of the waste water containing ammonium-nitrogen of present embodiment is, for example, following method：Make " bromine ", " chlorine
Change bromine ", " hypobromous acid " or " sodium bromide and hypochlorous reactant " and " sulfamic acid compound " are present in waste water containing ammonium-nitrogen
In.
In addition, the processing method of the waste water containing ammonium-nitrogen of present embodiment is, for example, following method：Make " bromine and sulfamic acid
The mixture of compound ", " mixture of bromine chloride and sulfamic acid compound " or " sodium bromide and hypochlorous reactant, with
The mixture of sulfamic acid compound " stabilizes hypobromous acid composition and is present in waste water containing ammonium-nitrogen.In addition, this embodiment party
The processing method of the waste water containing ammonium-nitrogen of formula is, for example, following method：Make " reaction product of bromine and sulfamic acid compound ", " chlorine
Change the reaction product of bromine and sulfamic acid compound " or " sodium bromide with hypochlorous reactant, with sulfamic acid compound
Reaction product " stabilizes hypobromous acid composition and is present in waste water containing ammonium-nitrogen.
Using these methods, the ammonium-nitrogen efficiency in waste water containing ammonium-nitrogen can be decomposed well, can be with easy
Method is handled waste water containing ammonium-nitrogen.For these methods, a kind of inorganic agent can be used to carry out waste water containing ammonium-nitrogen
Processing.In addition, using the minimizing effect (Disinfection Effect) with coli-group number and with decomposition ammonium-nitrogen effect into
It is allocated as disinfectant composition, therefore so that the load reduction of biological treatment such as nitrification denitrogenation of back segment etc., from the sight of wastewater treatment
Point sets out, and can also carry out favourable processing.
Sodium hypochlorite as chlorine system oxidant can react with the ammonium-nitrogen in waste water containing ammonium-nitrogen and generate combination
Halogen (chloramines), the decomposability of ammonium-nitrogen are greatly reduced, but aforementioned stable hypobromous acid composition can be directly by ammonium-nitrogen
Decompose and without combine halogen generation, therefore, compared with the chlorine such as sodium hypochlorite system oxidant, the discomposing effect of ammonium-nitrogen
It is high, it is believed that can more effectively to be handled.In addition, aforementioned stable hypobromous acid composition includes sulfamic acid compound, because
This thinks, when compared with hypobromous acid or its salt, the discomposing effect of ammonium-nitrogen is high.
In the processing method of the waste water containing ammonium-nitrogen of present embodiment, for example, note can be passed through in waste water containing ammonium-nitrogen
Teat pipette etc. injects " bromine system oxidant " or " reactant of bromine compounds and chlorine system oxidant " and " sulfamic acid compound ".
Can be added respectively in waste water containing ammonium-nitrogen " bromine system oxidant " or the reactant of chlorine system oxidant " bromine compounds with " and
" sulfamic acid compound ", or can be so that stoste is mixed with each other and is added to waste water containing ammonium-nitrogen after forming mixture.
In addition, for example, can by " reaction product of bromine system oxidant and sulfamic acid compound " or " bromine compounds with
The reactant of chlorine system oxidant, the reaction product with sulfamic acid compound " is injected into waste water containing ammonium-nitrogen by killer injecting pump etc.
In.
" bromine system oxidant " or " sulfamic acid compound " in " reactant of bromine compounds and chlorine system oxidant "
Equivalent is relative to the equivalent of the ratio between the equivalent of " bromine " or " sulfamic acid compound " relative to the ratio between equivalent of " bromine " preferably 0.1
Above, more preferably 0.5~1.5 scope, further preferred 1~1.5 scope.Herein, the equivalent of " sulfamic acid compound "
The ratio between equivalent relative to " bromine " refers to compare as follows：Stabilize the sulfamic acid compound containing ratio [weight in hypobromous acid composition
Amount %] divided by the molecular weight (being 97.1 when sulfamic acid compound is sulfamic acid) of sulfamic acid compound obtained from be worth phase
For stabilizing bromine containing ratio [weight %] divided by bromine (Br in hypobromous acid composition2) molecular weight (159.8) obtained from
The ratio between value.When the equivalent of " sulfamic acid compound " is less than 0.1 relative to the ratio between the equivalent of " bromine ", it can not obtain sometimes sufficiently
The discomposing effect of ammonium-nitrogen, during more than 1.5, manufacturing cost increases sometimes.The ratio between the equivalent if 0.5~1.5 scope, more
It is preferred that 0.7~1.5 scope, then well can be decomposed ammonium-nitrogen with efficiency.In addition, the ratio between the equivalent is if more than 1, then
The stability of preparation becomes good.
Effective halogen concentration in waste water containing ammonium-nitrogen is in terms of effective chlorine density conversion, preferably 1~50mg/L.It is less than
During 1mg/L, the discomposing effect of sufficient ammonium-nitrogen can not be obtained sometimes, during more than 50mg/L, it is possible to cause the corruption of pipe arrangement etc.
Erosion.
The molar concentration of effective halogen of effective chlorine density conversion in waste water containing ammonium-nitrogen (stabilizes hypobromous acid composition
Addition molar concentration) relative to ammonium-nitrogen (NH4- N) the ratio between molar concentration be preferably more than 1.6, more preferably 2.0 with
On., than becoming bigger, the minimizing effect of ammonium-nitrogen becomes higher for this.
As bromine system oxidant, can enumerate：Bromine (liquid bromine), bromine chloride, bromic acid, bromate, hypobromous acid etc..
Among these, using bromine " bromine and sulfamic acid compound (mixture of bromine and sulfamic acid compound) " or
The preparation of the preparation of " reaction product of bromine and sulfamic acid compound " and " hypochlorous acid with bromine compounds and sulfamic acid " and
Compared with the preparation of " bromine chloride is with sulfamic acid " etc., the secondary generation of bromic acid is few, cause the metal material of pipe arrangement etc. corrosion can
Energy property is low, therefore more preferably.
That is, the processing method of the waste water containing ammonium-nitrogen of present embodiment is preferably, and deposits bromine and sulfamic acid compound
In (the mixture presence for making bromine and sulfamic acid compound) in waste water containing ammonium-nitrogen.It is further preferred, that make bromine and amino
The reaction product of sulfoacid compound is present in waste water containing ammonium-nitrogen.
As bromine compounds, can enumerate：Sodium bromide, KBr, lithium bromide, ammonium bromide and hydrobromic acid etc..Among these, from
The viewpoints such as preparation cost are set out, preferably sodium bromide.
As chlorine system oxidant, such as can enumerate：Chlorine, chlorine dioxide, hypochlorous acid or its salt, chlorous acid or its salt, chlorine
Acid or its salt, perchloric acid or its salt, chlorinated isocyanuric acid or its salt etc..Among these, as salt, such as it can enumerate：Hypochlorous acid
The hypochlorous acid such as the alkali metal hypochlorites such as sodium, postassium hypochlorite, calcium hypochlorite, barium hypochlorite alkali salt, sodium chlorite, sub- chlorine
Other metal chlorites, the chlorine such as the chlorous acid such as the alkali metal chlorites such as sour potassium, barium chlorite alkali salt, chlorous acid nickel
Chloric acid alkali salts such as the chloric acid such as sour ammonium, sodium chlorate, potassium chlorate alkali metal salt, calcium chlorate, barium chlorate etc..These chlorine systems aoxidize
Agent can be used alone, and can also combine two or more use.It is excellent from viewpoints such as treatability as chlorine system oxidant
Choosing uses sodium hypochlorite.
Sulfamic acid compound is the compound shown in below general formula (1).
R2NSO3H (1)
(in formula, R independently is the alkyl of hydrogen atom or carbon number 1~8.)
As sulfamic acid compound, such as except 2 R bases are the sulfamic acid (amidosulfuric of hydrogen atom
Acid beyond), can also enumerate：N- methylsulfamic acids, N- ethylaminos sulfonic acid, N- propylcarbamics sulfonic acid, N- isopropylaminos
One of 2 R bases such as sulfonic acid, N- butylamino sulfonic acid are hydrogen atom, the amino sulphur for the alkyl that another one is carbon number 1~8
Acid compound；N, N- dimethylamino sulfonic acid, N, N- diethylaminos sulfonic acid, N, N- dipropylaminos sulfonic acid, N, N- dibutyl
2 R bases such as sulfamic acid, N- methyl-N-ethylaminos sulfonic acid, N- methyl-N-propylamino sulfonic acid are carbon number 1~8
Alkyl sulfamic acid compound；One of 2 R bases such as N- benzenesulfamics are hydrogen atom, another one is carbon number 6
The sulfamic acid compound of~10 aryl；Or their salt etc..As sulfamate, such as can enumerate：Sodium salt, sylvite etc.
Alkali metal salt；The alkali salts such as calcium salt, strontium salt, barium salt；Other metals such as manganese salt, mantoquita, zinc salt, molysite, cobalt salt, nickel salt
Salt；Ammonium salt and guanidinesalt etc..Sulfamic acid compound and these salt can be used alone, and can also combine two or more use.
As sulfamic acid compound, from the viewpoint of carrying capacity of environment etc., preferably using sulfamic acid (amidosulfuric
acid)。
In the processing method of the waste water containing ammonium-nitrogen of present embodiment, there can also be alkali.As alkali, can enumerate：Hydrogen-oxygen
Change alkali hydroxides such as sodium, potassium hydroxide etc..From low temperature when product stability etc. from the viewpoint of, hydroxide can be applied in combination
Sodium and potassium hydroxide.In addition, alkali can not be solid-state, but use in form of an aqueous solutions.
In the processing method of the waste water containing ammonium-nitrogen of present embodiment, the pH of the waste water containing ammonium-nitrogen of process object is preferably
3~10 scope, more preferably 4~9 scope.Process object the waste water containing ammonium-nitrogen pH be less than 3 when, hypobromous acid easily with
The form volatilization of bromine gas, the discomposing effect of ammonium-nitrogen reduces sometimes, and during more than 10, easily volatilization is simultaneously in the form of ammonia for ammonium-nitrogen
It is removed, is reduced sometimes using the validity of the processing of the present invention.
Waste water containing ammonium-nitrogen as the process object of the processing method of the waste water containing ammonium-nitrogen of present embodiment is, for example,
Enterprise's plant chimney stalk of plant chimney stalk comprising aquatic products processing factory etc., sewage etc..Waste water containing ammonium-nitrogen as process object
In ammonium-nitrogen concentration for example be preferably more than 5mg/L, more preferably 5mg/L~500mg/L scope.Utilize this embodiment party
The processing method of the waste water containing ammonium-nitrogen of formula, it is suitable for the place of the such sewage comprising more ammonium-nitrogen of more than 5mg/L etc.
Reason.For such sewage comprising more ammonium-nitrogen of more than 5mg/L etc., the reduction that can not only play coli-group number is imitated
Fruit, the effect for decomposing ammonium-nitrogen contained in waste water containing ammonium-nitrogen can also be played.Particularly, with reverse osmosis membrane to containing ammonia
In the case that the waste water of nitrogen is handled, if the pH of waste water is high, there are the following problems：Free ammonia can pass through counter-infiltration
Film, leaked into transmission water.On this point, if as the processing method of the waste water containing ammonium-nitrogen of present embodiment,
Addition stabilizes hypobromous acid composition in waste water containing ammonium-nitrogen, and after decomposing ammonium-nitrogen, ammonium-nitrogen is reduced with reverse osmosis membrane
Processing water handled, then can suppress the problem of free ammonia in water to through leaking, therefore it is preferred that.
＜ ammonium-nitrogen distintegrants ＞
The ammonium-nitrogen distintegrant of present embodiment contains：" bromine system oxidant " or " bromine compounds is anti-with chlorine system oxidant
Answer thing " and " sulfamic acid compound ", alkali can also be contained.
In addition, the ammonium-nitrogen distintegrant of present embodiment contains：" the mixing of bromine system oxidant and sulfamic acid compound
Thing " or " reactant of the bromine compounds with chlorine system oxidant, the mixture with sulfamic acid compound ", can also contain alkali.Separately
Outside, the ammonium-nitrogen distintegrant of present embodiment contains：" reaction product of bromine system oxidant and sulfamic acid compound " or " bromine
Reactant of the compound with chlorine system oxidant, the reaction product with sulfamic acid compound ", can also contain alkali.
For bromine system oxidant, bromine compounds, chlorine system oxidant and sulfamic acid compound, as described above.
As the ammonium-nitrogen distintegrant of present embodiment, from the corrosivity of the metal material to pipe arrangement etc. is low, pair of bromic acid
Generate lack etc. to set out, preferably comprise bromine and sulfamic acid compound (mixture containing bromine and sulfamic acid compound),
Such as mixture or the reaction product of bromine and sulfamic acid compound containing bromine, sulfamic acid compound, alkali and water, example
Such as the reaction product and alkali of bromine and sulfamic acid compound and the mixture of water.
The ammonium-nitrogen distintegrant of present embodiment, can be directly by ammonium-nitrogen point compared with the chlorine such as sodium hypochlorite system oxidant
Solution and without the generation for combining halogen, result, it is believed that the discomposing effect of ammonium-nitrogen is high.In addition, the ammonium-nitrogen of present embodiment
Distintegrant includes sulfamic acid compound, it is therefore contemplated that compared with hypobromous acid or its salt, the discomposing effect of ammonium-nitrogen is high.
The pH of ammonium-nitrogen distintegrant is for example more than 13.0, more preferably above 13.2.The pH of ammonium-nitrogen distintegrant be 13.0 with
When lower, effective halogen in distintegrant becomes unstable sometimes.
Bromic acid concentration in ammonium-nitrogen distintegrant is preferably shorter than 5mg/kg.Bromic acid concentration in ammonium-nitrogen distintegrant is 5mg/
During more than kg, the concentration for handling the bromic acid ion of water uprises sometimes.
The manufacture method ＞ of ＜ ammonium-nitrogen distintegrants
The ammonium-nitrogen distintegrant of present embodiment can by the way that bromine system oxidant is mixed with sulfamic acid compound or
Bromine compounds is mixed with the reactant and sulfamic acid compound of chlorine system oxidant and obtained, can also further mixed base.
As the ammonium-nitrogen distintegrant containing bromine and sulfamic acid compound or containing bromine and sulfamic acid compound
The manufacture method of the ammonium-nitrogen distintegrant of reaction product, preferably includes following process：Bromine is added under non-active gas atmosphere
The process reacted into the mixed liquor comprising water, alkali and sulfamic acid compound；Or under non-active gas atmosphere
Process bromine being added in the mixed liquor comprising water, alkali and sulfamic acid compound.By adding under non-active gas atmosphere
Calais is reacted or added under non-active gas atmosphere, so that the bromic acid ion concentration step-down in distintegrant.
Do not limited as the non-active gas used, but from manufacture etc. aspect, preferably in nitrogen and argon gas
It is at least one kind of, the aspect particularly from manufacturing cost etc., preferably nitrogen.
The oxygen concentration in reactor when adding bromine is preferably below 6% volume, more preferably below 4 volume %, enters one
Step is preferably below 2 volume %, particularly preferably below 1 volume %.If the oxygen concentration in reactor during bromine reaction is more than 6 bodies
Product %, then the growing amount increase of the bromic acid in reaction system sometimes.
The adding rate of bromine is preferably below 25 weight %, more preferably more than 1 weight % relative to the overall amount of distintegrant
And 20 below weight %.The adding rate of bromine is relative to the overall amount of distintegrant, if more than 25 weight %, sometimes in reaction system
Bromic acid growing amount increase.If being less than 1 weight %, the discomposing effect of ammonium-nitrogen has the time difference.
Reaction temperature when adding bromine is preferably controlled in more than 0 DEG C and less than 25 DEG C of scope, but from manufacturing cost etc.
Aspect set out, more preferably control more than 0 DEG C and in less than 15 DEG C of scope.If reaction temperature when adding bromine is more than 25
DEG C, then the growing amount increase of the bromic acid in reaction system sometimes, if less than 0 DEG C, freezes sometimes.
Embodiment
Hereinafter, enumerating embodiment and comparative example, more specifically the present invention is described in detail, but the present invention does not limit
In following examples.
The preparation ＞ of ＜ compositions
Stabilisation hypobromous acid composition A, B, C-1, C-2, C-3, the C-4 and hypobromite composition D used in embodiment
It is such as following.
[preparation for stabilizing hypobromous acid composition A]
In a nitrogen atmosphere, by liquid bromine：16.9 weight % (wt%), sulfamic acid：10.7 weight %, sodium hydroxide：
12.9 weight %, potassium hydroxide：3.94 weight %, water：Residual mixes, and prepares composition.The pH of composition is 14, bromine containing ratio
For 16.9 weight %.The detailed preparation method for stabilizing hypobromous acid composition A is for example following.
Used when controlling the flow of nitrogen with mass flow controller and be continuously injected into and enclose nitrogen and reaction is held
Oxygen concentration in device is maintained in 1 volume % 2L 4 mouthfuls of flasks, adds 1436g water, 361g sodium hydroxide is mixed
Close, be subsequently added into 300g sulfamic acid mixed after, on one side maintain cooling cause reaction solution temperature be 0~15 DEG C, one
Side adds 473g liquid bromine, and then adds 48 weight % potassium hydroxide solution 230g, obtains relative to the overall amount of composition
The target for being 1.04 as the ratio between equivalent of sulfamic acid 10.7%, the equivalent of bromine 16.9% and sulfamic acid and bromine using weight ratio meter
Stabilize hypobromous acid composition A.The pH of the solution of generation is determined by glass electrode method, is as a result 14.The solution of generation
Bromine is converted into after iodine and determined using the method for sodium thiosulfate progress redox titration by bromine containing ratio by using KI,
As a result it is 16.9 weight %, is the 100.0% of theoretical containing ratio (16.9 weight %).In addition, in reaction vessel during bromine reaction
Oxygen concentration using JIKCO Ltd. " Oxygen Monitor JKO-02LJDII " are determined.It should be noted that bromine
Acid concentration is less than 5mg/kg.
It should be noted that pH measure is carried out under the following conditions.
Electrode type：Glass electrode formula
PH testers：DKK-TOACORPORATION systems, IOL-30 types
The correction of electrode：With Kanto Kagaku K. K. neutral phosphate pH (6.86) titer (the 2nd kind), same public affairs
2 point calibrations for taking charge of preparing boric acid salt pH (9.18) titer (the 2nd kind) are carried out
Measurement temperature：25℃
Measured value：Electrode is impregnated in measure liquid, using the value after stabilization as measured value, the average value of 3 measure
[preparation for stabilizing hypobromous acid composition B]
Based on the International Patent Application Publication contents of No. 03/093171, prepare and stabilize hypobromous acid composition B.
Stabilize hypobromous acid composition B be containing liquid bromine, sulfamate, sodium hydroxide composition.Stabilize hypobromous acid combination
The equivalent that thing B pH is 14, bromine containing ratio is 16.1 weight %, sulfamic acid is 1.45 relative to the ratio between equivalent of bromine.
[preparation for stabilizing hypobromous acid composition C-1, C-2, C-3, C-4]
It is the composition made with following step based on the contents of Japanese Kohyo 11-506139 publications.Combination
The pH of thing is 14, bromine containing ratio is 11.3 weight %.
(1) 27.0 grams of the mixed liquor of 40 weight % aqueous sodium bromides is added in the pure water of the parts by weight shown in table 1 simultaneously
Stirring.
(2) 12 weight % liquor natrii hypochloritises 41.7g are added in the solution of (1) and are stirred.
(3) it is water-soluble to make the stabilisation being made up of 56.0g pure water, 26.0g sulfamic acid, 18.0g sodium hydroxide
Liquid.
(4) only stirred in the solution of (2) with the parts by weight shown in table 1 when adding the stabilizing solutions of (3), obtain mesh
Mark stabilizes hypobromous acid composition C-1, C-2, C-3, C-4.
[table 1]
It should be noted that for example stabilize equivalent of hypobromous acid composition C-1, the sulfamic acid equivalent relative to bromine
The ratio between calculated according to following formula.
The equivalent of sulfamic acid is relative to the ratio between equivalent of bromine=(2.6 × 0.26/97.1)/(11.3/159.8)=0.1
[hypobromite composition D preparation]
For the composition made with following step.Hypobromite composition D pH is 12, bromine containing ratio is 11.3 weights
Measure %.
(1) the mixed liquor 27.0g of 40 weight % aqueous sodium bromides is added in 31.3g pure water and is stirred.
(2) 12 weight % liquor natrii hypochloritises 41.7g are added in the solution of (1) and are stirred, obtain target hypobromite
Composition D.
＜ embodiments 1~3, comparative example 1,2 ＞
As simulated wastewater, ammonium chloride is dissolved with Xiang Moyuan cities water obtained from preparation eliminates residual chlorine with activated carbon
So that ammonium-nitrogen (NH4- N) concentration turn into 7.8mg-N/L (0.56mmol/L) the aqueous solution.The pH of the simulated wastewater of preparation is
7.2.In the simulated wastewater of preparation, addition stabilizes hypobromous acid composition A (embodiment 1-1), stabilizes hypobromous acid composition B
(embodiment 2), stabilize hypobromous acid composition C-1, C-2, C-3, C-4 (embodiment 3-1,3-2,3-3,3-4), hypobromite group
Compound D (comparative example 1) or sodium hypochlorite (comparative example 2) so that turn into 10mg/L asCl in terms of effective halogen2Or cause steady
Surely changing hypobromous acid composition A turns into 1mg/L asCl2(embodiment 1-2).While experimental liquid is stirred with digital agitator with 500rpm
Mix, side measure ammonium-nitrogen (NH4- N) concentration rheological parameters' change with time (after 10 minutes, after 30 minutes).After 30 minutes, determination test water
Total halogen concentration.Show the result in table 2.
It should be noted that total halogen concentration (effective chlorine converted score) determines according to following steps.
Effective halogen concentration is to dilute sample, (determine project with the entry water analysis meter DR/4000 of HACH companies
For " total chlorine "), value (the mg/L asCl that are determined using effective chlorine determination method (DPD (diethyl-p-phenylenediamine) method)2).Need
Illustrate, so-called effectively halogen refers to herein, the value determined using effective chlorine determination method (DPD methods).Furthermore it is possible to according to having
Cl concn is imitated, calculates effective bromine concentration (mg/L asCl of effective halogen concentration as chlorine conversion2), can be will utilize
Value obtained from the measured value of effect chlorine measurement method (DPD methods) is multiplied by 2.25 (159.8 (g/mol)/70.9 (g/mol)) is calculated
(chlorine (Cl2) molecular weight be 70.9 (g/mol), bromine (Br2) molecular weight be 159.8 (g/mol).).
Ammonium-nitrogen (NH4- N) concentration (mg/L asN) utilize Kyoritsu Chemical-Check Lab. Corp. PACK-TEST (ammoniums
State nitrogen, model WAK-NH4), determined using the colour developing principle of JIS K 0,102 42.2 indophenol blue absorption photometry.
[table 2]
In table 2, it can be seen from comparative example 2, for sodium hypochlorite, it can not decompose ammonium-nitrogen substantially.As its reason, recognize
For this is because, the ammonium-nitrogen in sodium hypochlorite and waste water reacts and generated with reference to halogen (chloramines), the decomposition of ammonium-nitrogen
Performance is greatly reduced.In addition, it can be seen from comparative example 1, also it fully can not decompose ammonium-nitrogen even if using hypobromite.Strictly according to the facts
Apply and show like that shown in example 1~3, during using stabilisation hypobromous acid composition containing sulfamic acid, can more effectively make ammonia
Property nitrogen decompose, the equivalent of sulfamic acid is bigger relative to the ratio between bromine equivalent, and the reducing effect of ammonium-nitrogen also becomes higher.Particularly
Show, the equivalent for stabilizing the sulfamic acid compound in hypobromous acid composition (is implemented relative to the ratio between equivalent of bromine for 0.50
Example 3-3) or more than 0.70 (embodiment 3-4) in the case of, the minimizing effect of ammonium-nitrogen uprises.In addition, according to embodiment 1-2 with
The comparison of comparative example 1,2 shows, stabilizes the discomposing effect of hypobromous acid composition A ammonium-nitrogens under less addition concentration
Also it is high.
＜ embodiment 1-3~1-7 ＞
As simulated wastewater, make in Xiang Moyuan cities water obtained from preparation activated carbon removes residual chlorine dissolved with ammonium chloride
Obtain ammonium-nitrogen (NH4- N) concentration turn into 7.8mg-N/L (0.56mmol/L) the aqueous solution.The pH of the simulated wastewater of preparation is
7.2.In the simulated wastewater of preparation, addition stabilizes hypobromous acid composition A (embodiment 1-3~1-7) and caused with effective halogen
Meter turns into 15mg/L asCl2(0.21mmol/L) (embodiment 1-3), 40mg/L asCl2(0.56mmol/L) (embodiment 1-4),
61mg/L asCl2(0.87mmol/L) (embodiment 1-5), 79mg/L asCl2(1.11mmol/L) (embodiment 1-6), 99mg/L
asCl2(1.40mmol/L) (embodiment 1-7).While experimental liquid is stirred with digital agitator with 500rpm, side measure ammonium-nitrogen
(NH4- N) concentration rheological parameters' change with time (after 10 minutes, after 30 minutes).After 30 minutes, total halogen concentration of determination test water.Will knot
Fruit is shown in table 3.It should be noted that total halogen concentration (effective chlorine converted score), ammonium-nitrogen (NH4- N) concentration (mg/L asN)
Manner described above determines.
Show in table 3, the molar concentration of effective halogen of the effective chlorine density conversion in the simulated wastewater of before processing is (stable
Change the addition molar concentration of hypobromous acid composition) relative to ammonium-nitrogen (NH4- N) the ratio between molar concentration (0.56mmol/L) become
Must be bigger, the minimizing effect of ammonium-nitrogen also becomes higher.Particularly show, the effective chlorine density in simulated wastewater converts effective
The molar concentration (the addition molar concentration for stabilizing hypobromous acid composition) of halogen is relative to ammonium-nitrogen (NH4- N) molar concentration
The ratio between be more than 1.6 (embodiment 1-5) in the case of, ammonium-nitrogen can be made substantially completely to decompose.
[table 3]
The ＞ of ＜ embodiments 4
Using as sewage water quality, containing ammonium-nitrogen described in table 4, implement to stabilize the ammonia of hypobromous acid composition
The evaluation test of property nitrogen decomposability and antiseptic property.In 300mL beakers, addition medicament (stabilizes hypobromous acid composition A)
So that turn into 5mg/L asCl in terms of effective halogen2, it is stirred using digital agitator with 250rpm.3 points after addition medicament
Zhong Hou, the treated water of ormal weight is gathered, in order to determine ammonium-nitrogen (NH4- N) concentration, and effective chlorine is inactivated, add sulphur
After sodium thiosulfate, the measure of coli-group number is carried out using Petrifilm CC plates.
[table 4]
| Analysis project | Measured value (before medicament addition) | Measured value (after medicament adds 3 minutes) |
| NH4- N concentration [mg/L] | 15 | 5 |
| Coli-group number [individual/mL] | 100,000 | 43 |
Confirmed according to table 4, stabilize hypobromous acid composition even for sewage comprising more ammonium-nitrogen etc., also play
The minimizing effect of coli-group number, and play the effect for decomposing ammonium-nitrogen.
Claims (14)
- A kind of 1. processing method of waste water containing ammonium-nitrogen, it is characterised in thatMake bromine system oxidant or bromine compounds and chlorine system oxidant reactant andSulfamic acid compoundIt is present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen.
- A kind of 2. processing method of waste water containing ammonium-nitrogen, it is characterised in thatMake bromine system oxidant or bromine compounds and chlorine system oxidant reactant, withSulfamic acid compoundMixture or reaction productIt is present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen.
- A kind of 3. processing method of waste water containing ammonium-nitrogen, it is characterised in thatThe mixture of bromine and sulfamic acid compound is set to be present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen；OrThe reaction product of bromine and sulfamic acid compound is set to be present in the waste water containing ammonium-nitrogen containing ammonium-nitrogen.
- 4. the processing method of the waste water according to claim 1 containing ammonium-nitrogen, it is characterised in thatMake the reactant of bromine system oxidant or the bromine compounds and chlorine system oxidant and the sulfamic acid compound It is present in the waste water containing ammonium-nitrogen, the processing water then further reduced with reverse osmosis membrane to ammonium-nitrogen is handled.
- 5. the processing method of the waste water according to claim 2 containing ammonium-nitrogen, it is characterised in thatMake the reactant of bromine system oxidant or the bromine compounds and chlorine system oxidant and the sulfamic acid chemical combination The mixture or reaction product of thing are present in the waste water containing ammonium-nitrogen, and then further ammonium-nitrogen is reduced with reverse osmosis membrane Processing water handled.
- 6. the processing method of the waste water according to claim 3 containing ammonium-nitrogen, it is characterised in thatThe mixture of the bromine and sulfamic acid compound is set to be present in rear in the waste water containing ammonium-nitrogen or make the bromine and ammonia After the reaction product of base sulfoacid compound is present in the waste water containing ammonium-nitrogen, further ammonium-nitrogen is reduced with reverse osmosis membrane Processing water handled.
- 7. according to the processing method of the waste water according to any one of claims 1 to 6 containing ammonium-nitrogen, it is characterised in thatThe equivalent of sulfamic acid compound is relative to the scope that the ratio between equivalent of bromine is 0.5~1.5.
- 8. according to the processing method of the waste water according to any one of claims 1 to 7 containing ammonium-nitrogen, it is characterised in thatIn the waste water containing ammonium-nitrogen effective chlorine density conversion effective halogen molar concentration relative to ammonium-nitrogen mole The ratio between concentration is more than 1.6.
- 9. according to the processing method of the waste water according to any one of claims 1 to 8 containing ammonium-nitrogen, it is characterised in thatThe concentration of ammonium-nitrogen in the waste water containing ammonium-nitrogen is more than 5mg/L.
- 10. a kind of ammonium-nitrogen distintegrant, it is characterised in that it is the ammonium-nitrogen for decomposing the ammonium-nitrogen in waste water containing ammonium-nitrogen Distintegrant,Comprising：The reactant of bromine system oxidant or bromine compounds and chlorine system oxidant andSulfamic acid compound.
- 11. a kind of ammonium-nitrogen distintegrant, it is characterised in that it is the ammonium-nitrogen for decomposing the ammonium-nitrogen in waste water containing ammonium-nitrogen Distintegrant,Comprising：The reactant of bromine system oxidant or bromine compounds and chlorine system oxidant, withSulfamic acid compoundMixture or reaction product.
- 12. a kind of ammonium-nitrogen distintegrant, it is characterised in that it is the ammonium-nitrogen for decomposing the ammonium-nitrogen in waste water containing ammonium-nitrogen Distintegrant,Comprising：The mixture or bromine of bromine and sulfamic acid compound and the reaction product of sulfamic acid compound.
- 13. the ammonium-nitrogen distintegrant according to any one of claim 10~12, it is characterised in thatThe equivalent of sulfamic acid compound is relative to the scope that the ratio between equivalent of bromine is 0.5~1.5.
- 14. the ammonium-nitrogen distintegrant according to any one of claim 10~13, it is characterised in thatThe concentration of ammonium-nitrogen in the waste water containing ammonium-nitrogen is more than 5mg/L.
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| JP7050414B2 (en) * | 2016-10-25 | 2022-04-08 | オルガノ株式会社 | Water treatment method using reverse osmosis membrane |
| JP7013141B2 (en) * | 2017-04-27 | 2022-02-15 | オルガノ株式会社 | Water treatment method using reverse osmosis membrane |
| JP6970698B2 (en) * | 2017-08-10 | 2021-11-24 | 水ｉｎｇ株式会社 | Disinfection method for ammonia-containing nitrogen-containing wastewater |
| JP6513151B2 (en) * | 2017-08-10 | 2019-05-15 | 水ｉｎｇ株式会社 | Method and disinfectant for disinfecting ammonia nitrogen containing wastewater |
| JP6490761B2 (en) * | 2017-08-10 | 2019-03-27 | 水ｉｎｇ株式会社 | Disinfection method of wastewater containing ammonia nitrogen |
| JP6996955B2 (en) | 2017-11-30 | 2022-01-17 | オルガノ株式会社 | Method for measuring the concentration of stabilized hypobromous acid composition |
| KR102462490B1 (en) * | 2021-02-22 | 2022-11-03 | (주) 테크윈 | Methods for treatment of refractory wastewater to simultaneously remove organic pollutants and ammonia nitrogen |
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| WO2016175006A1 (en) | 2016-11-03 |
| KR20170139676A (en) | 2017-12-19 |
| TW201700409A (en) | 2017-01-01 |
| JP6412639B2 (en) | 2018-10-24 |
| JPWO2016175006A1 (en) | 2017-12-21 |
| SG11201708538VA (en) | 2017-11-29 |
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| CN107531523B (en) | 2020-12-18 |
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