CN103553204B - Method for treating water by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide - Google Patents
Method for treating water by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide Download PDFInfo
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- CN103553204B CN103553204B CN201310589568.7A CN201310589568A CN103553204B CN 103553204 B CN103553204 B CN 103553204B CN 201310589568 A CN201310589568 A CN 201310589568A CN 103553204 B CN103553204 B CN 103553204B
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Abstract
The invention provides a method for treating water by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide and relates to a water treatment method. The water treatment method is used for solving the problems of a photosensitive method for generating singlet oxygen that a light source needs to be additionally added, secondary pollution is caused, and the utilization rate of singlet oxygen generated by adopting a chemical method is low. The method for treating water comprises the following steps: adding the inorganic solid peroxide and the peroxymonosulfate to water, reacting and stirring so as to complete the water treatment, wherein the water to be treated is source water and wastewater. According to the water treatment method, after the peroxide is dissolved in water, hydrogen peroxide slowly released reacts with the peroxymonosulfate rapidly to continuously generate the low-concentration high-activity singlet oxygen which can be efficiently utilized by pollutants, the self decomposition of the singlet oxygen is reduced, and the utilization rate of the singlet oxygen is increased. The method has the advantages that the pollution removal efficiency is high, no poisonous or harmful byproducts are generated, the additional equipment is not needed; and as solid reagents, the inorganic solid peroxide and the peroxymonosulfate are convenient to transport and store and are suitable for emergency treatment.
Description
Technical field
The present invention relates to water treatment method, be specifically related to a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen.
Background technology
Singlet oxygen (
1o
2) be a kind of molecular oxygen being in excited state, with superoxide radical (O
2 -), hydroxyl radical free radical (OH), potentiometric titrations (SO
4 -) isoreactivity oxygenate kind is similar, chemical property is active, unstable, be widespread in nature, one of the longest active oxygens related in field such as chemistry, environment, medical science, have that oxidation capacity is strong, reactive behavior is high, the survival time is short, do not produce the features such as poisonous and harmful by product after oxidation, belong to green, environmentally friendly oxygenant.
At present, the method producing singlet oxygen mainly contains photosensitization method and chemical process.Photosensitization method produces singlet oxygen and relates to a photoexcitation process, a kind of photosensitizers (rose-red, eosin, methylene blue, fluorescent yellow, chlorophyll and haematoporphyrin etc.), under rayed condition, ground state oxygen in the photosensitizers of excited state and system (
3o
2) effect, and then obtain singlet oxygen (
1o
2).Utilize photosensitization method can produce singlet oxygen fast, but the introducing of the restriction (needing stable light source) and photosensitizers that there is light can produce the problem of secondary pollution.Chemical process produces singlet oxygen and is realized by generation chemical reaction, and the most classical method is by hydrogen peroxide (H
2o
2) and chlorine (Cl
2) the aqueous solution or hypochlorite solution mixing can produce singlet oxygen.This formation speed utilizing chemical process to produce singlet oxygen is fast, and its second order rate constant is about 10
4m
-1s
-1, namely instantaneous generation is large, and self-decomposition speed is fast, and the survival time is short, and organism utilization rate is low; Chemical reagent is liquid hydrogen peroxide and hypochlorite solution or chlorine, and shipping storage is inconvenient, complex operation and there is the problem of potential safety hazard.
Summary of the invention
The object of this invention is to provide a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen, address the problem: producing singlet oxygen in (1) photosensitization method needs additional light source, be difficult to large-scale application, and the introducing of photosensitizers can produce secondary pollution; (2) chemical reaction method (H
2o
2-ClO
-) in large, the easily self-decomposition of the singlet oxygen amount of instantaneous generation, be difficult to contaminated thing efficiency utilization, and the hydrogen peroxide of liquid state and hypochlorite solution or chlorine, transport, store inconvenient, complicated operation and there is potential safety hazard.
Of the present inventionly a kind ofly utilize inoganic solids peroxide-induced peroxy-monosulfate to produce the water treatment method of singlet oxygen to be realized by following steps: be 1:(0.5 ~ 5 by inoganic solids superoxide and peroxy-monosulfate according to mass ratio) ratio join in pending water, stir, controlling the concentration of peroxy-monosulfate in pending water is 0.3 ~ 300mg/L, hydraulic retention reaction 5 ~ 60min, namely completes the water treatment utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen; Wherein, described pending water is source water and sewage.
A kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen of the present invention, can be 1:(0.5 ~ 5 according to mass ratio by inoganic solids superoxide, peroxy-monosulfate) make powder reagent mixing and add or individually add, be dry type and add method; Also inoganic solids superoxide, peroxy-monosulfate can be made solution respectively, add separately, be wet type and add method.
A kind of inoganic solids peroxide-induced peroxy-monosulfate that utilizes of the present invention produces in the water treatment method of singlet oxygen, inoganic solids superoxide (Na
2o
2, CaO
2, MgO
2, BaO
2, Na
2cO
4, K
2cO
4) water-soluble after can slowly release hydrogen peroxide (H
2o
2), see reaction formula (1) and (2), this hydrogen peroxide produced at water situ by inoganic solids superoxide, can rapidly and peroxy-monosulfate (HSO
5 -) reaction generation high reactivity singlet oxygen (
1o
2), see reaction formula (3), the strong oxidizing property singlet oxygen that lower concentration continues to produce can contaminated thing efficiency utilization, and reduce its self-decomposition, improve its utilization ratio, depollution is effective, and does not produce poisonous and harmful by product.
O
2 2-+2H
2O→H
2O
2+2OH
-(1)
CO
4 2-+H
2O→H
2O
2+CO
3 2-(2)
H
2O
2+HSO
5 -→
1O
2+SO
4 2-+H
2O+H
+(3)
A kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen of the present invention, tool has the following advantages: green emerging oxygenant peroxy-monosulfate compares stable chemical nature with the hydrogen peroxide of liquid state with hypochlorite solution or chlorine as pulverulent solids with inoganic solids superoxide, shipping storage is convenient, moderate, business is easy to get, operation is simple, and not needing additionally increases operational outfit (as O
3, UV needs to provide reaction unit and equipment), affect little (as Fenton reagent to affect larger by pH) by water condition, the environmentally friendly singlet oxygen with strong oxidizing property produced, depollution efficiency is high, poisonous and harmful by product is not produced in reaction process, large-scale application can be carried out in water factory, add emergency processing when being more suitable for water pollutions outburst as solid powder medicament.
Accompanying drawing explanation
Fig. 1 is the clearance graphic representation of endocrine disrupter-dihydroxyphenyl propane in source water in embodiment 21.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: present embodiment is a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen, it is realized by following steps: be 1:(0.5 ~ 5 by inoganic solids superoxide and peroxy-monosulfate according to mass ratio) ratio join in pending water, stir, controlling the concentration of peroxy-monosulfate in pending water is 0.3 ~ 300mg/L, hydraulic retention reaction 5 ~ 60min, namely completes the water treatment utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen; Wherein, described pending water is source water and sewage.
Inoganic solids superoxide in present embodiment and peroxy-monosulfate are separately deposited before use.
The superoxide of inoganic solids described in present embodiment and peroxy-monosulfate can be 1:(0.5 ~ 5 according to mass ratio) make powder reagent mixing add or individually add, be dry type and add method; Also inoganic solids superoxide and peroxy-monosulfate can be made solution respectively, add separately, be wet type and add method.
A kind of inoganic solids peroxide-induced peroxy-monosulfate that utilizes of present embodiment produces in the water treatment method of singlet oxygen, can slowly release hydrogen peroxide (H after inoganic solids superoxide is water-soluble
2o
2), this hydrogen peroxide produced at water situ by inoganic solids superoxide, can rapidly and peroxy-monosulfate (HSO
5 -) reaction generation high reactivity singlet oxygen (
1o
2), the strong oxidizing property singlet oxygen that lower concentration continues to produce can contaminated thing efficiency utilization, and reduce its self-decomposition, depollution is effective, and does not produce poisonous and harmful by product.
A kind of advantage utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce the water treatment method of singlet oxygen of present embodiment is: green emerging oxygenant peroxy-monosulfate compares stable chemical nature with the hydrogen peroxide of liquid state with hypochlorite solution or chlorine as pulverulent solids with inoganic solids superoxide, shipping storage is convenient, moderate, business is easy to get, operation is simple, do not need additionally to increase operational outfit, affect little by water condition, the strong oxidizing property singlet oxygen produced, depollution efficiency is high, poisonous and harmful by product is not produced in reaction process, large-scale application can be carried out in water factory, be more suitable for emergency processing.
Embodiment two: present embodiment and embodiment one unlike: described inoganic solids superoxide is sodium peroxide (Na
2o
2), calcium peroxide (CaO
2), Magnesium peroxide (MgO
2), barium peroxide (BaO
2), SPC-D (Na
2cO
4), antihypo (K
2cO
4) in one or more mixtures be mixed by any ratio.Other parameter is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: peroxy-monosulfate is permonosulphuric acid sodium (NaHSO
5), permonosulphuric acid potassium (KHSO
5), permonosulphuric acid ammonium (NH
4hSO
5), permonosulphuric acid calcium (Ca (HSO
5)
2), permonosulphuric acid magnesium (Mg (HSO
5)
2) in one or more mixtures be mixed by any ratio.Other parameter is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: permonosulphuric acid salt concn is 0.5 ~ 250mg/L.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: permonosulphuric acid salt concn is 1 ~ 200mg/L.Other step and parameter identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: permonosulphuric acid salt concn is 1.5 ~ 150mg/L.Other step and parameter identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six unlike: permonosulphuric acid salt concn is 2 ~ 100mg/L.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven unlike: permonosulphuric acid salt concn is 5 ~ 75mg/L.Other step and parameter identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight unlike: permonosulphuric acid salt concn is 10 ~ 50mg/L.Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine unlike: permonosulphuric acid salt concn is 15 ~ 30mg/L.Other step and parameter identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten unlike: permonosulphuric acid salt concn is 20mg/L.Other step and parameter identical with one of embodiment one to ten.
Embodiment 12: one of present embodiment and embodiment one to ten one unlike: the mass ratio of inoganic solids superoxide and peroxy-monosulfate is 1:(0.6 ~ 4).Other parameter is identical with one of embodiment one by one to ten one.
Embodiment 13: one of present embodiment and embodiment one to ten two unlike: the mass ratio of inoganic solids superoxide and peroxy-monosulfate is 1:(0.7 ~ 3).Other parameter is identical with one of embodiment one to ten two.
Embodiment 14: one of present embodiment and embodiment one to ten three unlike: the mass ratio of inoganic solids superoxide and peroxy-monosulfate is 1:(0.8 ~ 2).Other parameter is identical with one of embodiment one to ten three.
Embodiment 15: one of present embodiment and embodiment one to ten four unlike: the mass ratio of inoganic solids superoxide and peroxy-monosulfate is 1:(0.9 ~ 1.5).Other parameter is identical with one of embodiment one to ten four.
Embodiment 16: one of present embodiment and embodiment one to ten five unlike: the mass ratio of inoganic solids superoxide and peroxy-monosulfate is 1:1.Other parameter is identical with one of embodiment one to ten five.
Embodiment 17: one of present embodiment and embodiment one to ten six unlike: controlling the reaction times is 10 ~ 50min.Other step and parameter identical with one of embodiment one to ten six.
Embodiment 18: one of present embodiment and embodiment one to ten seven unlike: controlling the reaction times is 20 ~ 40min.Other step and parameter identical with one of embodiment one to ten seven.
Embodiment 19: one of present embodiment and embodiment one to ten eight unlike: controlling the reaction times is 30min.Other step and parameter identical with one of embodiment one to ten eight.
Embodiment 20: present embodiment is a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen, it is realized by following steps: be that 1:1 joins in treatment sewage by inoganic solids superoxide and peroxy-monosulfate according to mass ratio, stir, controlling the concentration of peroxy-monosulfate in treatment sewage is 100mg/L, the hydraulic retention reaction times is 30min, namely completes the water treatment utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen.
The dosing method of the superoxide of inoganic solids described in present embodiment and peroxy-monosulfate adds for making mixed powder dosage form according to mass ratio 1:1.Inoganic solids superoxide in present embodiment is any SPC-D of ratio and the mixture of antihypo; Peroxy-monosulfate is the permonosulphuric acid potassium of any ratio and the mixture of permonosulphuric acid sodium.
A kind of inoganic solids peroxide-induced peroxy-monosulfate that utilizes of present embodiment produces in the water treatment method of singlet oxygen, after oxide treatment, the clearance of the pollutent (chlorophenol, bromine phenol, iodine phenol, nitrophenol, aniline, atrazine, 2,4-D) in sewage reaches more than 90%.
Embodiment 21: present embodiment is a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen, it is realized by following steps: be that 1:2 joins in pending source water by inoganic solids calcium peroxide and permonosulphuric acid potassium according to mass ratio, stir, controlling the concentration of peroxy-monosulfate in treatment sewage is 20mg/L, the hydraulic retention reaction times is 30min, namely completes the water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen.
The dosing method of the calcium peroxide of inoganic solids described in present embodiment and permonosulphuric acid potassium is for add with powder reagent form respectively according to mass ratio 1:2.
A kind of inoganic solids peroxide-induced peroxy-monosulfate that utilizes of present embodiment produces in the water treatment method of singlet oxygen, endocrine disrupter-dihydroxyphenyl propane containing 0.1mg/L in source water, after oxide treatment, the clearance of dihydroxyphenyl propane reaches more than 99%, as shown in Figure 1.
Embodiment 22: present embodiment is a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen, it is realized by following steps: be that 1:2.5 joins in pending source water by inoganic solids calcium peroxide and permonosulphuric acid sodium according to mass ratio, stir, the hydraulic retention reaction times is 150mg/L, the hydraulic retention reaction times is 20min, namely completes the water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen.
The dosing method of the powder of solid bleach described in present embodiment and inoganic solids superoxide adds for being mixed with solution form respectively according to mass ratio 1:2.5.
A kind of inoganic solids peroxide-induced peroxy-monosulfate that utilizes of present embodiment produces in the water treatment method of singlet oxygen, after oxide treatment, the clearance of the pollutent (tsiklomitsin, penicillin, cephalo, Carbamzepine, triclosan, oestrone, nonyl phenol) in sewage reaches more than 90%.
Claims (8)
1. the water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen, the water treatment method that it is characterized in that utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen is realized by following steps: be 1:(0.5 ~ 5 by inoganic solids superoxide and peroxy-monosulfate according to mass ratio) ratio join in pending water, stir, controlling the concentration of peroxy-monosulfate in pending water is 0.3 ~ 300mg/L, hydraulic retention reaction 5 ~ 60min, namely the water treatment utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen is completed, wherein, described pending water is source water and sewage, described inoganic solids superoxide is one or more in sodium peroxide, Magnesium peroxide, barium peroxide, SPC-D, antihypo mixtures of being mixed by any ratio, described peroxy-monosulfate is one or more mixtures be mixed by any ratio in permonosulphuric acid sodium, permonosulphuric acid potassium, permonosulphuric acid ammonium, permonosulphuric acid calcium, permonosulphuric acid magnesium.
2. a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen according to claim 1, is characterized in that the mass ratio of described inoganic solids superoxide and peroxy-monosulfate is 1:(0.6 ~ 4).
3. a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen according to claim 2, is characterized in that the mass ratio of described inoganic solids superoxide and peroxy-monosulfate is 1:(0.7 ~ 3).
4. a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen according to claim 3, is characterized in that the mass ratio of described inoganic solids superoxide and peroxy-monosulfate is 1:(0.8 ~ 2).
5. a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen according to claim 4, is characterized in that the mass ratio of described inoganic solids superoxide and peroxy-monosulfate is 1:(0.9 ~ 1.5).
6. a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen according to claim 5, is characterized in that the mass ratio of described inoganic solids superoxide and peroxy-monosulfate is 1:1.
7. a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen according to claim 1, is characterized in that described peroxy-monosulfate concentration in pending water is 5 ~ 200mg/L.
8. a kind of water treatment method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen according to claim 7, is characterized in that described peroxy-monosulfate concentration in pending water is 20 ~ 100mg/L.
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| CN104787828B (en) * | 2015-05-08 | 2017-05-03 | 哈尔滨工业大学 | Water treatment method for removing pollution through singlet oxygen dissolved air flotation |
| CN105600910B (en) * | 2015-11-16 | 2018-01-05 | 哈尔滨理工大学 | A kind of method for treating water for being catalyzed peroxide and producing singlet oxygen depollution |
| CN105347458B (en) * | 2015-11-16 | 2017-08-29 | 哈尔滨理工大学 | A kind of method that utilization singlet oxygen handles reverse osmosis concentrated liquid |
| CN105236550B (en) * | 2015-11-16 | 2018-01-05 | 哈尔滨理工大学 | A kind of method that water ballast is handled using singlet oxygen |
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