CN103551044B - Method for cleaning polluted membrane by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide - Google Patents
Method for cleaning polluted membrane by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide Download PDFInfo
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- CN103551044B CN103551044B CN201310589567.2A CN201310589567A CN103551044B CN 103551044 B CN103551044 B CN 103551044B CN 201310589567 A CN201310589567 A CN 201310589567A CN 103551044 B CN103551044 B CN 103551044B
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Abstract
The invention provides a method for cleaning polluted membrane by using singlet oxygen produced from peroxymonosulfate under induction of inorganic solid peroxide and relates to a membrane cleaning method. The method for cleaning a polluted membrane comprises the following steps: adding the inorganic solid peroxide and the peroxymonosulfate in a tank containing a polluted membrane module, stirring, soaking, and finally rinsing. According to the method, after the peroxide is dissolved in water, hydrogen peroxide slowly released reacts with the peroxymonosulfate rapidly to generate the high-activity singlet oxygen which directly acts on biological cells polluting the membrane to rapidly destroy enzymatic structures, thus achieving a good membrane cleaning effect. As environmentally-friendly reagents, the inorganic solid peroxide and the peroxymonosulfate do not generate poisonous and harmful byproducts in the cleaning process, and waste liquid can be directly discharged after the membrane is cleaned; and as solid reagents, the inorganic solid peroxide and the peroxymonosulfate can be directly added for use without need of additional equipment. The method has the advantages that the operation is simple and practicable, and the reagents are convenient to transport and store, low in cost and easy to obtain.
Description
Technical field
The present invention relates to a kind of Membrane cleaning method, be specifically related to a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane.
Background technology
Along with the requirement of the high isolation and purification to material, membrane filtration technique arises at the historic moment, become a newborn high score from, concentrated, purify and purification techniques.Because it is without phase change, the advantage such as energy consumption is low, system is clean, be widely used in the fields such as medicine, food, chemical industry and water treatment, obtaining fast development in countries in the world.But, along with the growth of film running time, physics, chemistry and the mechanism by existing with membrane material such as the inorganic matter in processed material liquid, suspension, organic matter and microorganism, adsorb or be deposited in film surface or fenestra, membrane aperture is diminished or blocks, form fouling membrane, cause flux depression, cause the separating effect of film to be deteriorated.
Membrane cleaning object is by adopting rational cleaning method to clean contaminated film and regenerating, and destroys the Adsorption of solute layer on film surface, removes the impurity in fenestra road, make film return to original flux as far as possible.Membrane cleaning method can be divided into physical cleaning method and chemical cleaning method.Physical cleaning comprises waterpower cleaning, gas pulses cleaning, Ultrasonic Cleaning etc., and can remove the pollutant on film surface preferably, but can not remove the pollutant in fenestra road, cleaning performance is not good.Chemical cleaning is by using chemical agent to reach loosening, dissolve dirt, oxidation of organic compounds, inactivating microbial remove the effect of fouling membrane.Conventional cleaning method has pickling, alkali cleaning, alcohol wash, oxidant and bactericide (as ozone, hypochlorous acid, potassium permanganate etc.) by oxidation reaction cleaning fouling membrane etc.
Singlet oxygen (
1o
2) be a kind of molecular oxygen being in excitation 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 oxidability is strong, reactivity is high, the time-to-live is short, do not produce the features such as poisonous and harmful accessory substance after oxidation, belong to green, environmentally friendly oxidant.
At present, the method producing singlet oxygen mainly contains photoactivate method and chemical method.Photoactivate method produces singlet oxygen and relates to a photoexcitation process, a kind of sensitising agent (rose-red, eosin, methylene blue, fluorescein, chlorophyll and haematoporphyrin etc.), under light illuminate condition, ground state oxygen in the sensitising agent of excitation state and system (
3o
2) effect, and then obtain singlet oxygen (
1o
2).Utilize photoactivate method can produce singlet oxygen fast, but the introducing of the restriction (needing stable light source) and sensitising agent that there is light can produce the problem of secondary pollution.Chemical method 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 method to produce singlet oxygen is fast, and its second order reaction speed constant is about 10
4m
-1s
-1, namely instantaneous generation is large, and selfdecomposition speed is fast, and the time-to-live 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 method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane, to solve above-mentioned Problems existing.
A kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane of the present invention is realized by following steps: a, contaminated membrane module to be cleaned is put into the pond that running water is housed; B, be 1:(0.5 ~ 5 by inoganic solids peroxide and peroxy-monosulfate according to mass ratio) ratio join in the pond of step one, stir, controlling permonosulphuric acid salinity is 50 ~ 1000mg/L, soaks 10 ~ 180min; C, the membrane module after soaking is put into another pond that running water is housed and carried out rinsing, namely complete and utilize inoganic solids peroxide-induced persulfate to produce singlet oxygen cleaning fouling membrane.
A kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane of the present invention, can be 1:(0.5 ~ 5 according to mass ratio by inoganic solids peroxide, peroxy-monosulfate) make powder reagent mixing and add or individually add, be dry type and add method; Also inoganic solids peroxide, 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 method for singlet oxygen cleaning fouling membrane, inoganic solids peroxide (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 equation (1) and (2), this hydrogen peroxide produced at water situ by inoganic solids peroxide, can rapidly and peroxy-monosulfate (HSO
5 -) reaction generation high activity singlet oxygen (
1o
2), see reaction equation (3), the singlet oxygen of generation has oxidability by force, and can directly act on the biological cell of fouling membrane, rapid destructive enzyme structure, do not produce poisonous and harmful accessory substance, Membrane cleaning is effective.
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 method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane of the present invention, tool has the following advantages: green emerging oxidant peroxy-monosulfate compares stable chemical nature with the hydrogen peroxide of liquid state with hypochlorite solution or chlorine as pulverulent solids with inoganic solids peroxide, shipping storage is convenient, moderate, business is easy to get, operation is simple, and not needing additionally increases operational outfit; The high activity singlet oxygen produced due to its oxidability strong, can snap action in the biological cell of fouling membrane, rapid destructive enzyme structure, Membrane cleaning is effective; As environmental friendliness reagent, poisonous and harmful accessory substance is not produced in cleaning process, after cleaning, waste liquid can directly discharge without the need to process, avoids biological pollution in conventional Membrane cleaning method and does not wash clean clearly, easily produces poisonous and harmful accessory substance, produces the problem that waste liquid needs reprocessing.
Accompanying drawing explanation
Fig. 1 is the change of membrane flux before and after Membrane cleaning in detailed description of the invention 21, and is the membrane flux before fouling membrane, and ■ is the membrane flux after fouling membrane,
for the membrane flux after cleaning fouling membrane.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: present embodiment is a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane, and it is realized by following steps: a, contaminated membrane module to be cleaned is put into the pond that running water is housed; B, be 1:(0.5 ~ 5 by inoganic solids peroxide and peroxy-monosulfate according to mass ratio) ratio join in the pond of step one, stir, controlling permonosulphuric acid salinity is 50 ~ 1000mg/L, soaks 10 ~ 180min; C, step b is soaked after membrane module put into another pond that running water is housed and carry out rinsing, namely complete and utilize inoganic solids peroxide-induced persulfate to produce singlet oxygen cleaning fouling membrane.
The membrane material of the contaminated membrane module described in present embodiment is Kynoar (PVDF), polyether sulfone (PES), polyethylene (PE) or polyvinyl chloride (PVC).
Inoganic solids peroxide in present embodiment and peroxy-monosulfate are separately deposited before use.
Inoganic solids peroxide 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 peroxide 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 method for singlet oxygen cleaning fouling membrane, can slowly release hydrogen peroxide (H after inoganic solids peroxide is water-soluble
2o
2), can rapidly and peroxy-monosulfate (HSO
5 -) reaction generation high activity singlet oxygen (
1o
2), the singlet oxygen of generation has oxidability by force, and can directly act on the biological cell of fouling membrane, rapid destructive enzyme structure, do not produce poisonous and harmful accessory substance, Membrane cleaning is effective.
A kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane of present embodiment, tool has the following advantages: green emerging oxidant peroxy-monosulfate compares stable chemical nature with the hydrogen peroxide of liquid state with hypochlorite solution or chlorine as pulverulent solids with inoganic solids peroxide, shipping storage is convenient, moderate, business is easy to get, operation is simple, and not needing additionally increases operational outfit; The high activity singlet oxygen produced due to its oxidability strong, can snap action in the biological cell of fouling membrane, rapid destructive enzyme structure, Membrane cleaning is effective; As environmental friendliness reagent, poisonous and harmful accessory substance is not produced in cleaning process, after cleaning, waste liquid can directly discharge without the need to process, avoids biological pollution in conventional Membrane cleaning method and does not wash clean clearly, easily produces poisonous and harmful accessory substance, produces the problem that waste liquid needs reprocessing.
Detailed description of the invention two: present embodiment and detailed description of the invention one unlike: described inoganic solids peroxide is sodium peroxide (Na
2o
2), calper calcium peroxide (CaO
2), peromag (MgO
2), barium peroxide (BaO
2), SODIUM PERCARBONATE (Na
2cO
4), potassium percarbonate (K
2cO
4) in the mixture of one or more.Other parameter is identical with detailed description of the invention one.
When in present embodiment, inoganic solids peroxide is wherein several mixture, with arbitrarily than mixing.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two unlike peroxy-monosulfate are: 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 detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: permonosulphuric acid salinity is 60 ~ 900mg/L.Other step and parameter identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: permonosulphuric acid salinity is 70 ~ 800mg/L.Other step and parameter identical with one of detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: permonosulphuric acid salinity is 80 ~ 700mg/L.Other step and parameter identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six unlike: permonosulphuric acid salinity is 90 ~ 600mg/L.Other step and parameter identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven unlike: permonosulphuric acid salinity is 100 ~ 500mg/L.Other step and parameter identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight unlike: permonosulphuric acid salinity is 120 ~ 400mg/L.Other step and parameter identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine unlike: permonosulphuric acid salinity is 150 ~ 300mg/L.Other step and parameter identical with one of detailed description of the invention one to nine.
Detailed description of the invention 11: one of present embodiment and detailed description of the invention one to ten unlike: permonosulphuric acid salinity is 200mg/L.Other step and parameter identical with one of detailed description of the invention one to ten.
Detailed description of the invention 12: one of present embodiment and detailed description of the invention one to ten one unlike: the mass ratio of inoganic solids peroxide and peroxy-monosulfate is 1:(0.6 ~ 4).Other parameter is identical with one of detailed description of the invention one to ten one.
Detailed description of the invention 13: one of present embodiment and detailed description of the invention one to ten two unlike: the mass ratio of inoganic solids peroxide and peroxy-monosulfate is 1:(0.7 ~ 3).Other parameter is identical with one of detailed description of the invention one to ten two.
Detailed description of the invention 14: one of present embodiment and detailed description of the invention one to ten three unlike: the mass ratio of inoganic solids peroxide and peroxy-monosulfate is 1:(0.8 ~ 2).Other parameter is identical with one of detailed description of the invention one to ten three.
Detailed description of the invention 15: one of present embodiment and detailed description of the invention one to ten four unlike: the mass ratio of inoganic solids peroxide and peroxy-monosulfate is 1:(0.9 ~ 1.5).Other parameter is identical with one of detailed description of the invention one to ten four.
Detailed description of the invention 16: one of present embodiment and detailed description of the invention one to ten five unlike: the mass ratio of inoganic solids peroxide and peroxy-monosulfate is 1:1.Other parameter is identical with one of detailed description of the invention one to ten five.
Detailed description of the invention 17: one of present embodiment and detailed description of the invention one to ten six unlike: soak time is 20 ~ 120min.Other step and parameter identical with one of detailed description of the invention one to ten six.
Detailed description of the invention 18: one of present embodiment and detailed description of the invention one to ten seven unlike: soak time is 30 ~ 90min.Other step and parameter identical with one of detailed description of the invention one to ten seven.
Detailed description of the invention 19: one of present embodiment and detailed description of the invention one to ten eight unlike: soak time is 60min.Other step and parameter identical with one of detailed description of the invention one to ten eight.
Detailed description of the invention 20: present embodiment is a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane, and it is realized by following steps: a, contaminated membrane module to be cleaned is put into the pond that running water is housed; B, be that 1:1 joins in pond by inoganic solids peroxide and peroxy-monosulfate according to mass ratio, stir, controlling permonosulphuric acid salinity is 500mg/L, and soak time is 60min; C, soaked membrane module is put into another pond that running water is housed carry out rinsing, namely complete and utilize inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane.
The membrane material of the contaminated membrane module described in present embodiment is Kynoar (PVDF), polyether sulfone (PES), polyethylene (PE) or polyvinyl chloride (PVC).
After the singlet oxygen cleaning fouling membrane of present embodiment through producing, membrane flux recovers more than 90%.
The dosing method of the peroxide 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 peroxide in present embodiment is any sodium peroxide of ratio and the mixture of calper calcium peroxide; Peroxy-monosulfate is the permonosulphuric acid potassium of any ratio and the mixture of permonosulphuric acid sodium.
Detailed description of the invention 21: present embodiment is a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane, and it is realized by following steps: a, contaminated membrane module to be cleaned is put into the pond that running water is housed; B, be that 1:2 joins in pond by inoganic solids calper calcium peroxide and permonosulphuric acid potassium according to mass ratio, stir, controlling permonosulphuric acid salinity is 300mg/L, and soak time is 60min; C, soaked membrane module is put into another pond that running water is housed carry out rinsing, namely complete and utilize inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane.
The membrane material of present embodiment membrane module is Kynoar (PVDF), polyether sulfone (PES), polyethylene (PE) and polyvinyl chloride (PVC).
Present embodiment membrane flux recovery rate is shown in Fig. 1, as shown in Figure 1, after singlet oxygen cleaning fouling membrane through producing, the membrane flux recovery rate of Kynoar (PVDF), polyether sulfone (PES), polyethylene (PE) and polyvinyl chloride (PVC) all reaches more than 90%.
The dosing method of the calper 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.
Detailed description of the invention 22: present embodiment is a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane, and it is realized by following steps: a, contaminated membrane module to be cleaned is put into the pond that running water is housed; B, be that 1:1.5 joins in pond by inoganic solids peroxide and peroxy-monosulfate according to mass ratio, stir, controlling permonosulphuric acid salinity is 800mg/L, and soak time is 60min; C, cleaned membrane module is put into another pond that running water is housed carry out rinsing, namely complete and utilize inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane.
The membrane material of the contaminated membrane module described in present embodiment is Kynoar (PVDF), polyether sulfone (PES), polyethylene (PE) or polyvinyl chloride (PVC).
After the singlet oxygen cleaning fouling membrane of present embodiment through producing, membrane flux recovers more than 90%.
The dosing method of the peroxide of inoganic solids described in present embodiment and peroxy-monosulfate adds for making mixed-powder dosage form according to mass ratio 1:1.5.Inoganic solids peroxide in present embodiment is any SODIUM PERCARBONATE of ratio and the mixture of potassium percarbonate; Peroxy-monosulfate is the permonosulphuric acid potassium of any ratio and the mixture of permonosulphuric acid sodium.
Claims (8)
1. utilize inoganic solids peroxide-induced peroxy-monosulfate to produce a method for singlet oxygen cleaning fouling membrane, the method that it is characterized in that utilizing inoganic solids peroxide-induced persulfate to produce singlet oxygen cleaning fouling membrane is realized by following steps: a, contaminated membrane module to be cleaned is put into the pond that running water is housed; B, be 1:(0.5 ~ 5 by inoganic solids peroxide and peroxy-monosulfate according to mass ratio) ratio join in the pond of step one, stir, controlling permonosulphuric acid salinity is 50 ~ 1000mg/L, soaks 10 ~ 180min; C, the membrane module after soaking is put into another pond that running water is housed and carried out rinsing, namely complete and utilize inoganic solids peroxide-induced persulfate to produce singlet oxygen cleaning fouling membrane; Described inoganic solids peroxide is one or more in sodium peroxide, calper calcium peroxide, peromag, barium peroxide, SODIUM PERCARBONATE, potassium percarbonate 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 method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane according to claim 1, is characterized in that the mass ratio of described inoganic solids peroxide and peroxy-monosulfate is 1:(0.6 ~ 4).
3. a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane according to claim 2, is characterized in that the mass ratio of described inoganic solids peroxide and peroxy-monosulfate is 1:(0.7 ~ 3).
4. a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane according to claim 3, is characterized in that the mass ratio of described inoganic solids peroxide and peroxy-monosulfate is 1:(0.8 ~ 2).
5. a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane according to claim 4, is characterized in that the mass ratio of described inoganic solids peroxide and peroxy-monosulfate is 1:(0.9 ~ 1.5).
6. a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane according to claim 5, is characterized in that the mass ratio of described inoganic solids peroxide and peroxy-monosulfate is 1:1.
7. a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane according to claim 1, is characterized in that described control permonosulphuric acid salinity is 100 ~ 800mg/L.
8. a kind of method utilizing inoganic solids peroxide-induced peroxy-monosulfate to produce singlet oxygen cleaning fouling membrane according to claim 7, is characterized in that described control permonosulphuric acid salinity is 200 ~ 500mg/L.
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CN105289311B (en) * | 2015-11-16 | 2017-09-26 | 哈尔滨理工大学 | A kind of method that utilization singlet oxygen cleans fouling membrane |
CN108217841B (en) * | 2017-12-04 | 2020-09-29 | 山东聊城鲁西硝基复肥有限公司 | Reverse osmosis water treatment system cleaning method |
CN109607880A (en) * | 2019-01-28 | 2019-04-12 | 杭州秀澈环保科技有限公司 | Maintaining method suitable for containing sulfate radicals use in waste water treatment seperation film |
CN113426302A (en) * | 2021-06-29 | 2021-09-24 | 河北工业大学 | Ceramic membrane cleaning method and cleaning device |
CN115463559B (en) * | 2022-09-08 | 2024-05-31 | 哈尔滨工业大学水资源国家工程研究中心有限公司 | Method for performing enhanced cleaning on polluted delta-manganese dioxide modified membrane based on peroxymonosulfate catalytic oxidation |
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