CN109607885A - A kind of water treatment technology generated based on graphene-based material absorption/catalysis oxidation step coupling control bromate - Google Patents

A kind of water treatment technology generated based on graphene-based material absorption/catalysis oxidation step coupling control bromate Download PDF

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CN109607885A
CN109607885A CN201910122588.0A CN201910122588A CN109607885A CN 109607885 A CN109607885 A CN 109607885A CN 201910122588 A CN201910122588 A CN 201910122588A CN 109607885 A CN109607885 A CN 109607885A
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bromate
rgo
water
bromide ion
production quantity
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齐飞
宋子龙
王钰芳
张钰婷
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Beijing Forestry University
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Beijing Forestry University
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Abstract

The application provides a kind of water treatment technology generated based on graphene-based material absorption/catalysis oxidation step coupling control bromate, and the bromate processing unit which is mainly concerned with is that sulfur doping graphene (S-rGO) absorption bromide ion unit, graphene (rGO) catalytic oxidation unit and S-rGO adsorb bromate unit.Wherein, S-rGO has stronger absorption property for bromide ion and bromate, and rGO not only has superior catalytic oxidation performance, also has the ability of certain control bromate.Present invention process can formulate different operation process and method according to bromide ion concentration in different source waters, easily realize the generation of bromate in control advanced oxidation processes.It is easy to operate in terms of the advanced treating that the technique may be used on to drinking water, it is easy to accomplish.

Description

One kind is based on graphene-based material absorption/catalysis oxidation step coupling control bromate The water treatment technology of generation
Technical field
The present invention relates to a kind of water generated based on graphene-based material absorption/catalysis oxidation step coupling control bromate Treatment process.
Background technique
With the increasingly raising of living standard, people for Drinking Water water quality and safety attention degree increasingly It is high.Conventional drinking water treatment technique (coagulation → precipitating → filtering → disinfection → clear water reserviors water outlet) has been unable to meet people to water quality Requirement.And ozonation technology due to strong oxidizing property, non-selectivity, the green advantages such as without secondary pollution and be increasingly becoming A kind of wastewater treatment technology of advanced oxidation by favor.
However, turning when, there are when bromide ion, ozone and its secondary free radical can aoxidize the bromide ion in water body in water body It is melted into bromate, and subsequent process unit can not be effectively removed.Bromate is defined as 2B by international cancer research institution Grade (higher carcinogenic possibility) potential carcinogen.The maximum concentration of bromate is limited in 10 μ g/L by the World Health Organization (WHO). Regulation bromate concentration may not exceed 0.01mg/ in China newest " standards for drinking water quality " (GB5749-2006) L.But when bromide ion concentration is more than 100 μ g/L in water, after ozone Oxidation Treatment, bromate will be severely exceeded.Therefore, In the case where ozone oxidation water treatment technology applies increasingly extensive, the production quantity of bromate is efficiently controlled, ensures drinking water Water quality safety is of great significance.
In recent years, researchers at home and abroad are for controlling harmful by-products while ozone oxidation micro quantity organic pollutant The method of the production quantity of bromate has carried out a large amount of exploration.On the whole, following three aspects can be summarized as: 1) before End improvement, 2) pilot process improvement, 3) end treatment.
1) front end, which is administered, refers to through the method for absorption by the removal of bromate precursor bromide ion, to avoid ozonizing The generation of bromate in journey.103570099 A of patent CN provides a kind of method for controlling bromate precursor bromide ion, will Water body containing bromide ion carries out the forming amount that ozonation treatment can be substantially reduced bromate again after being ultrasonically treated.So And the energy consumption of this method ultrasound is high, is limited only to laboratory operation, practical application value is not high；107694612 A of patent CN will Fe2+And Fe3+Be supported on after resin surface plus alkali alkalization, form magnetized resin, the resin for bromate precursor and Bromate has an apparent adsorption effect, and removal efficiency is up to 95% or more；102276008 A of patent CN is using the poly- inclined of load silver Chlorovinyl activated carbon microballon is as adsorbent Adsorption bromide ion, to realize the reduction of bromate；Patent CN 107585831 A adsorb bromide ion by preparing calcium alginate/AgCl hydridization bead as adsorbent, to realize bromate It cuts down；Active carbon is added in 102020372 A of patent CN in the preposition filtrate of ozonization or the absorption of high-purity ormolu is gone Except bromide ion, to cut down the generation of bromate.However, metal/metal oxide class material is inevitable in the above method There are toxic metals Ion releases, bring secondary pollution.Such as in 107694612 A of patent CN Fe use, patent CN The use of precious metals ag in 102276008 A, and the use of Ag also will increase use cost.
2) pilot process improvement refers to the method by the way that chemical agent or solid-phase catalyst is added to change ozone reaction Path, thus the method for cutting down bromate forming amount.
(i) chemical method: 105236691 A of patent CN provide it is a kind of added before ozonation technology chlorine ammonia with The method for controlling bromate production quantity, can reduce by 60%~80% or so bromate production quantity；Meanwhile discovery is by reducing pH Method also can be reduced 50% or so bromate production quantity.Azanol work is added in 102701425 A of patent CN in ozonation The yield of control bromate is realized for bromic acid salt inhibitor；However, the addition of ammonia and azanol can all form a large amount of nitrogenous disinfections pairs Product, reducing pH will increase the production quantity of total organic bromine (TOBr), bring other risks.108821420 A of patent CN is to brominated Added in water body sodium thiosulfate method realize bromate it is synchronous with pollutant removal, but reducing agent sodium thiosulfate add Membership consumes ozone in large quantities, influences the enhancing degradation and removal effect of micro quantity organic pollutant.102303916 A of patent CN Using FeCl3101967020 A of bromate and patent CN 102234154 A and patent CN in the method removal water body of coagulation The method of hydrogen peroxide is added into water body to control the yield of bromate.However, these chemical agents are required to duration throwing Add, dramatically increases drinking water treatment process operation cost.
(ii) heterogeneous catalytic ozonation: 103846087 A of patent CN provides a kind of Fe-Al/Al2O3Heterogeneous catalysis The synchronous method for cutting down bromate during ozone oxidation degradation 2,4 dichlorophenoxyacetic acid.In ozonation, catalyst The reduction of surface bromate is the main reason for bromate is effectively controlled.102616916 A of patent CN provides one kind and draws Enter nano-TiO2Catalyst finds this method for bromic acid the method that controls bromate during drinking water ozone oxidation, research The production quantity of salt can cut down 90% or more.102513088 A of patent CN is formed using cerous nitrate and Titanium Nitrate coupling calcining Composite catalyst can complete the reduction of bromate.Inevitably there is metal ion in metal/metal oxide class material Dissolution, brings secondary pollution, the safety wind for increasing drinking water is dangerous.
108751386 A of patent CN couples cerium oxide with graphene oxide (GO) to realize in ozonation The reduction of bromate.103991943 A of patent CN report graphene coupled with active carbon after catalyst in ozonation In have for bromate and apparent cut down effect.However, having document report GO can be unstable by ozone oxidation；And Product increases organic carbon content in water outlet.Result of study shows that GO and its derivative catalysis material are not suitable for answering in drinking water With.(Zilong Song,Yuting Zhang,Chao Liu,Bingbing Xu,Fei Qi,Donghai Yuan, Shengyan Pu,Insight into*OH and O2*-Formation in Heterogeneous Catalytic Ozonation by Delocalized Electrons and Surface Oxygen-Containing Functional Groups in Layered-Structure Nanocarbons,Chemical Engineering Journal,357 (2019)655-666)。
3) end treatment refers to using sides such as absorption, catalysis reduction, photo catalytic reduction, electro-catalysis reduction and biodegrades The method that the bromate that method is formed after ozonizing is cut down.
(i) it adsorbs.105152258 A of patent CN is using load Fe2+Red mud porcelain granule, patent CN with β-FeOOH 103263887 A are using Al-Zn oxide, 203247158 U of patent CN using Mg-Al layered doubled hydroxide adsorption column for bromic acid Salt all has good adsorption effect.Inevitably there are digestion of metallic ion for the use of metal oxide-type material, bring Secondary pollution, the safety wind for increasing drinking water are dangerous.
Many researchers just use active carbon to carry out Adsorption bromate.107162159 A of patent CN is provided and a kind of will be lived Property charcoal and ozone are coupled the method to cut down bromate yield.The technique by added in water body effective chlorine by bromine from Son is converted into HOBr, recycles active carbon to be carried out adsorption treatment later.This method, which still remains, adds asking for chemical agent It inscribes and adding for chlorine there are problems that increasing chlorine-containing disinfecting by-product.106334523 A of patent CN is using hydrogen peroxide to activity Carbon surface is modified, 101637716 A of patent CN is modified activated carbon surface using ammonium hydroxide, and be significantly increased work Adsorption effect of the property charcoal for bromate；102294149 A of patent CN is by active carbon and polyethylene powder, Natural Manganese potassium powder and hair The raw materials such as hole powder combine the drinking water bromate adsorbent material that the commercialization of forming is prepared, and bromate removal rate can reach 95% or more.103466742 A of patent CN is realized using the adsorption column of modified crosslinking chitosan organic polymer adsorbent material The reduction of bromate in drinking water, this method is nontoxic, without secondary pollution.Realize that it is cut in applied activated carbon absorption bromate In the technique subtracted, active carbon not only adsorbs bromate, but also adsorbs organic pollutant present in water.Competitive Adsorption substantially reduces The adsorption efficiency of bromate and the service life of active carbon.
(ii) catalysis reduction.101585573 A of patent CN is in aluminium oxide area load noble metal, patent CN 101708884 A load ruthenium, patent in activated carbon surface in activated carbon surface carried noble metal Ag, 101890348 A of patent CN 102895986 A of CN uses palladium-supported mesoporous carbonitride (Pd/MCN), and 102976471 A of patent CN is using nitrogen dentate chelating tree Rouge loads nano zero-valence iron composite material, and 103232125 A of patent CN uses mesoporous carbon-loaded nano zero valence iron and patent CN 104437476 A prepare Pd/Al using nano-spray method2O3Composite material realizes bromic acid come the bromate being catalyzed in reduction water body The efficient reduction of salt.However, noble metal or Zero-valent Iron are oxidized in catalytic reduction process, metal ion is formed.This is not only Secondary pollution is caused, and the service life of reducing agent can also be greatly reduced.
(iii) photo catalytic reduction.201567248 U of patent CN 107902815 A and patent CN uses homogeneous ultraviolet radiation Catalytic reduction method restores bromate, the TiO that 205556153 U of patent CN uses precious metals ag modified2Light is carried out under ultraviolet light Catalysis reduction bromate, TiO 105772037 A of patent CN modified using HF and graphene2Photocatalysis is carried out under ultraviolet light Bromate is restored, the reduction of bromate is realized.However, this method needs to add new water treatment building, increase light source The investment of equipment, so that drinking water treatment operating cost greatly increases.Importantly, during photo catalytic reduction, water body It is middle to form Competition there are other oxysalt anion and organic pollutant, the inhibition on significant ground its to bromate The performance of reduction.
(iv) electro-catalysis restores.104671362 A of patent CN constitutes compound carbon paper using carbon paper, graphene film and palladium layers Electrode realizes the cathode electrocatalyst reduction of bromate in water；106915803 A of patent CN is using stud as anode, electro-deposition Palladium-nickel modification activated carbon fiber realizes that bromate removes while anode and cathode as cathode.It is similar with photo catalytic reduction, it should Method and cannot achieve synchronous removal of the bromate in ozonation due to the investment of electric energy, and processing cost also will be big It is big to increase.
(v) biological degradation method: 103103146 A of patent CN has found that Sphingomonas being capable of obvious degradation bromate； 106916761 A of patent CN has found the compound bacteria that hay bacillus kind, pseudomonad kind, milk-globule strain and Exiguobacterium sp kind are constituted Kind has the ability of obvious degradation bromate.Not only just the starting period is slow for bioanalysis, and the residence time is long；And in drinking water treatment Technique end is also easy to produce the leakage of microorganism, causes the biology to supply water dangerous.
In conclusion ensureing that drinking water goes out water security to completely eliminate the generation of bromate in ozonation.Individually Front end administer, pilot process is administered and the method for end treatment cannot achieve this target, and three should be had The coupling of machine.102020372 A of patent CN proposes the method for completely eliminating bromate: the filtrate of prefilter contains active carbon Or the combination of high-purity ormolu (KDF) or both, the filtrate of postposition filtering contain active carbon, ozone oxidation process is placed in Between preposition filtrate and postposition filtrate, filtering-ozone-biological active carbon water treatment technology is formed.However, the oxidability of ozone It is extremely limited, it not can be removed especially for many high stability organic micro-pollutants；The starting of bioactive carbon section Period is again very long.
This patent is based on the problem of current research process, proposes unique using sulfur doping graphene (S-rGO) 3D porous hydrogel plastic structure not only efficiently adsorbs organic pollutant and inorganic oxysalt, also has to bromide ion good Good absorption property.These features can be in reducing source water while bromide ion load, as bromate after ozonisation The last of risk control ensures together.The graphene surface (rGO) has a large amount of oxygen-containing functional group and defective bit, efficiently urges for it Change ozone and provide a large amount of active site, can not only realize the removal of persistent organic pollutants, and can be certain The production quantity that bromate is cut down in degree, does not increase water treatment building additionally.
Summary of the invention
The present invention is directed to the drinking water source water body containing micro bromide ion/bromate, to solve existing ozonation technology Harmful by-products bromate is led to the problem of, is innovatively proposed a kind of based on graphene-based material absorption/catalysis oxidation ladder The water treatment technology that grade coupling control bromate generates, and be illustrated for its application conditions.The present invention utilizes S-rGO pairs There is excellent absorption property in bromide ion and bromate, the superior catalysis oxidation depollution synchronously control bromate ability of rGO, Different operating schemes is formulated according to different source water bromide ion contamination loads, forms graphene-based material absorption/catalysis It aoxidizes step and couples water treatment technology, realize effective control of control ozone harmful by-products bromate.
It is generated the present invention provides a kind of based on graphene-based material absorption/catalysis oxidation step coupling control bromate Water treatment technology, it is characterised in that (one): will there is the sulfur doping graphene (S- of good adsorbent performance to bromide ion and bromate RGO) absorbing process is coupled with efficient graphene (rGO) catalytic ozonation technique step, realizes that bromide ion is not in source water With the efficient reduction of ozone oxidation harmful by-products bromate production quantity under loading condiction；It is characterized in that (two) are when bromine in the water of source Ion concentration be lower than 21 μ g/L when, can be realized its efficiently cut down bromate production quantity handling technology of water supply process be coagulation → Bromide ion → rGO catalytic ozonation → chlorination → clear water reserviors water outlet in precipitating → filtering → S-rGO absorption source water.Wherein, S-rGO can be realized the complete Adsorption of bromide ion in the water of source, guarantee that there is no bromates during O3 catalytic oxidation Precursor, to realize that it cuts down the purpose of bromate production quantity completely；It is characterized in that (three) are when bromide ion concentration in the water of source When between 21-61 μ g/L, can be realized its handling technology of water supply process for efficiently cutting down bromate production quantity is coagulation → precipitating → filtering → rGO catalytic ozonation → S-rGO absorption bromate → chlorination → clear water reserviors water outlet.Wherein, rGO is urged in ozone Change and is formed by bromate during capable of significantly cutting down ozone oxidation in oxidation process.And S-rGO can be by remaining bromic acid Salt absorption, to realize that it cuts down the purpose of bromate production quantity completely；It is characterized in that (four) are when bromide ion concentration in the water of source When between 61-82 μ g/L, can be realized its handling technology of water supply process for efficiently cutting down bromate production quantity is coagulation → precipitating Bromide ion → rGO catalytic ozonation → S-rGO adsorbs bromate → chlorination → clear water in → filtering → S-rGO absorption source water Pond water outlet.Wherein, S-rGO can be realized the Adsorption of source water part bromide ion, rGO energy during catalytic ozonation Enough to guarantee that remaining bromide ion, which is formed by bromate during ozone oxidation, substantially to be removed, last S-rGO can Remaining bromate is adsorbed, to realize that it cuts down the purpose of bromate production quantity completely.It is characterized in that (five) Dang Yuanshui When middle bromide ion concentration is greater than 82 μ g/L, it is mixed for can be realized it and efficiently cut down the handling technology of water supply process of bromate production quantity Bromide ion → rGO catalytic ozonation → (S-rGO adsorbs bromate) in solidifying → precipitating → filtering → S-rGO absorption source waterIt is several→ Chlorination → clear water reserviors water outlet.Wherein, the number that S-rGO adsorbs bromate technique unit is adjusted according to practical bromic acid salt residual quantity It is whole, realize that it cuts down the purpose of bromate production quantity completely.It is characterized in that (six) reaction condition are as follows: catalyst rGO and absorption The concentration of agent S-rGO is 0.1-1.0g/L, ozone concentration 0.5-5.0mg/L, and processing water body pH is 6.0-8.0, reaction temperature It is 20-25 DEG C.
The beneficial effects of the present invention are: rGO catalytic ozonation unit can be in effective degradable organic pollutant in the technique While control bromate generate.S-rGO absorbing unit can have the adsorption effect of good stable to bromide ion and bromate, The last of bromate risk control is discharged after oxidation being formed while Systemic Burden before bromate in source water is effectively reduced One of effective barrier.In addition, the difference according to bromide ion concentration in source water, can flexibly adjust operating scheme Control, it is easy to operate, it is the water treatment technology with bright prospects.
Accompanying drawing content
Attached drawing 1 is bromate during the rGO catalytic ozonation degradation organic pollutant that specific embodiment one obtains Generation situation, wherein ■ indicates the process that bromate is generated during independent ozone oxidation organic pollutant, ● indicate that rGO is urged Change the process that ozone oxidation removes generation bromate during removal organic polluter.It can be seen from the figure that rGO has in catalytic degradation There is good control effect (control rate 26.5%) for bromate while machine pollutant.Attached drawing 2 and 3 is specific implementation The S-rGO that mode one obtains evaluates the absorption property of bromate precursor (bromide ion) and bromate.It can be seen from the figure that S-rGO has apparent adsorption effect for bromide ion (adsorption rate 21%) and bromate (adsorption rate 35%).
Specific embodiment
By this water treatment technology generated based on graphene-based material absorption/catalysis oxidation step coupling control bromate Application be illustrated, technical solution of the present invention is not limited to following enumerated specific embodiment, further includes each specific implementation Any combination between mode.
Specific embodiment 1: in present embodiment graphene-based material preparation method (one) rGO's the preparation method comprises the following steps: (1) 0.1g graphite oxide is accurately weighed, grinds 20min using agate mortar；(2) above-mentioned powder is placed in porcelain crucible with cover It is interior, it places uniformly, is placed in Muffle furnace in the state of Ban Gaigai.Be arranged calcination temperature be 350 DEG C, calcination time 60min, Heating rate is 5 DEG C/min.Thus the fluffy graphene oxide of black is obtained.(2) S-rGO can be completed by following process Preparation: (1) by the graphite oxide ultrasonic disperse of 0.1g into 70mL aqueous solution, ultrasonic disperse 30min.(2) by the sulfydryl of 0.22g Acetic acid, which is added thereto, is mixed 30min；(3) obtained solution is transferred in the reaction kettle of 100mL, reaction temperature 160 DEG C, reaction time 16h.
When bromide ion concentration is lower than 21 μ g/L in the water of source, can be realized at its water supply for efficiently cutting down bromate production quantity Reason process flow is that coagulation → precipitating → filtering → S-rGO adsorbs bromide ion → rGO catalytic ozonation → chlorination in the water of source The water outlet of → clear water reserviors.The technique is realized by following steps: (1) O needed for technique3Concentration is 2.0mg/L；(2) technique institute Needing rGO catalyst throwing amount is 0.25g/L；(3) the throwing amount of bromide ion adsorbent S-rGO needed for technique is 0.25g/L；(4) it contacts Time is 30min；(5) reaction system pH is 6.01.
Prepared rGO is 26.5 for the reduction of bromate while catalytic degradation organic pollutant in the technique μg/L.But S-rGO is 21 μ g/L for the adsorbance of bromide ion, and the complete absorption that S-rGO can be realized bromide ion in the water of source is gone It removes, guarantees that there is no bromate precursors during O3 catalytic oxidation, to realize that it cuts down bromate production quantity completely Purpose.
Specific embodiment 2: the specific preparation method of graphene-based material refers to specific embodiment in present embodiment One.
When bromide ion concentration is between 21-61 μ g/L in the water of source, can be realized its efficiently cut down bromate production quantity to Water treatment technological process be coagulation → precipitating → filtering → rGO catalytic ozonation → S-rGO adsorb bromate → chlorination → Clear water reserviors water outlet.The technique is realized by following steps: (1) O needed for technique3Concentration is 2.0mg/L；(2) needed for technique RGO catalyst throwing amount is 0.25g/L；(3) the throwing amount of bromide ion adsorbent S-rGO needed for technique is 0.25g/L；(4) technique institute The throwing amount for needing bromate adsorbent S-rGO is 0.25g/L；(5) time of contact is 30min；(6) reaction system pH is 6.01.
Prepared rGO is 26.5 for the reduction of bromate while catalytic degradation organic pollutant in the technique μg/L.S-rGO is 35 μ g/L for the adsorbance of bromate.RGO can significantly cut down ozone during catalytic ozonation Bromate formed in oxidation process, S-rGO can adsorb remaining bromate, to realize that it cuts down bromate completely The purpose of production quantity.
Specific embodiment 3: the specific preparation method of graphene-based material refers to specific embodiment in present embodiment One.
When bromide ion concentration is between 61-82 μ g/L in the water of source, can be realized its efficiently cut down bromate production quantity to Water treatment technological process is that coagulation → precipitating → filtering → S-rGO adsorbs bromide ion → rGO catalytic ozonation → S- in the water of source RGO adsorbs bromate → chlorination → clear water reserviors water outlet.The technique is realized by following steps: (1) O needed for technique3It is dense Degree is 2.0mg/L；(2) rGO catalyst throwing amount needed for technique is 0.25g/L；(3) bromide ion adsorbent S-rGO needed for technique Throwing amount is 0.25g/L；(4) the throwing amount of bromate adsorbent S-rGO needed for technique is 0.25g/L；(5) time of contact is 30min；(6) reaction system pH is 6.01.
Prepared rGO is 26.5 for the reduction of bromate while catalytic degradation organic pollutant in the technique μg/L.S-rGO is 21 μ g/L for the adsorbance of bromide ion, and the adsorbance for bromate is 35 μ g/L.S-rGO can be realized The Adsorption of source water part bromide ion, rGO can guarantee remaining bromide ion during catalytic ozonation in ozone Bromate formed in oxidation process substantially removes.Last S-rGO can adsorb remaining bromate, thus real Its existing purpose for cutting down bromate production quantity completely.
Specific embodiment 4: the specific preparation method of graphene-based material refers to specific embodiment in present embodiment One.
When bromide ion concentration is greater than 82 μ g/L in the water of source, can be realized at its water supply for efficiently cutting down bromate production quantity Reason process flow is that coagulation → precipitating → filtering → S-rGO adsorbs bromide ion → rGO catalytic ozonation → (S-rGO in the water of source Adsorb bromate)It is several→ chlorination → clear water reserviors water outlet.The technique is realized by following steps: (1) O needed for technique3It is dense Degree is 2.0mg/L；(2) rGO catalyst throwing amount needed for technique is 0.25g/L；(3) bromide ion adsorbent S-rGO needed for technique Throwing amount is 0.25g/L；(4) the throwing amount of bromate adsorbent S-rGO needed for technique is 0.25g/L；(5) time of contact is 30min；(6) reaction system pH is 6.01.
Prepared rGO is 26.5 for the reduction of bromate while catalytic degradation organic pollutant in the technique μg/L.S-rGO is 21 μ g/L for the adsorbance of bromide ion, and the adsorbance for bromate is 35 μ g/L.S-rGO can be realized The Adsorption of source water part bromide ion, rGO can guarantee remaining bromide ion during catalytic ozonation in ozone Bromate formed in oxidation process substantially removes.The quantity of remaining bromate absorbing unit is needed according to practical The amount of remaining bromate is adjusted, and realizes that its cuts down the purpose of bromate production quantity completely.

Claims (9)

1. a kind of water treatment technology generated based on graphene-based material absorption/catalysis oxidation step coupling control bromate, It is characterized in that: will there is sulfur doping graphene (S-rGO) absorbing process and height of good adsorbent performance to bromide ion and bromate Graphene (rGO) catalytic ozonation technique step of effect couples, ozone under the conditions of bromide ion different load in realization source water Aoxidize the efficient reduction of harmful by-products bromate production quantity.
2. the water treatment technology that step coupling control bromate described in claim 1 generates, it is characterised in that: when bromine in the water of source Ion concentration be lower than 21 μ g/L when, can be realized its efficiently cut down bromate production quantity handling technology of water supply process be coagulation → Bromide ion → rGO catalytic ozonation → chlorination → clear water reserviors water outlet in precipitating → filtering → S-rGO absorption source water.
3. handling technology of water supply process as claimed in claim 2, it is characterised in that: S-rGO can be realized bromide ion in the water of source Complete Adsorption guarantees that there is no bromate precursors during O3 catalytic oxidation, to realize that it cuts down bromine completely The purpose of hydrochlorate production quantity.
4. the water treatment technology that step coupling control bromate described in claim 1 generates, it is characterised in that: when bromine in the water of source When ion concentration is between 21-61 μ g/L, it is mixed for can be realized it and efficiently cut down the handling technology of water supply process of bromate production quantity Solidifying → precipitating → filtering → rGO catalytic ozonation → S-rGO absorption bromate → chlorination → clear water reserviors water outlet.
5. handling technology of water supply process as claimed in claim 4, it is characterised in that: rGO can during catalytic ozonation Significant ozone oxidation of cutting down is formed by bromate in the process, and S-rGO can adsorb remaining bromate, to realize that its is complete The full purpose for cutting down bromate production quantity.
6. the water treatment technology that step coupling control bromate described in claim 1 generates, it is characterised in that: when bromine in the water of source When ion concentration is between 61-82 μ g/L, it is mixed for can be realized it and efficiently cut down the handling technology of water supply process of bromate production quantity Bromide ion → rGO catalytic ozonation → S-rGO absorption bromate → chlorine disappears in solidifying → precipitating → filtering → S-rGO absorption source water Poison → clear water reserviors water outlet.
7. handling technology of water supply process as claimed in claim 6, it is characterised in that: S-rGO can be realized source water part bromine from The Adsorption of son；RGO can guarantee remaining bromide ion during catalytic ozonation in ozone oxidation during institute shape At bromate substantially remove；Last S-rGO can adsorb remaining bromate, to realize that it cuts down bromine completely The purpose of hydrochlorate production quantity.
8. the water treatment technology that step coupling control bromate described in claim 1 generates, it is characterised in that: when bromine in the water of source When ion concentration is greater than 82 μ g/L, can be realized its handling technology of water supply process for efficiently cutting down bromate production quantity can be such as It is transformed in handling technology of water supply process as claimed in claim 6, the number that S-rGO adsorbs bromate technique unit can be according to Factually border remains the amount of bromate to be adjusted, and realizes that its cuts down the purpose of bromate production quantity completely.
9. method described in claim 1, application conditions are as follows: the concentration of catalyst rGO and adsorbent S-rGO are 0.1-1.0g/ L, ozone concentration 0.5-5.0mg/L, processing water body pH are 6.0-8.0, and reaction temperature is 20-25 DEG C.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613165A (en) * 2009-07-20 2009-12-30 广东省微生物研究所 Control method of bromate in bottled drinking water
CN102276050A (en) * 2011-05-30 2011-12-14 广东省微生物研究所 Device for controlling ozonization byproduct bromate in packaged drinking water
CN102381780A (en) * 2011-09-21 2012-03-21 哈尔滨工业大学 Method for controlling by-product generation amount in process of water treatment in micro polluted water source by step catalytic oxidation
CN102381811A (en) * 2011-09-21 2012-03-21 哈尔滨工业大学 Method for removing pollutants in water through stepwise catalytic oxidation-biological activated carbon-ultraviolet (UV) combination
CN108178152A (en) * 2018-03-01 2018-06-19 济南开发区星火科学技术研究院 It is a kind of can efficient absorption heavy metal ion graphite oxide aerogel preparation method
CN109231464A (en) * 2018-09-19 2019-01-18 河海大学 A kind of modularization agricultural drain step purification total nitrogen removal system and method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613165A (en) * 2009-07-20 2009-12-30 广东省微生物研究所 Control method of bromate in bottled drinking water
CN102276050A (en) * 2011-05-30 2011-12-14 广东省微生物研究所 Device for controlling ozonization byproduct bromate in packaged drinking water
CN102381780A (en) * 2011-09-21 2012-03-21 哈尔滨工业大学 Method for controlling by-product generation amount in process of water treatment in micro polluted water source by step catalytic oxidation
CN102381811A (en) * 2011-09-21 2012-03-21 哈尔滨工业大学 Method for removing pollutants in water through stepwise catalytic oxidation-biological activated carbon-ultraviolet (UV) combination
CN108178152A (en) * 2018-03-01 2018-06-19 济南开发区星火科学技术研究院 It is a kind of can efficient absorption heavy metal ion graphite oxide aerogel preparation method
CN109231464A (en) * 2018-09-19 2019-01-18 河海大学 A kind of modularization agricultural drain step purification total nitrogen removal system and method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MINGXI CHEN ET AL.: "A one-step method for reduction and self-assembling of graphene oxide into reduced graphene oxide aerogels", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
国家知识产权局专利局专利审查协作江苏中心: "《热点专利技术分析与运用 第1辑》", 31 October 2015 *
王隆勇: "石墨烯材料用于饮用水中溴酸盐的控制和去除", 《中国优秀硕士学位论文全文数据库 工程科技II辑》 *

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