CN114105277B - Method for removing organic pollutants in water by catalyzing hydrogen peroxide - Google Patents

Method for removing organic pollutants in water by catalyzing hydrogen peroxide Download PDF

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CN114105277B
CN114105277B CN202010873326.0A CN202010873326A CN114105277B CN 114105277 B CN114105277 B CN 114105277B CN 202010873326 A CN202010873326 A CN 202010873326A CN 114105277 B CN114105277 B CN 114105277B
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pollutants
free radicals
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CN114105277A (en
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崔玉虹
薛伟俊
刘正乾
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Abstract

The invention belongs to the technical field of water treatment, and discloses a method for removing organic pollutants in water by catalyzing hydrogen peroxide, which takes solution containing hydrogen peroxide and organic pollutants as reaction liquid, adds metal simple substances or metal ions into the reaction liquid, and reacts for 0.1 to 24 hours under the stirring condition; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radicals, and organic pollutants and the hydroxyl radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals; the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, and finally, the solid-liquid separation is carried out to remove the organic pollutants in the water. The invention can solve the technical problem of large oxidant consumption in the prior art when removing pollutants by using high-concentration hydrogen peroxide by optimally controlling the reaction mechanism.

Description

Method for removing organic pollutants in water by catalyzing hydrogen peroxide
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for removing organic pollutants in water by catalyzing hydrogen peroxide.
Background
With the rapid development of modern industrial production, the amount of industrial wastewater is increased year by year, and the wastewater contains a large amount of refractory organic pollutants, has the characteristics of high concentration and high toxicity, and is difficult to treat by adopting a common biological method. On the other hand, it is difficult to treat such organic wastewater by a simple physical and chemical treatment method. Advanced oxidation techniques for hydrogen peroxide, such as: UV/H 2 O 2 、O 3 /H 2 O 2 Fenton and Fenton-like technologies, etc., by generating hydroxyl radicals (HO) having strong oxidizing properties · ) The organic pollutant which is difficult to degrade can be decomposed into biodegradable small molecular organic matters and even mineralized, so the method is considered as an effective pretreatment means for the high-concentration organic wastewater which is difficult to degrade.
The traditional Fenton and Fenton-like technology utilizes H 2 O 2 Reaction with ferrous iron produces hydroxyl radicals HO · Thereby degrading the organic contaminants.
Fe 2+ +H 2 O 2 +H + →Fe 3+ +HO · +H 2 O
Fe 2+ Will follow HO · Is gradually consumed and converted into Fe 3+ Therefore, fe needs to be continuously supplemented 2+ . Zero-valent iron Fe can also be used 0 As Fe 2+ From a source of (Fe) 2+ Slowly released in the solution to supplement Fe 2+ To ensure HO · The rate of generation of (a).
Fe 0 +H 2 O 2 +2H + →Fe 2+ +2H 2 O
Fe 0 Fe in the solution can also be added 3+ Reduction to Fe 2+ Then Fe 2+ Is continued with H 2 O 2 The reaction generates hydroxyl radicals.
Fe 0 +2Fe 3+ →3Fe 2+
By controlling the reaction conditions, it is possible to prevent excessive Fe while maintaining the HO.generation rate 2+ To HO · The generated quenching effect is to increase H 2 O 2 The utilization ratio of (2).
However, the above systems still have some disadvantages: (1) Long reaction time, long maintenance time of Fe in the system 2+ Until most target pollutants are oxidized and decomposed into micromolecular organic matters and even are completely mineralized, the concentration of iron ions dissolved out in a system after reaction is high, and the subsequent treatment is not facilitated; (2) Long degradation path of target pollutant, oxidant (H) 2 O 2 ) The consumption is high, and the utilization rate is low; (3) The treated organic wastewater still contains a large amount of organic substances, the removal rate of COD or TOC is not high, and other derivative organic substances with higher toxicity can be generated in the oxidative decomposition process of target pollutants, so that the subsequent biological treatment is not facilitated.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a method for removing organic pollutants in water by catalyzing hydrogen peroxide, wherein a reaction mechanism is optimally controlled, the hydrogen peroxide is catalytically decomposed to generate hydroxyl radicals in the reaction process, meanwhile, the organic pollutants and the hydroxyl radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic matter radicals, polymerization reaction is generated among the organic matter radicals or between the organic matter radicals and the organic pollutants to form a solid organic polymer, and finally, the organic pollutants in the wastewater can be effectively removed through solid-liquid separation, so that the technical problem of large oxidant consumption in the method for removing the pollutants by using high-concentration hydrogen peroxide in the prior art is solved.
In order to achieve the above object, according to the present invention, there is provided a method for removing organic pollutants in water by catalyzing hydrogen peroxide, which is characterized in that a solution containing hydrogen peroxide and organic pollutants is used as a reaction solution, a metal simple substance and/or metal ions are added into the reaction solution, and the reaction solution is stirred and reacted for 0.1 to 24 hours under stirring conditions; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radical HO · The organic pollutants and the hydroxyl free radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals; the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, namely organic solid particles; finally, carrying out solid-liquid separation on the reaction system dispersed with the solid organic polymer, wherein the liquid obtained by separation is the wastewater after the organic pollutants are removed, thereby realizing the removal of the organic pollutants in the water;
and, in the stirring reaction, the reaction that specifically takes place includes, but is not limited to:
HO · + organic contaminants → OH - + organic solid particles + soluble oxidation products.
As a further preferred aspect of the present invention, when a simple metal is added to the reaction solution, the reaction further comprises:
M 0 +x H 2 O 2 →x HO · +x OH - +M x+ ；
wherein M is 0 Elemental metal, M, representing the zero valence state x+ Represents a metal ion in a valence state.
As a further preferable aspect of the present invention, when the simple metal having a multi-valence property is added to the reaction liquid, the reaction that occurs further includes:
M 0 +[(n-1)/2]H 2 O 2 →M (n-1)+ +(n-1)OH - ，M (n-1)+ +H 2 O 2 →HO · +OH - +M n+ ，M 0 +(n-1)M n+ →n M (n-1)+ ；
wherein M is 0 Elemental metal, M, representing the zero valence state n+ Represents a higher valence state of a metal ion, M, corresponding to a polyvalent metal ion (n-1)+ Represents a lower valence metal ion corresponding to the multi-valence metal ion.
As a further preference of the present invention, when another metal ion is simultaneously present in the reaction liquid, the reaction that occurs further includes:
M 0 +[(n-1)/x]N x+ →M (n-1)+ +[(n-1)/x]N 0 ；
wherein, N x+ And N 0 Respectively represent metal ions different from the M element and metal simple substances thereof.
As a further preferred aspect of the present invention, when another polyvalent metal ion is simultaneously present in the reaction liquid, the reaction that occurs further includes:
M n+ +N (y-1)+ →M (n-1)+ +N y+ ；
wherein N is y+ And N (y-1)+ Respectively represent a metal ion having a higher valence and a lower valence of a polyvalent metal ion different from M.
As a further preferred aspect of the present invention, when only a metal ion is added to the reaction solution, the metal ion is a polyvalent metal ion, and the reaction further comprises:
M (n-1)+ +H 2 O 2 →HO · +OH - +M n+ ；
wherein M is n+ Represents a higher valence state of a metal ion, M, corresponding to a polyvalent metal ion (n-1)+ Represents a lower valence metal ion corresponding to the multi-valence metal ion.
In a further preferred embodiment of the present invention, the concentration of hydrogen peroxide in the reaction solution is 1 to 1000mmol/L.
In a further preferred embodiment of the present invention, the reaction time of the stirring reaction is 0.1 to 5 hours.
As a further preferred aspect of the present invention, the corresponding metal element in the simple metal or the metal ion is at least one selected from iron, cobalt, manganese, zinc, aluminum, copper, silver, cerium, chromium, nickel, and cadmium;
and the ratio of the total amount of the metal ions eluted from the simple metal added to the reaction solution or the metal ions added directly to the simple metal added to the reaction solution to the amount of the hydrogen peroxide in the reaction solution is 1.
In a further preferred embodiment of the present invention, the organic contaminant is one or more of a phenol-based organic substance, an aniline-based organic substance, an alkoxybenzene-based organic substance, a nitrobenzene-based organic substance, a phenol ester-based organic substance, a biphenyl-based organic substance, and a heterocyclic compound.
As a further preferred aspect of the present invention, the solid-liquid separation is filtration, static precipitation or centrifugal separation.
Generally, through the above technical solutions conceived by the present invention, compared with the prior art, the following beneficial effects can be obtained:
(1) In the invention, the organic pollutants are mainly removed through polymerization, and are not required to be completely oxidized and decomposed, so the reaction time is short.
(2) The oxidant consumption is less, the utilization rate is high, and the resources are saved.
(3) Can effectively remove target organic pollutants in the wastewater, greatly reduce COD and TOC contained in the wastewater, reduce the possibility of generating toxic derivatives and reduce the difficulty of the subsequent biological treatment process.
(4) Organic carbon resources and energy can be recovered by separating solid organic polymers produced after the reaction.
The method for catalyzing hydrogen peroxide can control the generation amount of hydroxyl radicals by controlling key parameters in the reaction process, such as the concentration of hydrogen peroxide and the concentration of metal ions in the reaction process, can further ensure that most organic pollutants in wastewater are subjected to polymerization reaction to form organic solid particles, and then effectively removes the organic pollutants in the wastewater through solid-liquid separation operation. By optimally controlling reaction parameters, the ratio of the total amount of metal ions in a reaction liquid to the amount of hydrogen peroxide is controlled to be 1-1.
Compared with the existing Fenton and Fenton-like technology for removing organic pollutants in wastewater, in the reaction process, the organic pollutants are separated and removed from the water mainly through solid organic polymers generated by polymerization, are not required to be decomposed into small molecular substances and mineralized, the reaction time is short, and the oxidant (H) is used 2 O 2 ) The utilization rate is high, and the consumption of the oxidant is effectively reduced; after the reaction is finished, the reaction liquid is subjected to solid-liquid separation, so that target organic pollutants, COD (chemical oxygen demand) and TOC (total organic carbon) in the wastewater can be effectively removed, and meanwhile, the solid organic polymer can be recycled and used as an organic carbon resource. In addition, the pH of the solution does not need to be adjusted after the reaction, and the generated organic solid particles do not contain metal elements. Meanwhile, the invention has the advantages of simple operation, high efficiency, energy saving, reduction of the generation of toxic derivatives, reduction of the difficulty of the subsequent biological treatment process and the likeHas the advantages of simple process and low cost.
Drawings
FIG. 1 is a graph showing the time-course removal of o-cresol in example 1.
FIG. 2 shows the result H in practice in example 1 2 O 2 Consumption of H required to achieve the same TOC removal rate by oxidative decomposition 2 O 2 Comparison of consumption.
FIG. 3 is a graph showing the removal of o-cresol over time in example 2.
FIG. 4 shows the result of H in practical example 2 2 O 2 Consumption of H required to achieve the same TOC removal rate by oxidative decomposition 2 O 2 Comparison of consumption.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Generally speaking, the method for removing organic matters by catalyzing hydrogen peroxide in the invention takes solution containing hydrogen peroxide, metal elements and organic matters (namely organic pollutants) as reaction liquid, controls reaction parameters, enables the organic matters and hydroxyl radicals to generate electron transfer reaction or hydrogen transfer reaction to generate organic matter free radicals, and enables organic matter free radicals or organic matter free radicals and organic matters to generate polymerization reaction to form organic solid particles, and removes the organic solid particles through solid-liquid separation, thereby removing the organic matters.
During specific operation, hydrogen peroxide, metal or ions thereof and wastewater containing organic pollutants can be added into a reaction chamber to serve as reaction liquid, then the reaction liquid is stirred for 0.1 to 24 hours (especially 0.1 to 5 hours), the target pollutants are subjected to electron transfer reaction or hydrogen transfer reaction to generate organic matter free radicals, and then solid organic polymers with large molecular weight are generated to be separated out from the solution and uniformly dispersed in the solution; after the reaction is finished, carrying out solid-liquid separation on the reaction liquid, wherein the liquid obtained by separation treatment is the treated wastewater after the organic pollutants are removed.
The following experiments were carried out by self-dispensing simulated wastewater, the following being specific examples:
example 1
Fe was explored in this example 0 /Fe 2+ /H 2 O 2 The system has the effect of removing o-cresol in the aqueous solution (namely simultaneously adding Fe simple substance and Fe into the reaction solution) 2+ Ions). The results show that o-cresol polymerizes during the reaction and a brownish solid particulate material is formed. After reacting for 40min, filtering the reaction solution to realize solid-liquid separation, wherein the removal rate of o-cresol reaches 99%, the removal rate of COD reaches 77%, and the removal rate of TOC reaches 61%. It can be calculated that the H required to achieve the same TOC removal rate theoretically is achieved by oxidative decomposition 2 O 2 The consumption is at least 76mmol/L, while in this example H is actually consumed 2 O 2 The amount is less than 20mmol/L, and the reaction time is greatly shortened.
The operating conditions are as follows:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of o-cresol solution: 4mmol/L
Volume of o-cresol solution: 100mL
H 2 O 2 Adding amount: 20mmol/L
Fe 2+ Adding amount: 2mmol/L
Initial pH of the reaction: 1.6
The aperture of the filter membrane is as follows: 0.45 μm
FIG. 1 is a graph showing the removal of o-cresol with time in example 1, and it can be seen that the concentration of o-cresol decreases approximately linearly with time, and the removal rate of o-cresol reaches 99% at 40 min. FIG. 2 shows actual H in example 1 2 O 2 Consumption of H required to achieve the same TOC removal rate by oxidative decomposition 2 O 2 Comparison of consumption.
Example 2
Fe was explored in this example 0 /H 2 O 2 The system has the effect of removing o-cresol in the aqueous solution (namely adding Fe simple substance into the reaction solution). The results show that o-cresol polymerizes during the reaction and a brownish solid particulate material is formed. After reacting for 1h, filtering the reaction solution to realize solid-liquid separation, wherein the removal rate of o-cresol reaches 91%, the removal rate of COD reaches 63%, and the removal rate of TOC reaches 43%. It can be calculated that the H required to achieve the same TOC removal rate theoretically is achieved by oxidative decomposition 2 O 2 The consumption is at least 53mmol/L, while in this example H is actually consumed 2 O 2 The amount is less than 20mmol/L, and the reaction time is greatly shortened.
The operating conditions are as follows:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of o-cresol solution: 4mmol/L
Volume of o-cresol solution: 100mL
H 2 O 2 Adding amount: 20mmol/L
Initial pH of the reaction: 1.5
The aperture of the filter membrane is as follows: 0.45 μm
FIG. 3 is a graph showing the removal of o-cresol with time in example 2, and it can be seen that the concentration of o-cresol decreases approximately linearly with time, and the removal rate of o-cresol reaches 91% at 60 min. FIG. 4 shows actual H in example 2 2 O 2 Consumption of H required to achieve the same TOC removal rate by oxidative decomposition 2 O 2 Comparison of consumption.
Example 3
In this example, different H's are compared 2 O 2 Influence of concentration on the effect of removal of organic substances in aqueous solution, H 2 O 2 The amounts of (A) and (B) were 5, 10, 15, 20 and 25mmol/L, respectively, and the remaining reaction conditions were the same as in example 1. The results show that with H 2 O 2 The addition amount is increased, more solid organic particles are separated out from the solution, but when the addition amount exceeds 20mmol/L, the formed solid organic polymer particles are not increased continuously.
Example 4
In this example, different Fe's are compared 2+ Influence of dosage on the removal effect of organic matters in aqueous solution, fe 2+ The amounts of addition were 0.5, 1.5, 2.0, 2.5 and 3.0mmol/L, respectively, and the remaining reaction conditions were the same as in example 1. The results show that Fe 2+ The addition amount changes the reaction rate in the initial stage, and the proper Fe is added when the same o-cresol removal rate is achieved 2+ The addition amount will shorten the total reaction time. Simultaneously with Fe 2+ The increase of the dosage causes the yield of the formed solid organic polymer particles to change and the Fe content 2+ The peak was reached when the amount of addition was 2.0 mmol/L. Total iron ions (i.e., fe) in solution at the end of the reaction 2+ And Fe 3+ Sum) concentration, but not more than 8mmol/L.
Example 5
In this example, the effect of the solution pH on the organic matter removal was compared, with initial pH values of 1.5, 1.6, 1.8, 2.2 and 3.0, respectively, and the remaining reaction conditions were the same as in example 1. The results show that as the initial pH increases, the amount of solid organic polymer particles formed changes, and more solid organic polymer particles are formed at lower pH.
Example 6
In this example, fe was examined 0 /H 2 O 2 The system has the effect of removing aniline in an aqueous solution. The results show that during the reaction aniline was polymerised and solid particulate material was formed. After reacting for 1h, carrying out solid-liquid separation on the reaction solution, wherein the removal rate of aniline exceeds 90%, and the removal rate of COD can reach more than 60%.
The operating conditions are as follows:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of aniline solution: 4mmol/L
Volume of aniline solution: 100mL
H 2 O 2 Adding amount: 30mmol/L
The aperture of the filter membrane is as follows: 0.45 μm
Example 7
Herein is implementedIn the examples, fe was examined 0 /Fe 2+ /H 2 O 2 The system has treatment effect on aqueous solution containing various mixed organic matters. The results show that organic matter undergoes polymerization in the reactor solution during the reaction and organic solid particulate matter is formed. After 5 hours of reaction, the reaction solution is subjected to solid-liquid separation to obtain 50 percent of COD removal rate.
The operating conditions are as follows:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of phenol in aqueous solution: 50mmol/L
Concentration of aniline in aqueous solution: 20mmol/L
Concentration of o-cresol in aqueous solution: 10mmol/L
Concentration of 4-bromophenol in aqueous solution: 10mmol/L
Volume of aqueous solution: 100mL
H 2 O 2 Adding amount: 1000mmol/L
Fe 2+ Adding amount: 20mmol/L
The aperture of the filter membrane is as follows: 0.45 μm
Example 8
In this example, fe was investigated 0 Mixed metal ion/H 2 O 2 The system has the effect of removing mixed organic matters in the aqueous solution. The results show that organic substances are subjected to polymerization reaction in the reaction liquid in the reaction process and organic solid particulate matters are generated. After 4 hours of reaction, the reaction solution is subjected to solid-liquid separation, and the COD removal rate of over 50 percent can be obtained.
The operating conditions are as follows:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of phenol in aqueous solution: 50mmol/L
Concentration of aniline in aqueous solution: 10mmol/L
Volume of mixed solution: 100mL
H 2 O 2 Adding amount: 600mmol/L
Fe 2+ Adding amount: 15mmol/L
Cu 2+ Adding amount: 2.0mmol/L
Co 2+ Amount of addition：0.05mmol/L
The aperture of the filter membrane is as follows: 0.45 μm
Example 9
In this example, fe was explored 0 /Fe 2+ /H 2 O 2 The experimental parameters of the system for removing 2, 6-xylenol from the aqueous solution are the same as those of example 1. The result shows that 2, 6-xylenol generates polymerization reaction in the reaction liquid during the reaction process to generate organic solid particles which can be filtered and removed.
Example 10
In this example, fe was investigated 0 /Fe 2+ /H 2 O 2 The system has the same experimental parameters as example 1 for the effect of removing ascorbic acid from an aqueous solution. The result shows that organic matter is polymerized to produce solid organic matter and can be filtered to eliminate solid organic matter.
Example 11
In this example, fe was investigated 0 /Fe 2+ /H 2 O 2 The experimental parameters for the removal effect of the system on the removal effect of benzoic acid in an aqueous solution were the same as in example 1. The result shows that organic matter is polymerized to produce solid organic matter and can be filtered to eliminate solid organic matter.
Example 12
In this example, fe was explored 0 /Fe 2+ /H 2 O 2 The system has the effect of removing 2,2 '-dihydroxybiphenyl in an aqueous solution, the initial concentration of 2,2' -dihydroxybiphenyl is 1.0mmol/L, and the rest of the experimental parameters are the same as those in example 1. The result shows that organic matter is polymerized to produce solid organic matter and can be filtered to eliminate solid organic matter.
The usage amount of the hydrogen peroxide is related to the concentration of the pollutant, and the demand amount of the oxidant is correspondingly higher when the concentration of the pollutant is high; the invention can achieve equivalent pollutant removal effect by using less oxidant under the condition of the same concentration of the organic pollutants; and, considering the treatment time and the type and concentration of the contaminants, the present invention can greatly shorten the reaction time under the same contaminant conditions.
<xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> Bithiophene, aminothiophene, and the like.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A kind ofA method for removing organic pollutants in water by catalyzing hydrogen peroxide is characterized in that a solution containing hydrogen peroxide and organic pollutants is used as a reaction solution, zero-valent iron and ferrous ions are added into the reaction solution, and the reaction is stirred under the stirring condition; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radical HO · The organic pollutants and the hydroxyl free radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals; the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, namely organic solid particles; finally, carrying out solid-liquid separation on the reaction system dispersed with the solid organic polymer, wherein the liquid obtained by separation is the wastewater after the organic pollutants are removed, thereby realizing the removal of the organic pollutants in the water;
in the stirring reaction, the reaction specifically occurring includes:
HO · + organic contaminant → OH - + organic solid particulates + soluble oxidation products;
wherein the organic contaminant is o-cresol;
the operating conditions are specifically:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of organic contaminant solution: 4mmol/L
Volume of organic contaminant solution: 100mL
H 2 O 2 Adding amount: 20mmol/L
Fe 2+ Adding amount: 2mmol/L
Initial pH of the reaction: 1.6.
2. the method of claim 1, wherein H is 2 O 2 The dosage is 5, 10, 15 or 25mmol/L.
3. The method of claim 1, wherein the Fe is present 2+ The dosage is 0.5, 1.5, 2.5 or 3.0mmol/L.
4. The method of claim 1, wherein the reaction initiation pH is 1.5, 1.8, 2.2, or 3.0.
5. The method of claim 1, wherein the organic contaminant is 2, 6-xylenol, ascorbic acid, or benzoic acid.
6. A method for removing organic pollutants in water by catalyzing hydrogen peroxide is characterized in that a solution containing hydrogen peroxide and organic pollutants is used as a reaction solution, zero-valent iron and ferrous iron ions are added into the reaction solution, and the reaction is stirred under the stirring condition; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radicals HO · The organic pollutants and the hydroxyl free radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals; the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, namely organic solid particles; finally, carrying out solid-liquid separation on the reaction system dispersed with the solid organic polymer, wherein the liquid obtained by separation is the wastewater after the organic pollutants are removed, thereby realizing the removal of the organic pollutants in the water;
in the stirring reaction, the reaction specifically occurring includes:
HO · + organic contaminants → OH - + organic solid particulates + soluble oxidation products;
wherein the organic contaminants include phenol, aniline, o-cresol, and 4-bromophenol;
the operating conditions are specifically:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of phenol in organic contaminant solution: 50mmol/L
Aniline concentration in organic contaminant solution: 20mmol/L
Concentration of o-cresol in organic contaminant solution: 10mmol/L
Concentration of 4-bromophenol in organic contaminant solution: 10mmol/L
Volume of organic contaminant solution: 100mL
H 2 O 2 Adding amount: 1000mmol/L
Fe 2+ Adding amount: 20mmol/L.
7. A method for removing organic pollutants in water by catalyzing hydrogen peroxide is characterized in that a solution containing hydrogen peroxide and organic pollutants is used as a reaction solution, zero-valent iron and mixed metal ions are added into the reaction solution, and the reaction is stirred under the stirring condition; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radicals HO · The organic pollutants and the hydroxyl free radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals; the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, namely organic solid particles; finally, carrying out solid-liquid separation on the reaction system dispersed with the solid organic polymer, wherein the liquid obtained by separation is the wastewater after the organic pollutants are removed, thereby realizing the removal of the organic pollutants in the water;
in the stirring reaction, the reaction specifically occurring includes:
HO · + organic contaminants → OH - + organic solid particulates + soluble oxidation products;
wherein the organic contaminants comprise both phenol and aniline; the mixed metal ions also include Fe 2+ 、Cu 2+ And Co 2+ ；
The operating conditions are specifically:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of phenol in organic contaminant solution: 50mmol/L
Aniline concentration in organic contaminant solution: 10mmol/L
Volume of organic contaminant solution: 100mL
H 2 O 2 Adding amount:600mmol/L
Fe 2+ adding amount: 15mmol/L
Cu 2+ Adding amount: 2.0mmol/L
Co 2+ Adding amount: 0.05mmol/L.
8. A method for removing organic pollutants in water by catalyzing hydrogen peroxide is characterized in that a solution containing hydrogen peroxide and organic pollutants is used as a reaction solution, zero-valent iron and ferrous iron ions are added into the reaction solution, and the reaction is stirred under the stirring condition; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radical HO · The organic pollutants and the hydroxyl free radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals; the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, namely organic solid particles; finally, carrying out solid-liquid separation on the reaction system dispersed with the solid organic polymer, wherein the liquid obtained by separation is the wastewater after the organic pollutants are removed, thereby realizing the removal of the organic pollutants in the water;
in the stirring reaction, the reaction specifically occurring includes:
HO · + organic contaminants → OH - + organic solid particulates + soluble oxidation products;
wherein the organic contaminant is 2,2' -dihydroxybiphenyl;
the operating conditions are specifically:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of organic contaminant solution: 1.0mmol/L
Volume of organic contaminant solution: 100mL
H 2 O 2 Adding amount: 20mmol/L
Fe 2+ Adding amount: 2mmol/L
Initial pH of the reaction: 1.6.
9. catalysisA method for removing organic pollutants in water by hydrogen peroxide is characterized in that a solution containing hydrogen peroxide and organic pollutants is used as a reaction solution, zero-valent iron is added into the reaction solution, and the reaction solution is stirred under the stirring condition; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radical HO · The organic pollutants and the hydroxyl free radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals; the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, namely organic solid particles; finally, carrying out solid-liquid separation on the reaction system dispersed with the solid organic polymer, wherein the liquid obtained by separation is the wastewater after the organic pollutants are removed, thereby realizing the removal of the organic pollutants in the water;
in the stirring reaction, the reaction specifically occurring includes:
HO · + organic contaminant → OH - + organic solid particulates + soluble oxidation products;
wherein the organic contaminant is o-cresol;
the operating conditions are specifically:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of organic contaminant solution: 4mmol/L
Volume of organic contaminant solution: 100mL
H 2 O 2 Adding amount: 20mmol/L
Initial pH of the reaction: 1.5.
10. a method for removing organic pollutants in water by catalyzing hydrogen peroxide is characterized in that a solution containing hydrogen peroxide and organic pollutants is used as a reaction solution, zero-valent iron is added into the reaction solution, and the reaction solution is stirred and reacted under the stirring condition; in the stirring reaction, hydrogen peroxide is catalytically decomposed to generate hydroxyl radicals HO · The organic pollutants and the hydroxyl free radicals generate electron transfer reaction or hydrogen transfer reaction to generate organic free radicals;the organic free radicals or the organic free radicals and the organic pollutants are subjected to polymerization reaction to form solid organic polymers, namely organic solid particles; finally, carrying out solid-liquid separation on the reaction system dispersed with the solid organic polymer, wherein the liquid obtained by separation is the wastewater after the organic pollutants are removed, thereby realizing the removal of the organic pollutants in the water;
in the stirring reaction, the reaction specifically occurring includes:
HO · + organic contaminants → OH - + organic solid particulates + soluble oxidation products;
wherein the organic contaminant is aniline;
the operating conditions are specifically:
elemental metal: 1 iron sheet of 2cm x 2cm
Concentration of organic contaminant solution: 4mmol/L
Volume of organic contaminant solution: 100mL
H 2 O 2 Adding amount: 30mmol/L.
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CN102910725A (en) * 2012-11-20 2013-02-06 哈尔滨工业大学 Method for removing organic pollutants in water through modified Fenton and Fenton-like systems
CN108726640A (en) * 2017-04-20 2018-11-02 华中科技大学 A kind of method of electrochemistry collaboration persulfate removal Organic Pollutants in Wastewater
CN110872145A (en) * 2018-08-29 2020-03-10 华中科技大学 Method for removing organic matters by electrochemical cooperation with hydrogen peroxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102910725A (en) * 2012-11-20 2013-02-06 哈尔滨工业大学 Method for removing organic pollutants in water through modified Fenton and Fenton-like systems
CN108726640A (en) * 2017-04-20 2018-11-02 华中科技大学 A kind of method of electrochemistry collaboration persulfate removal Organic Pollutants in Wastewater
CN110872145A (en) * 2018-08-29 2020-03-10 华中科技大学 Method for removing organic matters by electrochemical cooperation with hydrogen peroxide

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