CN108675430B - Catalytic process for the production of sulfate radicals and reactive oxygen species and advanced oxidation of nonbiodegradable organic pollutants - Google Patents
Catalytic process for the production of sulfate radicals and reactive oxygen species and advanced oxidation of nonbiodegradable organic pollutants Download PDFInfo
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Abstract
The invention provides a catalytic method for generating sulfate radical free radicals and active oxygen species and an advanced oxidation method for organic pollutants difficult to biodegrade, which are used for solving the problems of low degradation efficiency and high cost of the organic pollutants in the prior art. The catalytic method for generating sulfate radical free radicals and active oxygen species adopts transition metal oxyhydroxide-based materials as a catalyst to generate sulfate radical free radicals, hydroxyl free radicals, superoxide free radicals and singlet oxygen non-free radicals, and further efficiently oxidizes nonbiodegradable organic pollutants. The invention takes the transition metal oxyhydroxide-based material as the catalyst, improves the activation efficiency of persulfate, generates various free radicals and active oxygen species, and thus improves the oxidative degradation rate of organic pollutants; the catalyst has stable structure, low heavy metal dissolution rate in the catalysis process and no secondary pollution, and can be widely applied to industrial production wastewater treatment, domestic sewage treatment, purification treatment of polluted underground water and surface water and treatment of polluted soil.
Description
Technical Field
The invention belongs to the technical field of environmental protection and pollutant prevention and treatment, and particularly relates to a catalytic method for simultaneously generating sulfate radical and active oxygen species and an advanced oxidation method for organic pollutants difficult to biodegrade.
Background
With the development and progress of society, the economic living standard of people is rapidly improved, and meanwhile, environmental problems become more serious, for example, the ball becomes warm, the ozone layer is damaged, acid rain, the crisis of fresh water resources, the shortage of energy sources, the disasters of land desertification garbage, the pollution of toxic chemicals and the like, and some of the problems threaten the survival of human beings.
Contamination with nonbiodegradable organic pollutants is one of the toxic chemical pollutants. With the production development of industry and agriculture, organic pollutants difficult to biodegrade become an indispensable industrial and living material; while the organic pollutants difficult to biodegrade are difficult to biodegrade in water, the organic pollutants enter water bodies through various ways to cause pollution and are gradually concentrated through a food chain to cause harm. The persistence and wide dispersion of the nonbiodegradable organic pollutants in the environment have great influence on the environment and the ecology, and are always important links of the vicious cycle of environmental pollution and ecological environment.
At present, through the efforts of environmental protection workers, a novel advanced oxidation technology is researched and developed, so that the organic pollutants difficult to biodegrade can be treated by efficiently mineralizing or oxidizing, the pollution is reduced, and the method has a good application prospect.
The traditional Advanced Oxidation Process (AOP) utilizes high-activity hydroxyl radicals to realize oxidative degradation, and mainly includes a Fenton method, a Fenton-like method, photochemical Oxidation, catalytic wet Oxidation, sonochemical Oxidation, ozone Oxidation, electrochemical Oxidation and the like. Compared with the traditional water treatment technology, the advanced oxidation technology AOP has the advantages of wide application range, high reaction rate, strong oxidation capacity, no pollution or little pollution. However, the oxidizing ability of hydroxyl radicals still has a certain bottleneck, and the applicable pH range is limited.
The novel advanced oxidation technology AOP is based on sulfate radicals(SO4 -·,E02.5-3.1V), has been shown to be more traditional based on hydroxyl radicals (OH, E)01.8-2.7V), a higher half-life, a wider adaptable pH range (pH 2-10), no volatility, more environmental friendliness, a stronger selective oxidizing property, and a long-term property maintenance. However, there are still factors that restrict sulfate radicals in advanced oxidation technologies, such as: the action mechanism of sulfate radical and various organic matters needs to be further explored; the activation generation mode has high energy consumption and low utilization rate; side reaction occurs, and the generation amount of sulfate radicals is low; oxidant and metal ions still remain after the reaction; can react with various interfering ions in the underground water or the wastewater, and the treatment efficiency is easily influenced.
In the prior art, the process of generating sulfate radicals in an advanced oxidation method is catalyzed by a homogeneous catalyst, but as the catalyst for generating the sulfate radicals, the homogeneous catalyst has the problems of difficult recovery, difficult separation, large consumption, difficult treatment of residue, secondary pollution and the like, and meanwhile, the addition amount of the catalyst has great influence on a reaction system and has the obvious defect of inorganic matter competition reaction.
Disclosure of Invention
The invention aims to solve the technical problem of providing a catalytic method for generating sulfate radical and active oxygen species and an advanced oxidation method for organic pollutants difficult to biodegrade, so as to solve the problem of pollution of the organic pollutants difficult to biodegrade in the prior art.
To solve the above technical problems, embodiments of the present invention provide a catalytic method for generating sulfate radicals and active oxygen species, which employs a transition metal oxyhydroxide as a catalyst.
Further, the transition metal oxyhydroxide includes: cobalt oxyhydroxide, manganese oxyhydroxide, iron oxyhydroxide, nickel oxyhydroxide;
the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
Further, the method comprises the steps of:
step S11, grinding the solid material of the transition metal oxyhydroxide to obtain catalyst powder;
step S12, adding persulfate or monopersulfate into water to prepare a first solution of 0.15-0.3 mol/L;
and step S13, adding the catalyst powder into the first solution, stirring at the speed of 100 r/min-400 r/min, and activating persulfate to generate sulfate radicals and active oxygen species.
Further, the synthesis process of the cobalt oxyhydroxide is as follows:
step S211, adding Co (NO)3)2·6H2Dissolving O in water to obtain a second solution with the concentration of 0.15-0.2 mol/L;
s212, dissolving NaOH in water to prepare 0.5-2 mol/L NaOH solution;
step S213, adding NaOH solution into the second solution dropwise according to the volume ratio of 1:1, wherein the supernatant is changed from rose red to transparent, and the reaction is complete to obtain a third solution;
step S214, placing the third solution in a water bath kettle, heating at a constant temperature of 60 ℃, and pouring out supernatant to obtain a fourth solution;
step S215, putting the fourth solution on a water bath kettle, and dripping H with the mass of 30 percent of the total solution while heating and stirring2O2Then carrying out water bath for 3h at the constant temperature of 60 ℃ to obtain a fifth solution;
and S216, centrifuging the fifth solution, washing the solid, and drying the solid in an oven for 24 hours to obtain the cobalt oxyhydroxide.
Further, the synthesis process of the nickel oxyhydroxide is as follows:
step S220, mixing NiSO4Adding the solid into water to prepare 0.15-0.3 mol/L NiSO4A solution;
step S221, according to the volume ratio of 1:1, the concentration is 0.15-0.3 mol/LK2S2O8The solution is dripped into the NiSO4Obtaining a sixth solution in the solution;
step S222, adding ammonia water into the sixth solution to adjust the pH value to 7-9;
step S223, standing the sixth solution for 72 hours at 35 ℃ to obtain a seventh solution;
step S224, centrifuging the seventh solution, washing the obtained solid and drying;
step S225, adding NaOH solid into NaClO solution with the concentration of 0.15-0.3 mol/L according to the concentration of 1-3% by mass to obtain eighth solution, and placing the solid dried in the step S224 into the eighth solution to be uniformly mixed to obtain ninth solution;
and step S226, centrifuging the ninth solution, washing a solid obtained after centrifuging, and drying in an oven for 24 hours to obtain the nickel oxyhydroxide.
Further, the synthesis process of the manganese oxyhydroxide comprises the following steps:
step S231, mixing MnSO according to the concentration of 1-3% by mass fraction4·H2Adding O into 0.1mol/L NaOH solution;
step S232, adding H accounting for 30-50% of the total solution mass into the solution obtained in step S2312O2And mixing uniformly;
step S233, adding the solution obtained in the step S232 into a reaction kettle, heating to 150 ℃ and keeping for 15 hours;
step S234, naturally cooling the product in the reaction kettle to room temperature, and washing the product with water until the pH value of the solid surface is neutral;
and step S235, placing the obtained solid in a vacuum drying oven, and carrying out vacuum drying for 4h at 50 ℃ to obtain the manganese oxyhydroxide.
Further, the synthesis process of the iron oxyhydroxide is as follows:
step S241, dropwise adding NaOH solution with the concentration of 1mol/L into Fe (NO) with the concentration of 1.2mol/L according to the volume ratio of 3:1 under the condition of stirring3)3Obtaining vermilion precipitate in the solution;
step S242, after the vermilion is completely precipitated, adjusting the pH value of the mixed solution to 8-12, standing for 1-4 h, and then putting the mixed solution into a heat preservation box to activate for 2h at the constant temperature of 30 ℃;
step S243, repeatedly washing the precipitate with water until the pH value is 7-9;
and step S244, drying the cleaned precipitate at constant temperature of 30 ℃ to obtain the iron oxyhydroxide.
Further, a metal oxide is loaded on the transition metal oxyhydroxide, or the transition metal oxyhydroxide is loaded on a non-metal carrier, or transition metal ions are doped in the transition metal oxyhydroxide.
Further, the transition metal oxyhydroxide includes: cobalt oxyhydroxide, manganese oxyhydroxide, iron oxyhydroxide, nickel oxyhydroxide; the metal oxide supported on the transition metal oxyhydroxide includes: TiO 22、ZnO、CuO、Al2O3、Fe3O4、MnO2、Bi2O3、CeO2、NiO、Co3O4And V2O5(ii) a The non-metal carrier includes: three-dimensional graphene, redox graphene, carbon nanotubes and molecular sieves; the molecular formula of the transition metal hydroxide doped with transition metal ions is MxN1-xOOH, wherein 0<x<1, M is Ni, Mn, Co, Zn and Fe elements, N is Ni, Mn, Co, Zn, Fe, Mg and Cu elements, and M and N are different elements.
According to another aspect of the present invention, there is also provided an advanced oxidation method for nonbiodegradable organic pollutants, which uses a transition metal oxyhydroxide species as a catalyst to generate sulfate radicals and active oxygen species, thereby oxidatively degrading the nonbiodegradable organic pollutants.
The technical scheme of the invention has the following beneficial effects:
the catalytic method for generating sulfate radicals and active oxygen species and the advanced oxidation method for nonbiodegradable organic pollutants of the embodiment adopt transition metal oxyhydroxide as a catalyst, and the transition metal oxyhydroxide catalyzes persulfate or monopersulfate to generate sulfate radicals and active oxygen species including hydroxyl radicals and superoxide radicalsThe organic pollutants difficult to be biodegraded are oxidatively degraded by radicals and singlet oxygen non-free radicals. Fine particles of a transition metal hydroxide catalyst are put into a reactor, persulfate is added to serve as an oxidant of a reaction system, and then organic pollutants are added for degradation. The invention takes the transition metal oxyhydroxide-based material as the catalyst, improves the efficiency of activating persulfate, improves the oxidative degradation rate of organic pollutants, and has stable structure and can not be oxidized by S2O8 2-The heavy metal dissolution rate in the catalytic process is low through oxidative decomposition, the problems of high heavy metal dissolution and harsh degradation conditions of the conventional homogeneous catalyst are effectively solved, secondary pollution of heavy metal ions is not caused in the catalytic process, secondary pollution is hardly caused to the environment, and the catalyst can be used for domestic sewage treatment, industrial and agricultural production wastewater treatment, purification treatment of underground water and surface water and remediation of soil polluted by organic matters. The method can greatly improve the removal efficiency of the organic pollutants difficult to biodegrade, and the removal rate of the organic matters can reach 88 to 100 percent.
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In order to more clearly illustrate the embodiments of the present invention and the prior art, the following technical scheme description figures of the present invention are briefly introduced, and it is obvious that other figures can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing the effect of example 8 of the present invention on the treatment of a solution containing dye contaminants;
FIG. 2 is a graph showing the effect of example 8 of the present invention on the treatment of a solution containing chlorophenol contaminants;
FIG. 3 is a graph showing the effect of example 8 of the present invention on the treatment of a solution containing antibiotic contaminants;
FIG. 4 is a graph showing the effect of example 8 of the present invention on the treatment of a solution containing chlorophenol contaminants;
FIG. 5 is a graph showing the effect of example 8 of the present invention on the treatment of a solution containing dye contaminants.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described below with reference to the accompanying drawings and specific embodiments.
The invention provides a catalytic method for generating sulfate radicals, hydroxyl radicals, superoxide radicals and singlet oxygen non-radicals and an Advanced Oxidation method for the organic pollutants difficult to biodegrade, aiming at the problem of processing the organic pollutants difficult to biodegrade in the prior art, based on Advanced Oxidation Process (AOP). The transition metal oxyhydroxide catalyst includes cobalt oxyhydroxide CoOOH, manganese oxyhydroxide MnOOH, iron oxyhydroxide FeOOH, nickel oxyhydroxide NiOOH, and the like. The catalyst has high electron transfer rate, has a plurality of surface active points, is a strong hydrophilic compound with high surface hydroxyl sites, supports heterogeneous reaction, can be used as catalysts (such as dispersed, loaded and colloidal) in different forms, has low dissolution rate of transition metal and high stability, and has the capability of efficiently activating persulfate and degrading organic pollutants in water or soil.
The present invention will be described in detail below with reference to specific examples.
Example 1
This example presents a catalytic process for the generation of sulfate radicals and active oxygen species using CoOOH as catalyst, comprising the following steps:
synthesis of CoOOH:
step S211, taking Co (NO)3)2·6H2Dissolving O in water to obtain a second solution with the concentration of 0.15-0.2 mol/L;
step S212, dissolving NaOH in water to prepare 1mol/L NaOH solution;
step S213, adding NaOH solution into the second solution dropwise according to the volume ratio of 1:1, wherein the supernatant is changed from rose red to transparent, and the reaction is complete to obtain a third solution;
step S214, placing the third solution in a water bath kettle, heating at a constant temperature of 60 ℃, and pouring out supernatant to obtain a fourth solution;
step S215, putting the fourth solution on a water bath kettle, and dripping H with the molar concentration of 30% while heating and stirring2O2Then carrying out water bath for 3h at the constant temperature of 60 ℃ to obtain a fifth solution;
and S216, centrifuging the fifth solution, washing the solid, and drying the solid in an oven for 24 hours to obtain the cobalt oxyhydroxide.
And (3) completing catalysis:
step S111, grinding the solid material of the cobalt oxyhydroxide into fine particles to obtain cobalt oxyhydroxide powder; the particle size of the particles is 1 um-30 um;
step S112, adding monopersulfate (PMS) into water to prepare monopersulfate water solution;
and step S113, adding the cobalt oxyhydroxide powder into the monopersulfate aqueous solution, and stirring at the speed of 400r/min to generate sulfate radicals and active oxygen species. Preferably, the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
Example 2
This example presents a catalytic process for the generation of sulfate radicals and active oxygen species using NiOOH as catalyst, comprising the following steps:
synthesizing NiOOH:
step S220, mixing NiSO4Adding the solid into water to prepare 0.15-0.3 mol/L NiSO4A solution;
step S221, according to the volume ratio of 1:1, the concentration is 0.15-0.3 mol/LK2S2O8The solution is dripped into the NiSO4Obtaining a sixth solution in the solution;
step S222, slowly adding ammonia water into the sixth solution to adjust the pH value to 7-9;
step S223, standing the sixth solution for 72 hours at 35 ℃ to obtain a seventh solution;
step S224, centrifuging the settled seventh solution, washing the obtained solid, and drying;
step S225, adding NaOH solid into NaClO solution with the concentration of 0.15-0.3 mol/L according to the concentration of 1-3% by mass to obtain eighth solution, and placing the solid dried in the step S224 into the eighth solution to be uniformly mixed to obtain ninth solution; and step S226, centrifuging the ninth solution, washing a solid obtained after centrifuging, and drying in an oven for 24 hours to obtain the nickel oxyhydroxide. And (3) completing catalysis:
step S121, grinding the solid material of the nickel oxyhydroxide into fine particles to obtain nickel oxyhydroxide powder; the particle size of the particles is 1 um-30 um;
step S122, adding persulfate into water to prepare a persulfate aqueous solution;
and step S123, adding the nickel oxyhydroxide powder into the persulfate aqueous solution, and stirring at the speed of 100r/min to generate sulfate radicals and active oxygen species. Preferably, the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
Example 3
This example presents a catalytic process for the generation of sulfate radicals and active oxygen species, using MnOOH as catalyst, comprising the following steps:
synthesizing MnOOH:
step S231, mixing MnSO according to the concentration of 1-3% by mass fraction4·H2Adding O into 0.1mol/L NaOH solution;
step S232, adding H accounting for 30-50% of the total solution mass into the solution obtained in step S2312O2And mixing uniformly;
step S233, adding the solution obtained in the step S232 into a reaction kettle, heating to 150 ℃ and keeping for 15 hours;
step S234, naturally cooling the product in the reaction kettle to room temperature, and washing the product with water until the pH value of the solid surface is neutral;
and step S235, placing the obtained solid in a vacuum drying oven, and carrying out vacuum drying for 4h at 50 ℃ to obtain the manganese oxyhydroxide.
And (3) completing catalysis:
step S131, grinding the solid material of the manganese oxyhydroxide into fine particles to obtain manganese oxyhydroxide powder; the particle size of the particles is 1 um-30 um;
step S132, adding persulfate and monopersulfate into water according to a certain ratio to prepare a composite saline solution;
and step S133, adding the manganese oxyhydroxide powder into the composite salt water solution, and stirring at the speed of 300r/min to generate sulfate radicals and active oxygen species. Preferably, the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
Example 4
The embodiment of the invention provides a catalytic method for generating sulfate radical and active oxygen species, which adopts FeOOH as a catalyst and comprises the following steps:
synthesizing FeOOH:
step S241, dropwise adding NaOH solution with the concentration of 1mol/L into Fe (NO) with the concentration of 1.2mol/L according to the volume ratio of 3:1 under the condition of stirring3)3Obtaining vermilion precipitate in the solution;
step S242, after the vermilion is completely precipitated, adjusting the pH value of the mixed solution to 8-12, standing for 1-4 h, and then putting the mixed solution into a heat preservation box to activate for 2h at the constant temperature of 30 ℃;
step S243, repeatedly washing the precipitate with water until the pH value is 7-9;
and step S244, drying the cleaned precipitate at constant temperature of 30 ℃ to obtain the iron oxyhydroxide.
And (3) completing catalysis:
step S141, grinding the solid material of the iron oxyhydroxide into fine particles to obtain iron oxyhydroxide powder; the particle size of the particles is 1 um-30 um;
step S142, adding persulfate into water to prepare persulfate aqueous solution;
and step S143, adding the iron oxyhydroxide powder into the persulfate aqueous solution, and stirring at the speed of 200r/min to generate sulfate radicals and active oxygen species. Preferably, the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
Example 5
This example presents a catalytic process for the generation of sulfate radicals and active oxygen species using a metal oxide Bi supported on CoOOH2O3Is a catalyst and comprises the following steps:
step S151 of loading Bi2O3Grinding the solid material of the CoOOH to fine particles, wherein the particle size of the particles is 1-30 um;
step S152, adding persulfate into water to prepare a persulfate aqueous solution;
step S153, loading Bi2O3The CoOOH powder of (a) is added to an aqueous persulfate solution and stirred at a rate of 200r/min to produce sulfate radicals and active oxygen species. Preferably, the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
In this embodiment, the load is Bi2O3The procedure for preparing a solid material of CoOOH (a) is substantially the same as the CoOOH synthesis procedure in example 1, except that step S211 is: mixing 2.91gCo (NO)3)2·6H2Bi with O dissolved in ultrasonic wave2O3Adding water to the solution to 200ml to prepare 0.05mol/L Co (NO)3)2And (3) solution.
In particular, the metal oxide Bi in the present embodiment2O3One or more of the following oxides may be substituted: TiO 22、ZnO、CuO、Al2O3、Fe3O4、MnO2、CeO2、NiO、Co3O4And V2O5(ii) a The transition metal oxyhydroxide cobalt oxyhydroxide in this embodiment may be replaced with manganese oxyhydroxide, iron oxyhydroxide, nickel oxyhydroxide.
Example 6
The embodiment provides a catalytic method for generating sulfate radical and active oxygen species, which adopts Ni ions doped in CoOOH as a catalyst and comprises the following steps:
step S161, grinding the CoOOH solid material doped with Ni ions to fine particles, wherein the particle size of the particles is 1-30 um;
step S162, adding persulfate into water to prepare a persulfate aqueous solution;
step S163, adding CoOOH powder doped with Ni ions into persulfate aqueous solution, and stirring at a speed of 200r/min to generate sulfate radicals and active oxygen species. Preferably, the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
The synthesis process of the Ni ion-doped CoOOH solid material in this embodiment is substantially the same as that of CoOOH in embodiment 1, except that step S211 is: the composition is prepared according to the following steps of Ni: co 0.05: 095 weighing 2.7645g of Co (NO)3)2·6H2O in 200ml water, 0.1455g of Ni (NO) were weighed out3)2·6H2O is dissolved in the solution and stirred uniformly.
In particular, the Ni ion-doped CoOOH or NiCoOOH in the present embodiment may be replaced with a compound of formula MxN1- xTransition metal oxyhydroxide of OOH containing transition metal ions, wherein 0<x<1, M is Ni, Mn, Co, Zn and Fe, N is Ni, Mn, Co, Zn, Fe, Mg and Cu, and M and N are different elements; the transition metal oxyhydroxide cobalt oxyhydroxide in this embodiment may be replaced with manganese oxyhydroxide, iron oxyhydroxide, nickel oxyhydroxide.
Example 7
The embodiment provides a catalytic method for generating sulfate radicals and active oxygen species, which adopts CoOOH loaded on graphene oxide as a catalyst and comprises the following steps:
step S171, grinding a CoOOH solid material loaded on graphene oxide to fine particles, wherein the particle size of the particles is 1-30 um;
step S172, adding persulfate into water to prepare a persulfate aqueous solution;
step S173, adding CoOOH powder loaded on graphene oxide into a persulfate aqueous solution, and stirring at the speed of 200r/min to generate sulfate radicals and active oxygen species. Preferably, the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals.
The preparation process of the solid material of CoOOH supported on graphene oxide in this embodiment is substantially the same as the synthesis process of CoOOH in embodiment 1, except that step S211 is: preparing graphene oxide with the concentration of 1mg/mL in a 500mL beaker, performing ultrasonic treatment for 12 hours, and performing ultrasonic treatment uniformly with 0.5mol/LCo (NO)3)2·6H2And mixing the O solution in equal proportion.
In particular, the graphene oxide serving as the carrier in this embodiment may be replaced by a carbon nanotube, a three-dimensional graphene, a redox graphene, or a molecular sieve; the transition metal oxyhydroxide cobalt oxyhydroxide in this embodiment may be replaced with manganese oxyhydroxide, iron oxyhydroxide, nickel oxyhydroxide.
The catalytic methods for generating free radicals described in examples 1 to 7, which use transition metal oxyhydroxides as catalysts, the transition metal oxyhydroxides have a large specific surface area and a high electron transfer rate, and the efficiency of activating persulfate and monopersulfate is improved; the transition metal oxyhydroxide catalyst has stable structure and can not be coated by S2O8 2-The heavy metal ions are decomposed by oxidation, the dissolution rate of the heavy metal ions is low, secondary pollution of the heavy metal ions can not be brought in the catalytic process, secondary pollution to the environment can be hardly brought in, and the potential hazard is small; meanwhile, the technical scheme of the embodiment of the invention can be used for domestic sewage treatment, industrial and agricultural production wastewater treatment, purification treatment of underground water and surface water and remediation of soil polluted by organic matters, greatly improves the removal efficiency of the nonbiodegradable organic pollutants, and has the removal rate of the organic matters reaching 88-100%. The catalysis method for generating sulfate radical free radicals and active oxygen species has certain reusability, has low economic cost compared with other treatment technologies, and has wide application prospect.
Example 8
The present example provides an advanced oxidation process for the oxidative degradation of nonbiodegradable organic pollutants by transition metal oxyhydroxides to catalyze persulfate or monopersulfate salts to produce sulfate radicals and active oxygen. Specifically, the method comprises the following steps:
step S32, adding persulfate or monopersulfate into water to prepare a degradation aqueous solution;
step S33, adding the degradation aqueous solution into a solution containing organic pollutants difficult to biodegrade;
and S34, adding a catalyst into the solution containing the nonbiodegradable organic pollutants obtained in the step S33, adding a prepared persulfate solution, stirring, and stirring at the speed of 100 r/min-400 r/min to finish the degradation of the nonbiodegradable organic pollutants in the solution to be treated. Wherein S in the aqueous solution of the step S322O8 2-The molar ratio to the nonbiodegradable organic pollutants is 20: 1; the solid-water ratio of the transition metal oxyhydroxide aqueous solution added in the step S32 is 0.1-0.4 g/L.
Further, the catalyst is a transition metal oxyhydroxide. Preferably, the transition metal oxyhydroxide is loaded with a metal oxide, or the transition metal oxyhydroxide is loaded with a non-metal carrier, or the transition metal oxyhydroxide is doped with transition metal ions.
Further, the transition metal oxyhydroxide includes: cobalt oxyhydroxide, manganese oxyhydroxide, iron oxyhydroxide, nickel oxyhydroxide; the metal oxide supported on the transition metal oxyhydroxide includes: TiO 22、ZnO、CuO、Al2O3、Fe3O4、MnO2、Bi2O3、CeO2、NiO、Co3O4And V2O5(ii) a The non-metal carrier includes: three-dimensional graphene, redox graphene, carbon nanotubes and molecular sieves; transition metal doped with transition metal ionThe molecular formula of the oxyhydroxide is MxN1-xOOH, wherein 0<x<1, M is Ni, Mn, Co, Zn and Fe elements, N is Ni, Mn, Co, Zn, Fe, Mg and Cu elements, and M and N are different elements.
By adopting the advanced oxidation method of the embodiment, the solution containing different organic pollutants difficult to be biodegraded is treated, wherein the different organic pollutants difficult to be biodegraded are respectively: dyes, chlorophenols, antibiotics.
FIG. 1 is a diagram showing the effect of the present example on the treatment of a solution containing dye pollutants, wherein the catalysts used are cobalt oxyhydroxide, manganese oxyhydroxide, iron oxyhydroxide, and nickel oxyhydroxide; the processing parameters are as follows: degradation of dye contaminant AO7The concentration of the pollutants is 150 mg/L; [ PMS ]]/[ contamination ]]20: 1; the solid-water ratio is 0.2 g/L; FIG. 2 is a diagram showing the effect of the treatment of the solution containing chlorophenol pollutants according to the present embodiment, wherein the catalysts used are cobalt oxyhydroxide, manganese oxyhydroxide, iron oxyhydroxide, and nickel oxyhydroxide; the processing parameters are as follows: degrading chlorophenol pollutant 2,4-DCP with pollutant concentration of 100 mg/L; [ PMS ]]/[ contamination ]]20: 1; the solid-water ratio is 0.2 g/L; FIG. 3 is a graph showing the effect of the present example on the treatment of a solution containing antibiotic contaminants, wherein the catalysts used are cobalt oxyhydroxide, manganese oxyhydroxide, iron oxyhydroxide, and nickel oxyhydroxide; the processing parameters are as follows: degrading antibiotic pollutant tetracycline, wherein the concentration of the pollutant is 100 mg/L; [ PMS ]]/[ contamination ]]20: 1; the solid-water ratio is 0.2 g/L; FIG. 4 is a graph showing the effect of the treatment of the solution containing chlorophenol-type contaminants using the present example, in which the catalyst is Bi-supported3O2Cobalt oxyhydroxide of (a); the processing parameters are as follows: degrading the chlorophenol pollutant, wherein the concentration of the 2,4-DCP pollutant is 150 mg/L; [ PMS ]]/[ contamination ]]20: 1; the solid-water ratio is 0.1 g/L; FIG. 5 is a graph showing the effect of treating a solution containing dye contaminants using this example, using a catalyst doped with NiCoOOH CoOOH; the processing parameters are as follows: degradation of dye AO7Pollutants, wherein the concentration of the pollutants is 100 mg/L; [ PMS ]]/[ contamination ]]20: 1; the solid-to-water ratio is 0.4 g/L.
From FIG. 1 can be seenIt is shown that the persulfate solution catalyzed by the heterogeneous transition metal hydroxide catalyst can effectively degrade dye pollutants, wherein the degradation effect sequence of four transition metal hydroxides on the dye pollutants after the persulfate is catalyzed by the four transition metal hydroxides is CoOOH>NiOOH>MnOOH>FeOOH; as can be seen from FIG. 2, persulfate solutions catalyzed by heterogeneous transition metal oxyhydroxide catalysts can effectively degrade chlorophenol pollutants, wherein the degradation effect sequence of four transition metal oxyhydroxides on chlorophenol pollutants catalyzed by persulfate is CoOOH>MnOOH>NiOOH>FeOOH; as can be seen from FIG. 3, the persulfate solutions catalyzed by heterogeneous transition metal oxyhydroxide catalysts can effectively degrade antibiotic pollutants, wherein the sequence of the degradation effects of four transition metal oxyhydroxides on the antibiotic pollutants after the catalysis of persulfate is CoOOH>NiOOH>MnOOH>FeOOH; as can be seen from fig. 4, the persulfate solution catalyzed by the transition metal oxyhydroxide catalyst loaded with the metal oxide can effectively degrade chlorophenol pollutants; as can be seen from FIG. 5, the dopant is of the formula MxN1-xThe persulfate solution catalyzed by transition metal hydroxide catalysts such as CoOOH of transition metal ions of OOH can effectively degrade dye pollutants. Therefore, the heterogeneous transition metal oxyhydroxide catalyst is used for catalyzing the peroxymonosulfuric acid, so that sulfate radicals and active oxygen for advanced oxidation reaction can be efficiently generated, and pollutants with benzene rings can be efficiently degraded.
Therefore, in the advanced oxidation method of the organic pollutants with difficult biodegradation, fine particles of the transition metal oxyhydroxide catalyst are put into the reactor, persulfate is added as the oxidant of the reaction system, and then the organic pollutants are put into the reactor for degradation, the transition metal oxyhydroxide catalyst improves the efficiency of activating the persulfate, and the transition metal oxyhydroxide catalyst has a stable structure and cannot be degraded by S2O8 2-Oxidative decomposition, effectively solves the problems of high heavy metal dissolution and heavy metal reduction of the existing homogeneous catalystThe method solves the problem of harsh conditions, does not bring secondary pollution of heavy metal ions in the catalytic process, hardly brings secondary pollution to the environment, and can be used for domestic sewage treatment, industrial and agricultural production wastewater treatment, purification treatment of underground water and surface water, and remediation of soil polluted by organic matters. The method can greatly improve the removal efficiency of the organic pollutants difficult to biodegrade, and the removal rate of the organic matters can reach 88 to 100 percent.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A catalytic process for the production of sulfate radicals and active oxygen species, wherein the catalytic process employs a transition metal oxyhydroxide as a catalyst to catalyze monopersulfates to produce sulfate radicals and active oxygen species;
the transition metal oxyhydroxide is manganese oxyhydroxide;
the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals;
the synthesis process of the manganese oxyhydroxide comprises the following steps:
step S231, mixing MnSO according to the concentration of 1-3% by mass fraction4·H2Adding O into 0.1mol/L NaOH solution;
step S232, adding H accounting for 30-50% of the total solution mass into the solution obtained in step S2312O2And mixing uniformly;
step S233, adding the solution obtained in the step S232 into a reaction kettle, heating to 150 ℃ and keeping for 15 hours;
step S234, naturally cooling the product in the reaction kettle to room temperature, and washing the product with water until the pH value of the solid surface is neutral;
and step S235, placing the obtained solid in a vacuum drying oven, and carrying out vacuum drying for 4h at 50 ℃ to obtain the manganese oxyhydroxide.
2. A catalytic process for the production of sulfate radicals and active oxygen species, wherein the catalytic process employs a transition metal oxyhydroxide as a catalyst to catalyze monopersulfates to produce sulfate radicals and active oxygen species;
the transition metal oxyhydroxide is cobalt oxyhydroxide;
the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals;
the synthesis process of the cobalt oxyhydroxide comprises the following steps:
step S211, adding Co (NO)3)2·6H2Dissolving O in water to obtain a second solution with the concentration of 0.15-0.2 mol/L;
s212, dissolving NaOH in water to prepare 0.5-2 mol/L NaOH solution;
step S213, adding NaOH solution into the second solution dropwise according to the volume ratio of 1:1, wherein the supernatant is changed from rose red to transparent, and the reaction is complete to obtain a third solution;
step S214, placing the third solution in a water bath kettle, heating at a constant temperature of 60 ℃, and pouring out supernatant to obtain a fourth solution;
step S215, putting the fourth solution on a water bath kettle, and dripping H with the mass of 30 percent of the total solution while heating and stirring2O2Then carrying out water bath for 3h at the constant temperature of 60 ℃ to obtain a fifth solution;
and S216, centrifuging the fifth solution, washing the solid, and drying the solid in an oven for 24 hours to obtain the cobalt oxyhydroxide.
3. A catalytic process for the production of sulfate radicals and active oxygen species, wherein the catalytic process employs a transition metal oxyhydroxide as a catalyst to catalyze monopersulfates to produce sulfate radicals and active oxygen species;
the oxyhydroxide is nickel oxyhydroxide;
the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals;
the synthesis process of the nickel oxyhydroxide comprises the following steps:
step S220, mixing NiSO4Adding the solid into water to prepare 0.15-0.3 mol/L NiSO4A solution;
step S221, according to the volume ratio of 1:1, the concentration is 0.15-0.3 mol/LK2S2O8The solution is dripped into the NiSO4Obtaining a sixth solution in the solution;
step S222, adding ammonia water into the sixth solution to adjust the pH value to 7-9;
step S223, standing the sixth solution for 72 hours at 35 ℃ to obtain a seventh solution;
step S224, centrifuging the seventh solution, washing the obtained solid and drying;
step S225, adding NaOH solid into NaClO solution with the concentration of 0.15-0.3 mol/L according to the concentration of 1-3% by mass to obtain eighth solution, and placing the solid dried in the step S224 into the eighth solution to be uniformly mixed to obtain ninth solution;
and step S226, centrifuging the ninth solution, washing a solid obtained after centrifuging, and drying in an oven for 24 hours to obtain the nickel oxyhydroxide.
4. A catalytic process for the production of sulfate radicals and active oxygen species, wherein the catalytic process employs a transition metal oxyhydroxide as a catalyst to catalyze monopersulfates to produce sulfate radicals and active oxygen species;
the oxyhydroxide is iron oxyhydroxide;
the reactive oxygen species include: hydroxyl radicals, superoxide radicals, and singlet oxygen non-radicals;
the synthesis process of the iron oxyhydroxide comprises the following steps:
step S241, dropwise adding NaOH solution with the concentration of 1mol/L into Fe (NO) with the concentration of 1.2mol/L according to the volume ratio of 3:1 under the condition of stirring3)3Obtaining vermilion precipitate in the solution;
step S242, after the vermilion is completely precipitated, adjusting the pH value of the mixed solution to 8-12, standing for 1-4 h, and then putting the mixed solution into a heat preservation box to activate for 2h at the constant temperature of 30 ℃;
step S243, repeatedly washing the precipitate with water until the pH value is 7-9;
and step S244, drying the cleaned precipitate at constant temperature of 30 ℃ to obtain the iron oxyhydroxide.
5. A catalytic process according to any one of claims 1 to 4, characterized in that it comprises the following steps:
step S11, grinding the solid material of the transition metal oxyhydroxide to obtain catalyst powder;
step S12, adding monopersulfate into water to prepare a first solution of 0.15-0.3 mol/L;
and step S13, adding the catalyst powder into the first solution, stirring at the speed of 100 r/min-400 r/min, and activating monopersulfate to generate sulfate radicals and active oxygen species.
6. The catalytic process according to any one of claims 1 to 4, wherein the transition metal oxyhydroxide is supported on a metal oxide, or the transition metal oxyhydroxide is supported on a non-metal support, or the transition metal oxyhydroxide is doped with other transition metal ions.
7. The catalytic process according to claim 6, wherein the metal oxide supported on the transition metal oxyhydroxide comprises: TiO 22、ZnO、CuO、Al2O3、Fe3O4、MnO2、Bi2O3、CeO2、NiO、Co3O4Or V2O5(ii) a The non-metal carrier includes: three-dimensional graphene, redox graphene, carbon nanotubes or molecular sieves; the molecular formula of the transition metal hydroxide doped with transition metal ions is MxN1-xOOH, wherein 0<x<1, M is Ni, Mn, Co, Zn or Fe element,n is Ni, Mn, Co, Zn, Fe, Mg or Cu, and M and N are different elements.
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