CN112340831A - Device and method for rapidly degrading organic pollutants in wastewater - Google Patents
Device and method for rapidly degrading organic pollutants in wastewater Download PDFInfo
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- CN112340831A CN112340831A CN202011280325.1A CN202011280325A CN112340831A CN 112340831 A CN112340831 A CN 112340831A CN 202011280325 A CN202011280325 A CN 202011280325A CN 112340831 A CN112340831 A CN 112340831A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 101
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 73
- 230000000593 degrading effect Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 102
- 239000011028 pyrite Substances 0.000 claims abstract description 100
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 99
- 230000001590 oxidative effect Effects 0.000 claims abstract description 43
- 239000007800 oxidant agent Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 23
- 230000015556 catabolic process Effects 0.000 claims description 22
- 238000006731 degradation reaction Methods 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 13
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 11
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- -1 hydroxyl radicals Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052960 marcasite Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007857 degradation product Substances 0.000 description 3
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229940095991 ferrous disulfide Drugs 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
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- 238000010170 biological method Methods 0.000 description 1
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- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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Images
Classifications
-
- 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention discloses a device and a method for rapidly degrading organic pollutants in wastewater, belongs to the field of organic wastewater treatment, and solves the problems of low reaction activity, low efficiency and the like when the organic pollutants in the wastewater are degraded by natural pyrite. The method for quickly degrading the organic pollutants in the wastewater comprises the steps of pre-reacting pyrite with an oxidant, and introducing a pre-reaction product into the wastewater to degrade the organic pollutants. The device comprises a cylinder, wherein a hollow cavity is arranged inside the cylinder and used for placing pyrite; the upper part of the cylinder is provided with a first feed inlet and a second feed inlet; the bottom of the column body is provided with a filter screen; the column body is connected with the wastewater pool through a conduit; the first feed inlet is used for introducing an oxidant aqueous solution, and the second feed inlet is used for introducing water. The method can quickly and effectively degrade organic pollutants in the wastewater, and the pyrite can be used for multiple times, so that the cost is low.
Description
Technical Field
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a device and a method for rapidly degrading organic pollutants in wastewater.
Background
In recent years, with the continuous development of economy and the rapid promotion of industrialization in China, more and more organic pollutants are discharged into water, and with the long-term accumulation and enrichment of the organic pollutants, the organic pollutants threaten water environment and aquatic organisms, and finally influence the health of human beings. Because of the complex components of these organic pollutants, it is difficult to perform harmless treatment on organic wastewater by conventional physical, chemical or biological methods, such as adsorption, biodegradation, photocatalysis or electrochemical oxidation. In recent years, the advanced oxidation technology is widely applied due to simple operation and good effect of treating organic pollutants in wastewater.
The advanced oxidation technology is a high-efficiency organic wastewater treatment method, and mainly degrades organic molecules through strong-oxidative-activity free radical oxidation. The most typical advanced oxidation technique is the Fenton process, with Fe2+And H2O2The reaction produces strongly oxidizing hydroxyl radicals. The homogeneous Fenton process has the defects of difficult catalyst recovery, narrow operation pH range (2.5-3.5), generation of a large amount of iron mud and the like, and has obvious defects in practical application. Researchers develop iron-based solid catalysts (such as zero-valent iron, ferroferric oxide, goethite and the like) to realize the degradation of organic pollutants through heterogeneous Fenton reaction, but the problems of narrow operation pH range, low efficiency, difficult separation of catalyst particles and the like still exist. Chemically synthesized FeS2Or high purity natural pyrite has been reported for use in heterogeneous Fenton catalysts, chemically synthesized FeS2Or the high-purity natural pyrite is high in price and narrow in operation pH range; the natural pyrite has low price, low reactivity and narrow operation pH range.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide an apparatus and a method for rapidly degrading organic pollutants in wastewater, which can solve at least one of the following technical problems: (1) when the existing natural pyrite is used for degrading organic pollutants in wastewater, the reaction activity is low; (2) the existing natural pyrite has long time and low efficiency when being used for degrading organic pollutants in wastewater; (3) when the existing natural pyrite is used for degrading organic pollutants in wastewater, the degradation effect is poor, and the operation pH range is narrow; (4) when the existing natural pyrite is used for degrading organic pollutants in wastewater, the surface activity of the pyrite is easily polluted, so that the catalytic efficiency is reduced.
The purpose of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides a method for rapidly degrading organic pollutants in wastewater, which comprises the steps of pre-reacting pyrite with an oxidant, and introducing a pre-reaction product into the wastewater to degrade the organic pollutants.
Further, the method comprises the following steps:
and 3, opening a valve at the bottom of the column body, enabling liquid-phase reaction products in the inner cavity of the column body to completely enter the wastewater tank, opening a stirring device for stirring, and after full reaction, finishing degradation of wastewater.
Further, in the step 1, the pyrite in the column is divided into three size fractions, which are a first size fraction, a second size fraction and a third size fraction from bottom to top, and the average particle sizes of the pyrites in the three size fractions meet the following relationship: first particle size stage > second particle size stage > third particle size stage.
Further, the particle size of the pyrite is 0.8-8.0 mm.
Further, the oxidant is hydrogen peroxide or peroxyacetic acid.
Further, the mass ratio of the oxidant aqueous solution to the wastewater is 1: 10-100.
Further, in the step 3, the reaction time is 5-50 min.
On the other hand, the invention also provides a device for rapidly degrading organic pollutants in wastewater, which comprises a cylinder, wherein a hollow cavity is arranged inside the cylinder and used for placing pyrite; the upper part of the cylinder is provided with a first feed inlet and a second feed inlet; the bottom of the column body is provided with a filter screen; the column body is connected with the wastewater pool through a conduit; the first feed inlet is used for introducing an oxidant aqueous solution, and the second feed inlet is used for introducing water.
Further, a stirring device is arranged in the wastewater pool.
Further, the filter screen is a ceramic filter screen.
Further, the hollow cavity of the inside of cylinder is the three-section, is first hollow cavity section, second hollow cavity section and third hollow cavity from bottom to top in proper order, places first size fraction pyrite, second size fraction pyrite, third size fraction pyrite in proper order, and the average granularity of the pyrite of three size fractions accords with following relation: first size fraction > second size fraction > third size fraction.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) the method for rapidly degrading the organic pollutants in the wastewater provided by the invention comprises the steps of pre-reacting pyrite with an oxidant, introducing a liquid reaction product into the wastewater to degrade the organic pollutants, wherein a large amount of hydroxyl free radicals are generated in the process, the hydroxyl free radicals with strong oxidizing property are nonselective to the degradation of the organic pollutants, and can basically degrade most of the organic pollutants, so that the oxidative degradation of the organic pollutants in the water is realized, and the mineralization degree of the organic pollutants is larger. The method can obviously improve the catalytic reaction efficiency and greatly shorten the reaction time; so that the degradation time of the organic pollutants is reduced to 1/2-1/3 (for example, reduced to 7-60min from the original 2-5 h).
2) In the method provided by the invention, the pre-reaction process of pyrite and oxidant can generate a large amount of H+And S2 2-，H+The solution pH can be spontaneously reduced, thus the pH application range is wider (for example, the pH is 3-10); s2 2-Can promote Fe2+/Fe3+The ion circulation obviously improves the catalytic efficiency; the reaction system is suitable for degrading different organic pollutants.
3) The device for rapidly degrading the organic pollutants in the wastewater provided by the invention can be better suitable for the method provided by the invention, and the problem of separating the catalyst (pyrite) is well solved.
Additional features and advantages of the invention will be set forth in the description which follows, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
Fig. 1 is a schematic structural view of an apparatus for rapidly degrading organic pollutants in wastewater according to the present invention.
Reference numerals:
1-a first feed port; 2-a second feed port; 3-a column; 4-stirring paddle; 5-a catheter; 6-a wastewater pond.
Detailed Description
An apparatus and method for rapidly degrading organic pollutants in wastewater will be described in further detail with reference to specific examples, which are provided for purposes of comparison and explanation only and to which the present invention is not limited.
It is noted that relational terms such as first, second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily implying or requiring any such actual relationship or order between such entities or actions. In the present invention, descriptions used herein to indicate orientations or positional relationships such as "upper, lower, left, right, front, rear, inside, outside, vertical, horizontal, top, bottom, middle" and the like are used only for convenience of description and understanding of the present invention, and do not indicate or imply that the device or element must have a particular orientation, be constructed or operated in a particular orientation.
The existing method for degrading organic pollutants in wastewater by using natural pyrite generally comprises the steps of directly adding pyrite and an oxidant (such as hydrogen peroxide) into wastewater and stirring to generate hydroxyl free radicals with strong oxidizing property, wherein the hydroxyl free radicals can degrade the organic pollutants in the wastewater. The method has the advantages of low reactivity of the pyrite, long required time, low efficiency and narrow operation pH range; and the pyrite is directly added into the wastewater and needs to be separated and recovered, the surface of the pyrite is easily polluted by degradation products in the wastewater, the catalytic activity is reduced, and the service life is prolonged.
The invention provides a device for rapidly degrading organic pollutants in wastewater, which comprises a cylinder 3, wherein a hollow cavity is arranged inside the cylinder 3 and is used for placing pyrite, and the cylinder 3 is provided with a plurality of holes; the upper part of the cylinder 3 is provided with a first feed inlet 1 and a second feed inlet 2; the bottom of the cylinder 3 is provided with a filter screen which is used for preventing pyrite particles from flowing out; the column 3 is connected with a wastewater pool 6 through a conduit 5; the first inlet 1 is used for introducing the oxidant water solution, and the second inlet 2 is used for introducing water.
It should be noted that the heat insulating layer is arranged outside the column body 3, because the catalytic reaction is an exothermic reaction, the temperature in the column body 3 is raised by the heat generated by the reaction, and the raised temperature is favorable for the catalytic reaction; therefore, the heat loss can be reduced and the reaction can be promoted by arranging the heat preservation layer.
Specifically, the pyrite placed in the column 3 is divided into three grain size sections, which are a first grain size section, a second grain size section and a third grain size section from bottom to top in sequence, and the average particle size of the pyrite in the three grain size sections conforms to the following relationship: a first particle size stage > a second particle size stage > a third particle size stage; the small-sized pyrite of the third size fraction is firstly contacted with the oxidant solution at the upper part of the column 3, the large specific surface area of the small-sized pyrite is beneficial to catalytic reaction, and the large-sized pyrite of the first size fraction can reduce the flow resistance of the solution at the bottom.
In consideration of the use conditions of the filter screens in the present application, the filter screens are required to have good acid-base resistance and corrosion resistance, and therefore, ceramic filter screens are used as the filter screens. And the ceramic filter screen never blocks up, long service life, filter effect are excellent, can significantly reduce the cost of labor of clearance filter screen, improve the efficiency of the organic pollutant in the degradation waste water.
Specifically, the size of the filter screen is too large to prevent the pyrite particles from flowing out; the undersize of the screen increases the outflow resistance of the water in the column. Therefore, the pore size of the control screen is smaller than the minimum particle size of the pyrite granule.
Specifically, the mesh of filter screen is the shape of falling V that upper portion diameter is little, the big diameter of lower part diameter, and the diameter on the upper portion of filter screen is less than the minimum particle diameter of pyrite granule, can prevent that the pyrite granule from flowing out, and simultaneously, the design of the shape of falling V can reduce the resistance that solution passes through.
In order to accelerate the degradation speed of organic pollutants in the wastewater, the stirring device is arranged inside the wastewater pool 6, and the stirring device is adopted to stir the wastewater in the process of degrading the organic wastewater, so that the degradation speed of the organic wastewater can be accelerated. Illustratively, the stirring device is a stirring paddle 4.
In order to effectively control the adding amount of each raw material, a one-way valve is arranged at the joint of the cylinder 3 and the conduit 5 and used for controlling the adding amount of the raw materials.
Specifically, a water injection port is arranged at the top of the wastewater pool 6 and is used for injecting wastewater into the wastewater pool 6; the bottom of the wastewater pool 6 is provided with a water outlet, a valve is arranged on the water outlet, the treated clean water in the wastewater pool 6 is led out through the water outlet, and the valve is used for controlling water flow.
The invention provides a method for rapidly degrading organic pollutants in wastewater.
Specifically, the method for rapidly degrading organic pollutants in wastewater adopts the device for rapidly degrading organic pollutants in wastewater, and comprises the following steps:
and step 3, opening a valve at the bottom of the column body 3, enabling the liquid-phase reaction product in the inner cavity of the column body 3 to completely enter the wastewater tank, opening a stirring device for stirring, and after full reaction, finishing degradation of wastewater.
Specifically, the organic pollutants in the wastewater comprise beneficiation reagents, pesticides, medicines, dyes and phenolic compounds.
Specifically, in the step 1, natural pyrite is selected as the pyrite. Wherein the FeS in the pyrite2The content of (A) is 15-40%.
Specifically, in the step 1, the particle size of the pyrite is too large, the specific surface area of the particles is reduced, the contact of the surface active sites of the pyrite with the oxidant is reduced, and the reaction efficiency is reduced; the size is too small, the liquid mobility is poor in the cylinder, excessive reaction is easily caused by continuous reaction of the cylinder, and the utilization efficiency of the catalyst is reduced, so that the particle size of the natural pyrite is controlled to be 0.8-8.0 mm.
Further, the pyrite in the column 3 is divided into three size fractions, which are a first size fraction, a second size fraction and a third size fraction from bottom to top, and the average particle sizes of the pyrites in the three size fractions meet the following relationship: a first particle size stage > a second particle size stage > a third particle size stage; the small-sized pyrite of the third size fraction is firstly contacted with the oxidant solution at the upper part of the column 3, the large specific surface area of the small-sized pyrite is beneficial to catalytic reaction, and the large-sized pyrite of the first size fraction can reduce the flow resistance of the solution at the bottom.
Specifically, the average particle size of the pyrite in the third grading section is 0.8-2.0 mm (accounting for 30% -40% of the total volume of the pyrite), the average particle size of the pyrite in the second grading section is 2.0-4.0 mm (accounting for 30% -40% of the total volume of the pyrite), and the average particle size of the pyrite in the first grading section is 4.0-8.0 mm (accounting for 35% -45% of the total volume of the pyrite).
Specifically, in the step 2, the pre-reaction time is related to the concentration of the oxidant, the pre-reaction is mainly a reaction of a pyrite catalyst and the oxidant, the pH of the solution is reduced, the dissolution of ferrous ions and a catalytic reaction are promoted, the reaction time is short, and the reduction of the pH of the solution is limited due to insufficient reaction; the excessive loss of the active center of the catalyst caused by the overlong reaction time, so that the pre-reaction time is controlled to be 2-10 min.
Specifically, in the step 2, the oxidant is hydrogen peroxide or peracetic acid, and both the hydrogen peroxide and the peracetic acid are green oxidants, so that secondary pollution is not generated, and the price is low; the addition amount of the oxidant aqueous solution is related to the quality of the wastewater in the step 3, and the low utilization rate of the oxidant and the excessive residual amount of the oxidant in the wastewater can be caused by the excessive addition amount of the oxidant aqueous solution; too little can result in insufficient degradation of the organic material. Therefore, the mass ratio of the oxidant aqueous solution to the wastewater is controlled to be 1: 10-100 parts of; when the oxidant is hydrogen peroxide, the mass concentration of the aqueous solution of the hydrogen peroxide is 5 to 10 percent, and when the oxidant is peroxyacetic acid, the mass concentration of the aqueous solution of the peroxyacetic acid is 2 to 8 percent; the mass concentration of the organic pollutants in the wastewater is 10-200 mg/L.
Specifically, in the step 3, the electric energy is consumed when the stirring speed is too high; the reaction efficiency is low and the time consumption is long due to the undersize stirring speed. Therefore, the stirring speed is controlled to be 50 to 300 revolutions per minute. The overlong reaction time can increase the operation cost and reduce the wastewater treatment efficiency; the time is too short, and the organic wastewater is not sufficiently treated. Therefore, the reaction time is controlled to be 5-50 min.
Specifically, in step 3, considering that the concentration of the aqueous solution of the oxidizing agent is too high, the amount of the solution is small, and there is a residue in the column, at this time, water may be introduced into the column 3 through the second inlet 2, so that the liquid-phase reaction product in the column may completely enter the wastewater tank.
Specifically, in the above method, the pyrite in the column 3 can be used many times.
It should be noted that the main component of pyrite is ferrous disulfide, and ferrous iron of ferrous disulfide can react with oxidant to generate active radicals with strong oxidizing property, and the active radicals with strong oxidizing property can degrade organic pollutants in wastewater. The reaction rate of hydrogen peroxide and pyrite added into the wastewater in the practical application process is slow, so that the degradation rate of the wastewater is slow. Compared with the prior art, the applicant finds out through intensive research that: taking hydrogen peroxide as an example, firstly, pyrite reacts with hydrogen peroxide with a certain concentration to generate hydrogen ions (see the following formulas 1 and 2), so that the pH is reduced, the acid environment is favorable for dissolving out ferrous ions in the pyrite, the reaction of ferrous ions and hydrogen peroxide is further promoted to generate a large amount of strong oxidative hydroxyl radicals (formula 3), and S generated in the dissolving process of the pyrite2-The ions have good reducibility and can promote Fe2+/Fe3+And (2) circulation is carried out, so that high catalytic efficiency is maintained. Therefore, the method can obviously improve the catalytic reaction efficiency and greatly shorten the reaction time by firstly reacting the pyrite with hydrogen peroxide with certain concentration and then introducing the liquid reaction product into the wastewater for degrading organic pollutants; so that the degradation time of the organic pollutants is reduced to 1/2-1/3; the pH of the solution can be reduced spontaneously in the reaction process, so that the pH application range is wider (3-10); the reaction system is suitable for degrading different organic pollutants; the natural pyrite as the catalyst has lower cost.
FeS2+15/2H2O2→Fe3++2SO4 2-+H++7H2O (1)
FeS2+14Fe3++8H2O→15Fe2++2SO4 2-+16H+ (2)
H2O2+Fe2++H+→Fe3++·OH+H2O (3)
The device for rapidly degrading the organic pollutants in the wastewater can be well suitable for the method provided by the invention, and the problem of pyrite separation is well solved. Since hydrogen peroxide reacts with pyrite to produce Fe including2+Ion, S2 2-Liquid reactants of ions, hydroxyl radicals and unreacted hydrogen peroxide, the liquid reactants entering a wastewater basin containing organic contaminants, Fe2+The ions continue to generate hydroxyl radicals, S, with hydrogen peroxide2 2-Ion promoted Fe2+/Fe3+And (4) circulating to efficiently degrade the organic pollutants. In addition, in the existing reaction process for degrading organic pollutants in wastewater, a catalyst (pyrite) and hydrogen peroxide are added into the wastewater containing the organic pollutants, the catalyst (pyrite) after reaction is difficult to separate, and degradation products of the organic pollutants can be attached to the surface of the catalyst (pyrite) so that the activity of the catalyst (pyrite) is reducedAnd (3) contamination.
The technical scheme of the invention can greatly shorten the reaction time, avoid the influence of organic matter degradation products on the surface activity of the catalyst (pyrite), and has remarkable economic benefit.
Example 1
The embodiment provides a device for rapidly degrading organic pollutants in wastewater, as shown in fig. 1, the device comprises a cylinder 3, wherein a hollow cavity is arranged inside the cylinder 3 and used for containing pyrite; the upper part of the cylinder 3 is provided with a first feed inlet 1 and a second feed inlet 2; the bottom of the cylinder 3 is provided with a ceramic filter screen which is used for preventing pyrite particles from flowing out; the column 3 is connected with a wastewater pool 6 through a conduit 5; the first feed port 1 is used for introducing hydrogen peroxide, and the second feed port 2 is used for introducing water; the outside of the column 3 is provided with a heat preservation layer. Wherein, the pyrite inside the column 3 is divided into three grain grades, namely a first grain grade, a second grain grade and a third grain grade from bottom to top; the average particle size of the pyrite in the third fraction is 0.8 to 2.0mm (30%), the average particle size of the pyrite in the second fraction is 2.0 to 4.0mm (30%), and the average particle size of the pyrite in the first fraction is 4.0 to 8.0mm (40%).
Wherein the mesh of filter screen is the shape of an inverted V that upper portion diameter is little, the diameter of lower part is big, and the diameter size of the upper portion of filter screen is 0.75 mm.
Specifically, a stirring paddle 4 is arranged inside the wastewater tank 6; a one-way valve is arranged at the joint of the cylinder 3 and the conduit 5; the top of the wastewater pool 6 is provided with a water injection port; the bottom of the wastewater pool 6 is provided with a water outlet, a valve is arranged on the water outlet, the treated clean water in the wastewater pool 6 is led out through the water outlet, and the valve is used for controlling water flow.
Example 2
This example provides a method for rapidly degrading organic pollutants in wastewater using the apparatus of example 1 above. The method comprises the following steps:
And 3, opening a valve at the bottom of the column body 3 to enable liquid-phase reaction products in the inner cavity of the column body 3 to completely enter the wastewater pool, opening a stirring device to stir at the stirring speed of 50-300 r/min, and after reacting for 5-50min, finishing degradation of wastewater.
Specifically, in step 1, FeS is contained in pyrite2The content of (B) is 30%.
In order to study the wide application range of the method of the present invention, the present example uses different oxidants to treat various waste waters, and the experimental conditions and results are shown in table 1 below:
TABLE 1 Experimental conditions and results
Specifically, in this example, the solution of the organic contaminant has a pH of 3 to 10.
Specifically, in this embodiment, the pyrite in the column 3 can be used for multiple times, and continuously used for 5 times, and the degradation rate of the pyrite on the organic pollutants is still kept to be more than 95% of the initial degradation rate.
Comparative example 1
The comparative example provides a method for degrading organic pollutants in wastewater, the existing process is adopted, hydrogen peroxide with the mass concentration of 10% and pyrite are added into the wastewater No. 1-4 (the pH of the solution is 5-8) at the same time, after stirring reaction is carried out for 2-5h, the degradation rate of the organic pollutants in the wastewater is 30% -65%, and the mineralization rate (the total organic carbon removal rate) is 10% -30%. And the degradation rate of organic pollutants is reduced to 50-70% of the initial degradation rate when the pyrite is repeatedly used.
As can be seen from the comparison of example 1 and comparative example 1, the reaction time of the method for rapidly degrading organic pollutants in wastewater according to the invention is short (for example, the total reaction time is 7-60min), which is much shorter than that of the prior art, namely 2-5 h; the pH is applicable to a wide range (such as pH3-10), the reaction system is suitable for degrading different organic pollutants, the degradation effect on the organic pollutants is good (such as the degradation rate is greater than 90%, the mineralization rate (total organic carbon removal rate) is greater than 50%), the degradation rate is higher than 30% -65% of that of the prior art, and the mineralization rate is higher than 10% -30% of that of the prior art; and the pyrite can be used for many times, the cost is low, and the economic benefit is obvious.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. A method for rapidly degrading organic pollutants in wastewater is characterized in that pyrite and an oxidant are pre-reacted, and then a pre-reaction product is introduced into the wastewater to degrade the organic pollutants.
2. The method for rapidly degrading organic pollutants in wastewater according to claim 1, which comprises the following steps:
step 1, closing a valve at the bottom of a column body (3), and filling pyrite into an internal cavity of the column body (3);
step 2, introducing an oxidant aqueous solution into the inner cavity of the column body (3) to pre-react the oxidant and the natural pyrite for 2-10min to obtain a liquid-phase reaction product;
and 3, opening a valve at the bottom of the column body (3) to enable liquid-phase reaction products in the inner cavity of the column body (3) to completely enter the wastewater pool, opening a stirring device to stir, and after full reaction, finishing degradation of wastewater.
3. The method for rapidly degrading organic pollutants in wastewater according to claim 2, wherein in the step 1, the pyrite in the cylinder (3) is divided into three grades, namely a first grade, a second grade and a third grade from bottom to top, and the average particle sizes of the pyrite in the three grades meet the following relation: first particle size stage > second particle size stage > third particle size stage.
4. The method for rapidly degrading organic pollutants in wastewater according to claim 2, wherein the particle size of the pyrite is 0.8-8.0 mm.
5. The method for rapidly degrading organic pollutants in wastewater according to claim 2, wherein the oxidant is hydrogen peroxide or peracetic acid.
6. The method for rapidly degrading organic pollutants in wastewater according to claim 2, wherein the mass ratio of the oxidant aqueous solution to the wastewater is 1: 10-100.
7. The method for rapidly degrading organic pollutants in wastewater according to claims 2 to 6, wherein in the step 3, the reaction time is 5 to 50 min.
8. The device for rapidly degrading the organic pollutants in the wastewater is characterized by comprising a cylinder (3), wherein a hollow cavity is arranged inside the cylinder (3) and used for placing pyrite; the upper part of the cylinder (3) is provided with a first feed inlet (1) and a second feed inlet (2); the bottom of the cylinder (3) is provided with a filter screen; the column body (3) is connected with a wastewater pool (6) through a conduit (5); the first feed opening (1) is used for feeding an oxidant aqueous solution, and the second feed opening (2) is used for feeding water.
9. An apparatus for rapidly degrading organic pollutants in wastewater according to claim 8, characterized in that a stirring device is arranged inside the wastewater tank (6).
10. The apparatus for rapidly degrading organic pollutants in wastewater according to claim 8, wherein the filter screen is a ceramic filter screen.
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