CN112340831B - 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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- CN112340831B CN112340831B CN202011280325.1A CN202011280325A CN112340831B CN 112340831 B CN112340831 B CN 112340831B CN 202011280325 A CN202011280325 A CN 202011280325A CN 112340831 B CN112340831 B CN 112340831B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 94
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 64
- 230000000593 degrading effect Effects 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000011028 pyrite Substances 0.000 claims abstract description 111
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 111
- 239000007800 oxidant agent Substances 0.000 claims abstract description 41
- 230000001590 oxidative effect Effects 0.000 claims abstract description 41
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 230000015556 catabolic process Effects 0.000 claims description 19
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000033558 biomineral tissue development Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007857 degradation product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940095991 ferrous disulfide Drugs 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 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
- 238000001914 filtration Methods 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral 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
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
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 reactivity, low efficiency and the like when the organic pollutants in the wastewater are degraded by the existing natural pyrite. The method for rapidly degrading organic pollutants in wastewater comprises the steps of pre-reacting pyrite with an oxidant, and then introducing a pre-reaction product into the wastewater to degrade the organic pollutants. The device comprises a column body, wherein a hollow cavity is formed in the column body and is used for placing pyrite; the upper part of the column body is provided with a first feeding hole and a second feeding hole; 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 the oxidant aqueous solution, and the second feed inlet is used for introducing water. The method can rapidly and effectively degrade the 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, advanced oxidation technology has been widely used because of 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 aims to oxidize and degrade organic molecules through strong oxidative active free radicals. The most typical advanced oxidation technique is Fenton technology, which uses Fe 2+ And H 2 O 2 The reaction produces highly oxidative hydroxyl radicals. Because the homogeneous Fenton process has the defects of difficult recovery of the catalyst, narrow pH range (2.5-3.5) of operation, large amount of iron mud production and the like, the method has obvious practical applicationAnd defects are displayed. Researchers develop iron-based solid catalysts (such as zero-valent iron, ferroferric oxide, goethite and the like) to degrade organic pollutants through heterogeneous Fenton reaction, but the problems of narrow operating pH range, low efficiency, difficult separation of catalyst particles and the like still exist. Chemically synthesized FeS 2 Or high purity natural pyrite has been reported for heterogeneous Fenton catalysts, chemically synthesized FeS 2 Or the high-purity natural pyrite has higher price and narrow operating pH range; natural pyrite is low in price but low in reactivity, and the operating pH range is narrow.
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) The existing natural pyrite has low reactivity when being used for degrading organic pollutants in wastewater; (2) The existing natural pyrite is long in time and low in efficiency when being used for degrading organic pollutants in wastewater; (3) The existing natural pyrite has poor degradation effect when being used for degrading organic pollutants in wastewater, and has narrow operation pH range; (4) When the existing natural pyrite is used for degrading organic pollutants in wastewater, the pyrite surface activity is easy to be polluted, so that the catalytic efficiency is reduced.
The aim 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, wherein pyrite and an oxidant are pre-reacted, and then a pre-reaction product is introduced into the wastewater to degrade the organic pollutants.
Further, the method comprises the following steps:
step 1, closing a valve at the bottom of a column body, and filling pyrite into an inner cavity of the column body;
step 2, introducing an oxidant aqueous solution into an inner cavity of the column body, and pre-reacting the oxidant with 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, so that liquid phase reaction products in the inner cavity of the column body completely enter a wastewater tank, opening a stirring device for stirring, and degrading wastewater after full reaction.
Further, in the step 1, the pyrite in the column is divided into three size fractions, namely a first size fraction, a second size fraction and a third size fraction from bottom to top, and the average particle sizes of the pyrite in the three size fractions accord with the following relationship: the first fraction > the second fraction > the third fraction.
Further, the particle size of the pyrite is 0.8-8.0 mm.
Further, the oxidant is hydrogen peroxide or peracetic 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 5-50min.
On the other hand, the invention also provides a device for rapidly degrading the organic pollutants in the wastewater, which comprises a column body, wherein the interior of the column body is a hollow cavity for placing pyrite; the upper part of the column body is provided with a first feeding hole and a second feeding hole; 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 the oxidant aqueous solution, and the second feed inlet is used for introducing water.
Further, a stirring device is arranged in the wastewater tank.
Further, the filter screen is a ceramic filter screen.
Further, the hollow cavity in the cylinder is divided into three sections, namely a first hollow cavity section, a second hollow cavity section and a third hollow cavity from bottom to top, and the first-size-fraction pyrite, the second-size-fraction pyrite and the third-size-fraction pyrite are sequentially placed, wherein the average granularity of the three-size-fraction pyrite accords with the following relation: the first fraction > the second fraction > the third fraction.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) According to the method for rapidly degrading the organic pollutants in the wastewater, pyrite and an oxidant are pre-reacted, and then the liquid reaction product is introduced into the wastewater to degrade the organic pollutants, so that a large amount of hydroxyl free radicals are generated in the process, and the hydroxyl free radicals with strong oxidability are non-selective to the degradation of the organic pollutants, so that most of the organic pollutants can be basically degraded, further, the oxidative degradation of the organic pollutants in water is realized, and the mineralization degree of the organic pollutants is higher. 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, from original 2-5h to 7-60 min).
2) In the method provided by the invention, a large amount of H can be generated in the pre-reaction process of pyrite and the oxidant + And S is 2 2- ，H + The pH of the solution can be spontaneously reduced, so that the pH application range is wider (for example, pH 3-10); s is S 2 2 Can promote Fe 2+ /Fe 3+ Ion circulation, the catalytic efficiency is obviously improved; the reaction system is suitable for degrading different kinds of organic pollutants.
3) The device for rapidly degrading the organic pollutants in the wastewater can be well applied to the method provided by the invention, and well solves the problem of separation of the catalyst (pyrite), and after the device is adopted, the pollution of impurities and organic pollutant degradation products contained in the organic wastewater to the surface of the catalyst (pyrite) is avoided, the activity of the catalyst (pyrite) is improved, and the service life of the catalyst (pyrite) is prolonged.
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 may 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, like numbers referring to like parts throughout the drawings.
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 inlet; 2-a second feed inlet; 3-column; 4-stirring paddles; 5-a catheter; 6-a wastewater tank.
Detailed Description
An apparatus and method for rapidly degrading organic contaminants in wastewater is described in further detail below with reference to specific examples, which are for comparison and explanation purposes only, and the present invention is not limited to these examples.
It is noted that relational terms such as first, second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily implying or requiring any actual such relationship or order between such entities or actions. In the present invention, the description of the indicated orientations or positional relationships such as "upper, lower, left, right, front, rear, inner, outer, vertical, horizontal, top, bottom, middle", etc. is used merely for convenience in describing and understanding the present invention, and does not indicate or imply that the devices or elements must have a specific orientation, be constructed or operated in a specific orientation.
The existing method for degrading organic pollutants in wastewater by using natural pyrite is generally to directly add pyrite and an oxidant (such as hydrogen peroxide) into the wastewater for stirring, so that hydroxyl radicals with strong oxidability are generated, and the hydroxyl radicals can degrade the organic pollutants in the wastewater. The pyrite reaction activity of the method is low, the required time is long, the efficiency is low, and the operation pH range is narrow; and pyrite is directly added into the wastewater, separation and recovery are needed, the surface of pyrite is easy to be polluted by degradation products in the wastewater, and the catalytic activity and the service life are reduced.
The invention provides a device for rapidly degrading organic pollutants in wastewater, which is shown in fig. 1, and comprises a column body 3, wherein the interior of the column body 3 is a hollow cavity for placing pyrite; the upper part of the column body 3 is provided with a first feeding hole 1 and a second feeding hole 2; the bottom of the column body 3 is provided with a filter screen which is used for preventing pyrite particles from flowing out; the column body 3 is connected with a wastewater tank 6 through a conduit 5; the first feed port 1 is used for introducing an aqueous oxidant solution, and the second feed port 2 is used for introducing water.
It should be noted that, the heat-insulating layer is disposed outside the column 3, because the catalytic reaction is exothermic, the reaction generates heat to raise the temperature in the column 3, and the raised temperature is beneficial to the catalytic reaction; therefore, the heat loss can be reduced by providing the heat insulating layer, and the reaction is promoted.
Specifically, pyrite placed in the column 3 is divided into three size fractions, namely a first size fraction, a second size fraction and a third size fraction from bottom to top, and the average particle sizes of the pyrite in the three size fractions accord with the following relationship: the first fraction > the second fraction > the third fraction; 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 specific surface area of the small-sized pyrite is large, the catalytic reaction is facilitated, and the large-sized pyrite of the first size fraction can reduce the flow resistance of the solution at the bottom.
Considering the conditions of use of the filter screen in the present application, the filter screen is required to have good acid and alkali resistance and corrosion resistance, and therefore, a ceramic filter screen is used as the filter screen. And the ceramic filter screen is never blocked, has long service life and excellent filtering effect, can greatly reduce the labor cost for cleaning the filter screen, and improves the efficiency for degrading organic pollutants in wastewater.
Specifically, the filter screen is oversized and cannot prevent pyrite particles from flowing out; too small a size of the screen increases the outflow resistance of the water in the column. Thus, the pore size of the control screen is smaller than the minimum particle size of pyrite particles.
Specifically, the mesh of filter screen is the big type of falling V of upper portion diameter little, lower part diameter, and the diameter of upper portion of filter screen is less than the minimum particle diameter of pyrite granule, can prevent that pyrite granule from flowing out, simultaneously, the resistance that the solution passed through can be reduced in the design of falling V type.
In order to accelerate the degradation speed of organic pollutants in the wastewater, the stirring device is arranged in the wastewater tank 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. The stirring device is, for example, a stirring paddle 4.
In order to effectively control the addition of the raw materials, a one-way valve is arranged at the joint of the cylinder 3 and the guide pipe 5 and is used for controlling the addition of the raw materials.
Specifically, the top of the wastewater tank 6 is provided with a water injection port, and the water injection port is used for injecting wastewater into the wastewater tank 6; the bottom of the wastewater tank 6 is provided with a water outlet port, the water outlet port is provided with a valve, the treated clean water in the wastewater tank 6 is led out through the water outlet port, and the valve is used for controlling water flow.
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.
Specifically, the method for rapidly degrading the organic pollutants in the wastewater adopts the device for rapidly degrading the organic pollutants in the wastewater, and comprises the following steps:
step 1, closing a valve at the bottom of a column body 3, and filling pyrite into an inner cavity of the column body 3;
step 2, introducing an oxidant aqueous solution into the inner cavity of the column 3 to pre-react the oxidant with the natural pyrite, so as to obtain a liquid phase reaction product;
and 3, opening a valve at the bottom of the column body 3, so that liquid phase reaction products in the inner cavity of the column body 3 completely enter a wastewater tank, and opening a stirring device for stirring, and after full reaction, degrading the wastewater.
Specifically, the organic pollutants in the wastewater comprise mineral processing agents, pesticides, medicines, dyes and phenolic compounds.
Specifically, in the step 1, the pyrite is selected from natural pyrite. Wherein FeS in pyrite 2 The content of (2) is 15% -40%.
Specifically, in the step 1, the particle size of pyrite is too large, the specific surface area of the particle is reduced, the contact between the surface active site of pyrite and the oxidant is reduced, and the reaction efficiency is reduced; the size is too small, the fluidity of the liquid in the column is poor, and the excessive reaction is easily caused by the continuous reaction of the column, so that the utilization efficiency of the catalyst is reduced, and the particle size of the natural pyrite is controlled to be 0.8-8.0 mm.
Further, pyrite in the column 3 is divided into three size fractions, namely a first size fraction, a second size fraction and a third size fraction from bottom to top, and the average particle sizes of the pyrite in the three size fractions accord with the following relationship: the first fraction > the second fraction > the third fraction; 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 specific surface area of the small-sized pyrite is large, the catalytic reaction is facilitated, 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 of the third size fraction is 0.8-2.0 mm (30% -40% of the total volume of the pyrite), the average particle size of the pyrite of the second size fraction is 2.0-4.0 mm (30% -40% of the total volume of the pyrite), and the average particle size of the pyrite of the first size fraction is 4.0-8.0 mm (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 mainly comprises the reaction of the pyrite catalyst and the oxidant, the pH of the solution is reduced, the dissolution of ferrous ions and the catalytic reaction are promoted, the reaction time is short, and the pH of the solution is reduced to a limited extent due to insufficient reaction; the excessive reaction time causes excessive loss of the active center of the catalyst, so that the pre-reaction time is controlled to be 2-10min.
Specifically, in the step 2, the oxidant is hydrogen peroxide or peracetic acid, and the hydrogen peroxide and the peracetic acid are both green oxidants, so that secondary pollution is avoided, 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 excessive addition amount of the oxidant aqueous solution can cause low oxidant utilization rate and excessive residual amount of the oxidant in the wastewater; too small may result in insufficient degradation of the organic matter. Therefore, the mass ratio of the oxidant aqueous solution to the wastewater is controlled to be 1:10-100; when the oxidant is hydrogen peroxide, the mass concentration of the hydrogen peroxide aqueous solution is 5-10%, and when the oxidant is peracetic acid, the mass concentration of the peracetic acid aqueous solution is 2-8%; the mass concentration of the organic pollutants in the wastewater is 10-200mg/L.
Specifically, in the step 3, the electric energy is consumed due to the excessive stirring speed; too small stirring speed causes low reaction efficiency and long time consumption. Therefore, the stirring speed is controlled to be 50-300 rpm. The long reaction time can increase the running cost and reduce the wastewater treatment efficiency; the time is too short, and the organic wastewater is insufficiently treated. Thus, the reaction time was controlled to be 5 to 50 minutes.
Specifically, in the 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 residues remain in the column, at this time, water may be introduced into the column 3 through the second feed inlet 2, so that the liquid phase reaction product in the column completely enters the wastewater tank.
Specifically, in the above method, pyrite in the column 3 can be used multiple times.
The main component of pyrite is ferrous disulfide, ferrous iron of ferrous disulfide can react with an oxidant to generate active free radicals with strong oxidability, and the active free radicals with strong oxidability 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 discovers through intensive research: taking hydrogen peroxide as an example, pyrite is reacted with hydrogen peroxide with a certain concentration to generate hydrogen ions (shown in the following formulas 1 and 2), so that the pH is reduced, the acidic environment is favorable for dissolving ferrous ions in the pyrite, the reaction of the ferrous ions with the hydrogen peroxide is further promoted to generate a large amount of strong oxidative hydroxyl free radicals (formula 3), and S generated in the dissolving process of the pyrite 2- The ion has good reducibility and can promote Fe 2+ /Fe 3+ The cycle (formula 2) maintains higher catalytic efficiency. Therefore, the invention can obviously improve the catalytic reaction efficiency and greatly shorten the reaction time by firstly reacting pyrite with hydrogen peroxide with a certain concentration and then introducing the liquid reaction product into the wastewater to degrade the 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 spontaneously reduced in the reaction process, so that the pH application range is wider (3-10); the reaction system is suitable for degrading different kinds of organic pollutants; the natural pyrite is used as a catalyst with lower cost.
FeS 2 + 15/2 H 2 O 2 → Fe 3+ + 2SO 4 2- + H + + 7H 2 O (1)
FeS 2 + 14Fe 3+ + 8H 2 O → 15Fe 2+ + 2SO 4 2- + 16H + (2)
H 2 O 2 + Fe 2+ + H + → Fe 3+ + ·OH + H 2 O (3)
The device for rapidly degrading organic pollutants in wastewater can be well applied to the method provided by the invention, and the problem of pyrite separation is well solved. Due to the reaction of hydrogen peroxide with pyrite, fe is included 2+ Ions, S 2 2- Liquid reactants of ions, hydroxyl radicals and unreacted hydrogen peroxide, wherein the liquid reactants enter a wastewater pool containing organic pollutants, and Fe 2+ Ions and hydrogen peroxide continue to generate hydroxyl radicals, S 2 2- Ion promotion of Fe 2+ /Fe 3+ And the organic pollutants are efficiently degraded by circulation. In addition, the existing reaction process for degrading the organic pollutants in the wastewater is to add the catalyst (pyrite) and hydrogen peroxide into the organic pollutant wastewater, the catalyst (pyrite) after the 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 reduced.
The technical scheme of the invention can greatly shorten the reaction time, avoid the influence of organic 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, which is shown in fig. 1, and comprises a column body 3, wherein the interior of the column body 3 is a hollow cavity for placing pyrite; the upper part of the column body 3 is provided with a first feeding hole 1 and a second feeding hole 2; the bottom of the column body 3 is provided with a ceramic filter screen which is used for preventing pyrite particles from flowing out; the column body 3 is connected with a wastewater tank 6 through a conduit 5; the first feed inlet 1 is used for introducing hydrogen peroxide, and the second feed inlet 2 is used for introducing water; the outside of the column body 3 is provided with an insulating layer. The pyrite in the column 3 is divided into three particle fractions, namely a first particle fraction, a second particle fraction and a third particle fraction from bottom to top; the average particle size of the pyrite of the third size fraction is 0.8-2.0 mm (30%), the average particle size of the pyrite of the second size fraction is 2.0-4.0 mm (30%), and the average particle size of the pyrite of the first size fraction is 4.0-8.0 mm (40%).
Wherein the mesh of the filter screen is of an inverted V shape with small diameter at the upper part and large diameter at the lower part, and the diameter size of the upper part of the filter screen is 0.75mm.
Specifically, a stirring paddle 4 is arranged in the wastewater tank 6; a one-way valve is arranged at the joint of the column body 3 and the guide pipe 5; the top of the wastewater tank 6 is provided with a water filling port; the bottom of the wastewater tank 6 is provided with a water outlet port, the water outlet port is provided with a valve, the treated clean water in the wastewater tank 6 is led out through the water outlet port, and the valve is used for controlling water flow.
Example 2
This example provides a method for rapidly degrading organic contaminants in wastewater using the apparatus of example 1 above. Comprising the following steps:
step 1, closing a valve at the bottom of a column body 3, and filling pyrite into an inner cavity of the column body 3; adding wastewater containing organic pollutants into a wastewater pool; the pyrite in the column 3 is divided into three particle fractions, namely a first particle fraction, a second particle fraction and a third particle fraction from bottom to top; the average grain diameter of the pyrite of the third grain stage is 1.0-1.8 mm (accounting for 30%), the average grain diameter of the pyrite of the second grain stage is 2.5-4.0 mm (accounting for 30%), and the average grain diameter of the pyrite of the first grain stage is 5.0-7.0 mm (accounting for 40%);
step 2, introducing an oxidant aqueous solution into the inner cavity of the column 3 to pre-react the oxidant with the natural pyrite for 2-10min; wherein, the mass ratio of the oxidant aqueous solution to the wastewater is 1:10-100.
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 a wastewater tank, opening a stirring device to stir at a stirring speed of 50-300 r/min, and after reacting for 5-50min, degrading the wastewater.
Specifically, in step 1, feS in pyrite 2 The content of (2) was 30%.
In order to study the wide application range of the method of the invention, different oxidants are adopted to treat various waste water in the embodiment, and experimental conditions and results are shown in the following table 1:
TABLE 1 Experimental conditions and results
Specifically, in this embodiment, the organic contaminant solution has a pH of 3 to 10.
Specifically, in this embodiment, pyrite in the column 3 can be used several times, and used 5 times in succession, and the degradation rate of organic pollutants still keeps more than 95% of the original degradation rate.
Comparative example 1
The comparative example provides a method for degrading organic pollutants in wastewater, which adopts the prior art, hydrogen peroxide with the mass concentration of 10% and pyrite are simultaneously added into wastewater of # 1 and # 4 (the pH of the solution is 5-8), and after stirring reaction is carried out for 2-5 hours, the degradation rate of the organic pollutants in the wastewater is 30% -65%, and the mineralization rate (total organic carbon removal rate) is 10% -30%. And the degradation rate of the organic pollutants in the reuse of pyrite is reduced to 50-70% of the initial degradation rate.
As can be seen from comparative example 1 and comparative example 1, the method for rapidly degrading organic pollutants in wastewater by using the method of the invention has short reaction time (for example, the total reaction time is 7-60 min) which is far lower than that of the prior art for 2-5h; the pH is applicable in a wide range (for example, pH 3-10), the reaction system is applicable to degradation of different types of organic pollutants, the degradation effect on various organic pollutants is good (for example, the degradation rate is more than 90%, the mineralization rate (total organic carbon removal rate) is more than 50%), the degradation rate is higher than 30% -65% of the existing technology, and the mineralization rate is higher than 10% -30% of the existing technology; and pyrite can be used for multiple times, and has low cost and remarkable economic benefit.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (2)
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;
the method for rapidly degrading the organic pollutants in the wastewater comprises the following steps:
step 1, closing a valve at the bottom of a column body (3), and filling pyrite into an inner 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 with the natural pyrite for 2-10min, so as to obtain a liquid phase reaction product; the oxidant is hydrogen peroxide; when the oxidant is hydrogen peroxide, the mass concentration of the hydrogen peroxide aqueous solution is 5% -10%;
step 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 a wastewater tank, opening a stirring device for stirring, and after full reaction, completing degradation of wastewater, wherein the reaction time is 5-50min;
the hydrogen peroxide reacts with pyrite to produce Fe 2+ Ions, S 2 2- Liquid reactants of ions, hydroxyl radicals and unreacted hydrogen peroxide, wherein the liquid reactants enter a wastewater pool containing organic pollutants, and Fe 2+ Ions and hydrogen peroxide continue to generate hydroxyl radicals, S 2 2- Ion promotion of Fe 2+ /Fe 3+ The organic pollutants are efficiently degraded by circulation;
in the step 1, pyrite in the column (3) is divided into three particle fractions, namely a first particle fraction, a second particle fraction and a third particle fraction from bottom to top, and the average particle sizes of the pyrite in the three particle fractions accord with the following relationship: the first fraction > the second fraction > the third fraction;
the particle size of the pyrite is 0.8-8.0 mm;
the average grain diameter of the pyrite in the third grain stage is 0.8-2.0 mm, accounting for 30% -40% of the total volume of the pyrite; the average grain diameter of the pyrite in the second grain stage is 2.0-4.0 mm, accounting for 30% -40% of the total volume of the pyrite; the average particle size of the pyrite in the first size fraction is 4.0-8.0 mm, accounting for 35-45% of the total volume of the pyrite.
2. The method for rapid degradation of organic contaminants in wastewater according to claim 1, characterized in that the mass ratio of said aqueous oxidant solution to wastewater is 1:10-100.
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