CN113816484A - Method and apparatus for treating wastewater - Google Patents
Method and apparatus for treating wastewater Download PDFInfo
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- CN113816484A CN113816484A CN202111019918.7A CN202111019918A CN113816484A CN 113816484 A CN113816484 A CN 113816484A CN 202111019918 A CN202111019918 A CN 202111019918A CN 113816484 A CN113816484 A CN 113816484A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
Abstract
The invention relates to the field of environmental protection and discloses a method and a device for treating wastewater. The device comprises a catalytic oxidation tower, an optional water inlet and outlet system and an optional ozone treatment system, wherein the catalytic oxidation tower is respectively provided with an ozone exhaust port, a water outlet, a catalyst filling layer, an ozone inlet and a water inlet from top to bottom, the catalyst filling layer comprises a stepped annular ozone catalyst, the ozone catalyst comprises a carrier and a catalytic active component, the carrier is silicon oxide and/or aluminum oxide, the catalytic active component is at least one selected from transition metals, and the specific surface area of the ozone catalyst is 210-250 m-2/m3The radial compressive strength is 150-180N/cm. The method comprises the following steps: the wastewater to be treated is contacted with ozone in the presence of a catalyst for catalytic oxidation reaction, wherein the catalyst comprises the ozone catalyst in the form of a stepped ring. The invention can obtain the technical effects of good wastewater treatment effect and long service life of the catalyst, and the catalyst has the advantages of high activity, high stability, and low costThe device can continuously and stably operate for a long time and is not easy to block.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a method and a device for treating wastewater.
Background
The oxidation-reduction potential of ozone in water is high and can reach 2.07V, and the ozone has strong oxidizing capability, so that the chromaticity, odor and organic pollutants of wastewater can be quickly removed, and the ozone is concerned in wastewater treatment application. However, in the ozone oxidation process, ozone reacts slowly with some organic pollutants such as saturated aromatic hydrocarbons, and reacts with partial organic matters to generate aldehydes and carboxylic acids, and the substances are not easily oxidized by ozone, so that the effect of treating wastewater by using ozone alone is not satisfactory.
The ozone catalytic oxidation technology is a method for treating wastewater by adding a catalyst and oxidizing and decomposing organic matters in the wastewater by using hydroxyl radicals (. OH) generated by the reaction of the catalyst and ozone on the basis of treating the wastewater by using ozone only. The oxidation-reduction potential of hydroxyl free radical (OH) can reach 2.8V, and the method has the characteristics of strong oxidation capacity, no reaction selectivity and good treatment effect, and greatly widens the application range of ozone oxidation in wastewater treatment. Although the catalytic ozonation technology has a good treatment effect in the wastewater treatment process, some problems exist at the same time, and are mainly reflected in the following two aspects:
(1) the mass transfer efficiency of the ozone catalytic oxidation device is low, and the wastewater treatment method is not proper.
(2) The catalytic capability and the service life of the selected ozone catalyst still need to be further improved, the filling amount is large, and the catalytic oxidation tower is extremely easy to block, so that the operation is inconvenient.
Disclosure of Invention
The present invention is directed to overcoming the above problems with the prior art and providing a method and apparatus for treating wastewater.
In order to achieve the above object, in one aspect, the present invention provides an apparatus with a wastewater treatment function, the apparatus includes a catalytic oxidation tower, an optional water inlet and outlet system, and an optional ozone treatment system, wherein the catalytic oxidation tower is provided with an ozone exhaust port, a water outlet, a catalyst filling layer, an ozone inlet and a water inlet from top to bottom, the catalyst filling layer includes an ozone catalyst in a stepped ring form, the ozone catalyst includes a carrier and a catalytic active component, the carrier is silicon oxide and/or aluminum oxide, the catalytic active component is at least one selected from transition metals, and the specific surface area of the ozone catalyst is 210-250 m-2/m3The radial compressive strength is 150-180N/cm.
In a second aspect the present invention provides a method of treating wastewater, the method comprising: the wastewater to be treated is contacted with ozone in the presence of a catalyst for catalytic oxidation reaction, wherein the catalyst comprises the ozone catalyst in the form of a stepped ring.
Through the technical scheme, the device can obtain the technical effects of good wastewater treatment effect and long service life of the catalyst, can continuously and stably run for a long time, is not easy to block, and does not need to back wash the catalyst filling layer.
Drawings
Fig. 1 is a schematic view of the structure of an apparatus according to a preferred embodiment of the present invention.
Description of the reference numerals
1 a water inlet pool, 2 a water inlet pump, 3 a water inlet flow meter,
4 water inlet pipeline, 5 catalytic oxidation tower, 6 ozone exhaust port,
7 water outlet, 8 pall ring filling layers, 9 return water outlet,
10 catalyst filling layer, 11 tubular aerator, 12 ozone inlet,
13 backflow water inlet, 14 water inlet, 15 backflow water inlet pump,
16 reflux water inlet flow meter, 17 reflux pipeline, 18 ozone generator,
19 ozone inlet pipe, 20 ozone inlet flowmeter, 21 water outlet pipe,
22 water outlet pool, 23 ozone exhaust pipeline and 24 ozone tail gas treatment device.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a device with a wastewater treatment function, which comprises a catalytic oxidation tower 5, an optional water inlet and outlet system and an optional ozone treatment system, and is characterized in that the catalytic oxidation tower is respectively provided with an ozone exhaust port 6, a water outlet 7, a catalyst filling layer 10, an ozone inlet 12 and a water inlet 14 from top to bottom, the catalyst filling layer 10 comprises a stepped ring-shaped ozone catalyst, the ozone catalyst comprises a carrier and a catalytic active component, the carrier is silicon oxide and/or aluminum oxide, the catalytic active component is at least one selected from transition metals, and the specific surface area of the ozone catalyst is 210-250m2/m3(e.g., 215 m)2/m3、225m2/m3、230m2/m3、240m2/m3、250m2/m3Or onAny value between the above values), the radial compressive strength is 150-180N/cm (155N/cm, 160N/cm, 170N/cm, 175N/cm, 180N/cm or any value between the above values).
In the present invention, the "ozone catalyst in the form of a stepped ring" means that the ozone catalyst is cast in the form of a stepped ring, the diameter of the ring may be 25mm, the height of the ring may be 15mm, and the wall thickness of the ring may be 3 mm. The ozone catalyst can catalyze ozone to generate hydroxyl free radicals with strong oxidizing property, so that the reaction efficiency between ozone and pollutants is improved, and the wastewater treatment effect is improved. The ozone inlet 12 and the catalyst filling layer 10 are arranged at intervals, so that ozone is fully mixed with wastewater in the catalytic oxidation tower, and the phenomenon that the ozone is directly contacted with the catalyst to cause uneven gas-liquid mass transfer is avoided. By filling a specific ozone catalyst, the device can be used for effectively treating wastewater, continuously and stably operates for a long time, and is not easy to block.
According to the invention, the pore volume of the ozone catalyst can be 0.2-0.5cm3/g。
According to the present invention, the ozone catalyst preferably has a void volume of 60-80% (e.g., 62%, 65%, 68%, 72%, 75%, 78%, or any value therebetween).
According to the invention, the bulk weight of the ozone catalyst is preferably 650-750kg/m3(e.g., 660 kg/m)3、670kg/m3、680kg/m3、700kg/m3、740kg/m3Or any value therebetween).
According to the present invention, the number of the ozone catalyst piled is preferably 70000-3(e.g. 71000per m3、71500per/m3、72500per/m3、73000per/m3、74000per/m3、74500per/m3Or any value therebetween).
According to the invention, the dry packing factor of the ozone catalyst is preferably 500-600m-1(e.g., 505 m)-1、510m-1、520m-1、550m-1、580m-1、600m-1Or any value therebetween).
According to the invention, the catalytically active component is preferably present in an amount of 1 to 10 (e.g. 1, 2, 3, 4, 5, 5.5, 5.8, 6.2, 6.5, 8, 10 or any value between the above values) parts by weight per 100 parts by weight of carrier.
According to the present invention, the catalytically active component may be a transition metal commonly used in the art, preferably, the catalytically active component is selected from at least one of Mn, Fe, Cu, Ni, Zn and Co, more preferably, the catalytically active component is Mn and Fe in a weight ratio of 1:1 to 3:1 (e.g., 1:1, 1:1.1, 1:1.2, 1:1.5, 1:2, 1:3 or any value therebetween). The catalytically active component is usually present and acts in the form of oxides, and the invention is only illustrative of the type and amount of the metal elements and does not give any further details of the type of oxide.
According to a preferred embodiment of the present invention, in order to further improve the compressive strength of the ozone catalyst and thus prolong the service life of the catalyst, the carrier is silica and alumina in a weight ratio of 1:10 to 1:15 (e.g., 1:10, 1:11:, 1:12, 1:13, 1:14, 1:15 or any value therebetween).
According to the present invention, the filling rate of the catalyst filling layer may be 10 to 30%. In the present invention, the "filling ratio of the catalyst-packed layer" means a ratio of the amount of the packed catalyst to the volume of the catalytic oxidation tower.
According to the present invention, in order to obtain an ozone catalyst having a better performance, the method for preparing the ozone catalyst preferably comprises:
the method comprises the following steps: mixing a carrier precursor, a catalytic active component precursor and an auxiliary agent with water;
step two: casting the obtained mixture into a stepped ring form, and standing at room temperature;
step three: and (4) drying and calcining the product obtained in the step two.
According to the present invention, the particle size of the carrier precursor is in the range of 1 to 5 μm. The support precursor is preferably a mixture of silica (silicon dioxide) and a fast-release powder.
According to the present invention, water may be used in an amount of 5 to 15 parts by weight, relative to 100 parts by weight of the carrier precursor.
According to the present invention, the amount of the catalytically active component precursor is such that the amount of the catalytically active component is preferably 1 to 10 parts by weight (e.g., 1, 2, 3, 4, 5, 5.5, 5.8, 6.2, 6.5, 8, 10 or any value therebetween) relative to 100 parts by weight of the carrier in the ozone catalyst, relative to 100 parts by weight of the carrier precursor.
According to the invention, the precursor of the catalytic active component is a precursor of the transition metal, and the precursor of the catalytic active component is calcined at high temperature to become a metal oxide, which can be a salt (such as nitrate) of the transition metal, preferably at least one of a manganese precursor, an iron precursor, a copper precursor, a nickel precursor, a zinc precursor and a cobalt precursor, more preferably a manganese precursor and an iron precursor, and more preferably the precursor of the catalytic active component is a manganese precursor and an iron precursor, and the manganese precursor and the iron precursor are used in such amounts that the weight ratio of Mn to Fe in the ozone catalyst is 1:1-3:1 (such as 1:1, 1:1.1, 1:1.2, 1:1.5, 1:2, 1:3 or any value therebetween).
According to the invention, the auxiliary agent may be chosen from binders and/or structural auxiliary agents. The adhesive is added, so that the carrier can be effectively combined with the catalytic active component, and the loss of the catalytic active component is avoided. The structural auxiliary agent is added, so that the prepared catalyst has larger specific surface area and porosity, and the catalytic performance of the catalyst is improved.
According to a preferred embodiment of the present invention, the adjuvant is used in an amount of 2 to 15 (e.g., 2, 3, 4.5, 4.8, 5, 5.2, 5.5, 6, 8, 10, 12, 15 or any value therebetween) parts by weight relative to 100 parts by weight of the carrier precursor. According to a more preferred embodiment of the present invention, the binder is used in an amount of 1 to 10 parts by weight and the structural assistant is used in an amount of 1 to 5 parts by weight, relative to 100 parts by weight of the carrier precursor.
More preferably, the binder is selected from at least one of an aluminum sol and sesbania powder.
More preferably, the structural assistant is selected from at least one of activated carbon fiber powder, ammonium oxalate and ammonium carbonate.
According to the invention, the time for standing at room temperature is 24-48h (such as 24h, 25h, 30h, 40h, 48h or any value between the above values). Wherein "room temperature" is usually "15-40 ℃.
According to the present invention, the temperature of the drying may be 100-120 ℃. The drying time may be 2-4 h.
According to the present invention, the temperature of the calcination may be 400-600 deg.C (e.g., 400 deg.C, 450 deg.C, 490 deg.C, 495 deg.C, 505 deg.C, 510 deg.C, 550 deg.C, 600 deg.C or any value therebetween). The calcination time may be 2 to 4 hours (e.g., 2 hours, 3 hours, 3.8 hours, 4 hours, or any value therebetween).
According to the invention, the catalytic oxidation tower 5 further comprises a backflow water inlet 13 arranged between the ozone inlet 12 and the water inlet 14 and a backflow water outlet 9 arranged between the water outlet 7 and the catalyst filling layer 10 (that is, the catalytic oxidation tower is respectively provided with the ozone exhaust port 6, the water outlet 7, the backflow water outlet 9, the catalyst filling layer 10, the ozone inlet 12, the backflow water inlet 13 and the water inlet 14 from top to bottom), and the backflow water inlet 13 is connected with the backflow water outlet 9. The return water outlet 9 is positioned in the middle of the catalytic oxidation tower and below the water outlet 7. Through setting up backward flow water inlet 13 and backward flow delivery port 9, can realize the backward flow of waste water, further improve the treatment effeciency of waste water.
According to the invention, the catalytic oxidation tower 5 further comprises a pall ring packing layer 8 arranged between the water outlet 7 and the catalyst packing layer 10, and the pall ring packing layer 8 is arranged above the return water outlet 9 (i.e. the return water outlet 9 is arranged between the pall ring packing layer 8 and the catalyst packing layer 10). The pall ring packing layer 8 is arranged between the water outlet 7 and the backflow water outlet 9, and has the main functions of: absorb ozone behind the catalyst filling layer and will cut the ozone behind the catalyst filling layer (after contacting with the catalyst, ozone can gather the increase) into the small bubble to further increase the mass transfer efficiency of ozone and waste water, thereby further improve the ozone utilization ratio and further improve the waste water treatment effect.
According to the invention, the catalytic oxidation tower 5 is also provided with a tubular aerator 11 connected to the ozone inlet 12. The ozone bubbles which are about to pass through the catalyst filling layer are cut into tiny bubbles (such as 1-3mm), so that the mass transfer efficiency between the ozone and the wastewater is improved, and the ozone utilization rate is improved.
According to the invention, the return water inlet 13 is arranged below the catalyst-filled layer 10. The backflow water inlet 13 is positioned at the bottom of the catalytic oxidation tower, so that the backflow wastewater can be guaranteed to pass through the catalyst filling layer again to be subjected to catalytic oxidation reaction with ozone, and the catalytic oxidation efficiency of the wastewater is improved while the retention time of the ozone in the catalytic oxidation tower is prolonged.
According to the present invention, the pall ring packing layer 8 may be filled with a packing commonly used in the art, but preferably, the pall ring packing layer 8 includes polyvinyl chloride in the form of a pall ring. More preferably, the pall ring packing layer 8 may have a packing rate of 10 to 30%.
According to the invention, the ozone exhaust port 6 is arranged at the top of the catalytic oxidation tower 5, and the water inlet 14 is arranged at the bottom of the catalytic oxidation tower 5, so as to further prolong the retention time of the wastewater in the catalytic oxidation tower.
According to the invention, the water inlet and outlet system comprises a water inlet pool 1, a water inlet pump 2, a water inlet flow meter 3, a water inlet pipeline 4, a backflow water inlet pump 15, a backflow water inlet flow meter 16, a backflow pipeline 17, a water outlet pipeline 21 and a water outlet pool 22. The wastewater to be treated is introduced into the catalytic oxidation tower from the water inlet pool 1 through the water inlet pump 2 and the water inlet pipeline 4 from the water inlet 14. The water inlet flow meter 3 and the backflow water inlet flow meter 16 are respectively used for controlling the flow of inlet water and the flow of backflow inlet water. The return water outlet 9 is connected with the return water inlet 13 through a return water inlet pump 15 and a return pipeline 17. The water outlet 7 of the catalytic oxidation tower 5 is connected with an outlet water pool 22 through an outlet water pipeline 21. The wastewater after catalytic oxidation is lifted to a higher position to be discharged, rather than being directly discharged from the bottom of the catalytic oxidation tower, so that on one hand, the ozone can be prevented from directly losing from the bottom of the tower, and on the other hand, the retention time of wastewater treatment can be conveniently controlled.
According to the present invention, the ozone treatment system comprises an ozone generator 18, an ozone inlet pipe 19, an ozone inlet flow meter 20, an ozone exhaust pipe 23, and an ozone off-gas treatment device 24. The ozone generator 18 is connected with the ozone inlet 12 through an ozone inlet pipeline 19 and an ozone inlet flowmeter 20, and the ozone inlet 12 is connected with the tubular aerator 11. The ozone tail gas destruction device 24 is connected to the ozone exhaust port 6 through the ozone exhaust duct 23.
The invention also provides a method for treating wastewater, which is characterized by comprising the following steps: the wastewater to be treated is contacted with ozone in the presence of a catalyst for catalytic oxidation reaction, wherein the catalyst comprises the ozone catalyst in the form of a stepped ring. The present invention can effectively treat wastewater by using a specific ozone catalyst.
In the preferred embodiment of the present invention, the method is implemented in the device as described above, the wastewater to be treated is introduced into the catalytic oxidation tower 5 from the water inlet 14 by an optional water inlet and outlet system, and ozone is introduced into the catalytic oxidation tower 5 from the ozone inlet 12, so that the wastewater to be treated is contacted with the ozone to perform catalytic oxidation reaction; the treated part of wastewater leaves the catalytic oxidation tower 5 from a water outlet 7, and the gas phase after the catalytic oxidation reaction leaves the catalytic oxidation tower 5 from an ozone exhaust port 6 and enters an optional ozone treatment system.
In the present invention, the ozone is brought into contact with the wastewater to be treated in the form of fine bubbles (e.g., 1 to 3 mm).
The device of the invention can effectively reduce the dosage of the ozone, and the dosage of the ozone can be 50-200mg (such as 50mg, 90mg, 95mg, 98mg, 102mg, 105mg, 110mg, 150mg, 180mg, 200mg or any value between the above values) relative to each liter of wastewater to be treated.
In the invention, the Total Organic Carbon (TOC) of the wastewater to be treated can be 40-50mg/L, the Chemical Oxygen Demand (COD) can be 110-130mg/L, and the chroma can be 280-320. The process of the invention is particularly suitable for the composition of waste water as described above. In the invention, the TOC, COD and chromaticity test methods are respectively a combustion oxidation-non-dispersive infrared absorption method, a dichromate determination method for chemical oxygen demand of water quality (HJ 828-2017) and ISO 7887-1985 water color inspection and determination.
In the present invention, the retention time of the wastewater to be treated in the catalytic oxidation tower 5 may be 30-120min (e.g. 30min, 50min, 55min, 58min, 62min, 65min, 70min, 80min, 90min, 100min, 110min, 120min or any value therebetween). The process temperature is generally not controlled.
In the present invention, the reflux ratio of the catalytic oxidation tower 5 may be controlled to be 50 to 200% (e.g., 50%, 80%, 90%, 95%, 98%, 102%, 105%, 110%, 150%, 180%, 200%, or any value therebetween). The reflux ratio refers to the ratio of the reflux flow returning to the catalytic oxidation tower to the discharge flow at the water outlet.
The present invention will be described in detail below by way of examples. In the following examples, the quick release powder was purchased from Pingxiang globus new materials science and technology ltd; the activated carbon fiber powder was purchased from Shenyang Shenmin activated carbon plant.
Preparation example 1
The embodiment of the invention uses a self-made catalyst, and the preparation steps are as follows:
the method comprises the following steps: mixing 100 parts by weight of carrier powder (silicon dioxide and quick-release powder with a weight ratio of 1:10, wherein the particle size is within a range of 1-5 mu m), a catalytic active component precursor (3 parts by weight of manganese nitrate calculated by manganese element +3 parts by weight of ferric nitrate calculated by iron element), 10 parts by weight of water and a catalytic assistant (5 parts by weight of activated carbon fiber powder), and putting the mixture into a stirrer to prepare slurry;
step two: placing the prepared slurry into a liquid die-casting mould, casting into a stepped ring form, curing at room temperature for 24h, and placing into an air-blast drying oven, wherein the drying temperature is 105 ℃, and the drying time is 2 h;
step three: and (3) putting the dried catalyst into a muffle furnace, and calcining for 4h at 500 ℃ to finally obtain the ozone catalyst.
The prepared ozone catalyst was characterized with the following results:
size: 25mm × 15mm × 3mm, and a specific surface area of 220m2/m3Pore volume: 0.4cm3G, emptyThe void ratio: 70%, radial compressive strength: 165N/cm, stack weight: 650kg/m3And the stacking number is as follows: 72000per m3Dry packing factor: 500m-1。
Example 1
(1) Ozone catalytic oxidation wastewater treatment device
As shown in FIG. 1, the ozone catalytic oxidation wastewater treatment device comprises an inlet and outlet water system, a catalytic oxidation tower 5 and an ozone treatment system. The water inlet and outlet system comprises a water inlet pool 1, a water inlet pump 2, a water inlet flow meter 3, a water inlet pipeline 4, a backflow water inlet pump 15, a backflow water inlet flow meter 16, a backflow pipeline 17, a water outlet pipeline 21 and a water outlet pool 22;
the catalytic oxidation tower 5 is respectively provided with an ozone exhaust port 6, a water outlet 7, a backflow water outlet 9, an ozone inlet 12, a backflow water inlet 13 and a water inlet 14 from top to bottom. The water inlet 14 is connected with the water inlet pool 1 through the water inlet pump 2, the water inlet flowmeter 3 and the water inlet pipeline 4. The return water outlet 9 is connected with the return water inlet 13 through a return water inlet pump 15, a return water inlet flow meter 16 and a return pipeline 17. The water outlet 7 is connected with a water outlet pool 22 through a water outlet pipeline 21. The middle upper part, the middle lower part and the bottom of the catalytic oxidation tower 5 are respectively provided with a pall ring filling layer 8, a catalyst filling layer 10 and a tubular aerator 11. The pall ring filler is made of PVC (purchased from Jinbaoli environmental protection equipment Co., Ltd., Yixing). The filled catalyst was the catalyst prepared in preparation example 1. The return water outlet 9 is positioned in the middle of the catalytic oxidation tower, below the pall ring filling layer 8 and above the catalyst filling layer 10.
The ozone treatment system comprises an ozone generator 18, an ozone inlet pipe 19, an ozone inlet flowmeter 20, an ozone exhaust pipe 23 and an ozone tail gas treatment device 24. The ozone generator 18 is connected with the ozone inlet 12 through an ozone inlet pipeline 19 and an ozone inlet flowmeter 20, and the ozone inlet 12 is connected with the tubular aerator 11. The ozone off-gas destruction device 24 is connected to the ozone exhaust port 6 through the ozone exhaust duct 23.
(2) The ozone catalytic oxidation wastewater treatment method comprises the following steps:
step one, wastewater to be treated enters a catalytic oxidation tower 5 from a water inlet pool 1 through a water inlet pump 2 via a water inlet flow meter 3, a water inlet pipeline 4 and a water inlet 14, and sequentially passes through a catalyst filling layer 10 and a pall ring filling layer 8 from bottom to top. Meanwhile, ozone is generated by an ozone generator 18 and enters the catalytic oxidation tower 5 through an ozone inlet pipeline 19, an ozone inlet flow meter 20 and an ozone inlet 12, the ozone is divided into tiny ozone bubbles (1mm) under the action of a tubular aerator 11, the ozone bubbles and wastewater are fully mixed in the catalytic oxidation tower and upwards contact with a catalyst filling layer, and catalytic oxidation reaction is carried out under the action of a catalyst.
And step two, part of the treated wastewater enters the catalytic oxidation tower 5 from the backflow water outlet 9 under the lifting action of the backflow water inlet pump 15 through the backflow water inlet flowmeter 16, the backflow pipeline 17 and the backflow water inlet 13, and the backflow water flows upwards through the catalyst filling layer 10 and contacts with ozone to continue catalytic oxidation reaction.
And step three, the finally treated wastewater leaves the catalytic oxidation tower 5 from the water outlet 7 through the water outlet pipeline 21 and is discharged into the water outlet pool 22. After reaction, the ozone leaves the catalytic oxidation tower 5 from the ozone exhaust port 6 through the ozone exhaust pipeline 23 and enters the ozone tail gas destruction device 24.
The wastewater treatment is carried out according to the methods of the first step, the second step and the third step, but the treatment conditions are different, and the method specifically comprises the following steps:
route one: the retention time of wastewater treatment is 60min, the adding amount of ozone is 100mg/L, the filling rate of the catalyst is 20%, the filling rate of pall ring is 20%, and the reflux ratio of wastewater is 100%.
And a second route: the retention time of wastewater treatment is 60min, the adding amount of ozone is 100mg/L, the filling rate of the catalyst is 20%, the filling rate of pall ring is 20%, and the reflux ratio of wastewater is 100%. The catalyst adopts the traditional active alumina ball as a carrier, and the preparation process is as follows:
the method comprises the following steps: mixing 100 parts by weight of activated alumina balls (the particle size is 3-5mm), a catalytic active component precursor (3 parts by weight of manganese nitrate calculated by manganese element +3 parts by weight of ferric nitrate calculated by iron element) and 100 parts by weight of water, putting into an impregnation kettle, and impregnating for 24 hours;
step two: taking out the impregnated catalyst, washing with clear water, maintaining at room temperature for 24h, and then putting into an air-blast drying oven, wherein the drying temperature is 105 ℃, and the drying time is 2 h;
step three: and (3) putting the dried catalyst into a muffle furnace, and calcining for 4h at 500 ℃ to finally obtain the traditional ozone catalyst.
And a third route: the retention time of wastewater treatment is 60min, the adding amount of ozone is 100mg/L, the filling rate of the catalyst is 20 percent, and the reflux ratio is 100 percent. The catalytic oxidation tower is not filled with pall ring packing.
And a fourth route: the retention time of wastewater treatment is 60min, the adding amount of ozone is 100mg/L, the filling amount of the catalyst is 20%, and the filling rate of pall rings is 20%. The catalytic oxidation tower does not reflux.
The results of biochemical effluent of a sewage treatment plant in a chemical industry park after being treated by the different routes are shown in the following table 1:
TABLE 1
| Item | COD of inlet water | COD of effluent | Influent TOC | Effluent TOC | Color of inlet water | Color of effluent |
| Unit of | mg/L | mg/L | mg/L | mg/L | — | — |
| Line one | 120 | 55 | 45 | 22 | 300 | 15 |
| Line two | 120 | 80 | 45 | 30 | 300 | 30 |
| Line three | 120 | 75 | 45 | 28 | 300 | 26 |
| Line four | 120 | 70 | 45 | 25 | 300 | 24 |
According to the treatment effects of the four process routes, the treatment effect of the wastewater by the route is the best, and the treatment effect of the wastewater by the route is as follows: 120 mg/L; TOC: 45 mg/L; chroma: 300, the pollution index can be reduced to that: COD: 55 mg/L; TOC: 22 mg/L; chroma: and 15, the treatment effect is far better than that of other routes. That is, as can be seen from the first line, the treatment of wastewater (particularly, wastewater of a specific composition) in a specific apparatus using the ozone catalyst of a specific stepped loop form can achieve an excellent wastewater treatment effect. Also, although the results are not shown, more excellent treatment effects can be obtained when the ozone catalyst, the apparatus or the composition of wastewater falls within the preferred embodiments defined in the present invention.
The two pairs of lines have the worst wastewater treatment effect, and the wastewater quality indexes after treatment are as follows: COD: 80 mg/L; TOC: 30 mg/L; chroma: 30, this is probably because the second line adopts the traditional ozone catalyst, which has lower catalytic activity, and under the condition of the treatment of the present invention, ozone cannot be catalyzed to generate more hydroxyl radicals, so the treatment effect is not good.
The three pairs of wastewater treatment effects of the circuit are general, and the water quality indexes of the treated wastewater are as follows: COD: 75 mg/L; TOC: 28 mg/L; chroma: 26. comparing the results of the first line and the third line, it can be seen that the pall ring filler filled in the catalytic oxidation tower is more beneficial to improving the wastewater treatment effect.
The fourth circuit has the inferior treatment effect on the wastewater, and the water quality indexes of the treated wastewater are as follows: COD: 70 mg/L; TOC: 25 mg/L; chroma: 24. comparing the results of line one with line four, it can be seen that the return flow according to the present invention is more advantageous in improving the wastewater treatment effect.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A device with wastewater treatment function comprises catalytic oxidationThe catalytic oxidation tower is provided with an ozone exhaust port (6), a water outlet (7), a catalyst filling layer (10), an ozone inlet (12) and a water inlet (14) from top to bottom, the catalyst filling layer (10) comprises a stepped ring-shaped ozone catalyst, the ozone catalyst comprises a carrier and a catalytic active component, the carrier is silicon oxide and/or aluminum oxide, the catalytic active component is at least one selected from transition metals, and the specific surface area of the ozone catalyst is 210-250 m-2/m3The radial compressive strength is 150-180N/cm.
2. The apparatus as claimed in claim 1, wherein the ozone catalyst has a void ratio of 60-80% and a bulk weight of 650-750kg/m3The number of the stacks was 70000-75000per m3The dry packing factor is 500-600m-1；
And/or, the content of the catalytically active component is 1 to 10 parts by weight relative to 100 parts by weight of the carrier;
and/or the catalytically active component is selected from at least one of Mn, Fe, Cu, Ni, Zn and Co;
and/or the carrier is silicon oxide and aluminum oxide with the weight ratio of 1:10-1: 15;
and/or the filling rate of the catalyst filling layer is 10-30%.
3. The device of claim 1 or 2, wherein the catalytically active components are Mn and Fe in a weight ratio of 1:1-3: 1;
and/or, the preparation method of the ozone catalyst comprises the following steps:
the method comprises the following steps: mixing a carrier precursor, a catalytic active component precursor and an auxiliary agent with water;
step two: casting the obtained mixture into a stepped ring form, and standing at room temperature;
step three: and (4) drying and calcining the product obtained in the step two.
4. The apparatus of claim 3, wherein the particle size of the carrier precursor is in the range of 1-5 μm;
and/or the auxiliary agent is selected from a binder and/or a structural auxiliary agent;
and/or the room temperature is kept for 24-48 h;
and/or the drying temperature is 100-120 ℃, and the drying time is 2-4 h;
and/or the calcining temperature is 400-600 ℃, and the calcining time is 2-4 h.
5. The apparatus of claim 4, wherein the binder is used in an amount of 1-10 parts by weight and the structural assistant is used in an amount of 1-5 parts by weight, relative to 100 parts by weight of the carrier precursor;
and/or, the binder is selected from at least one of aluminum sol and sesbania powder;
and/or the structural auxiliary agent is selected from at least one of activated carbon fiber powder, ammonium oxalate and ammonium carbonate.
6. The device according to claim 1, wherein the catalytic oxidation tower (5) further comprises a return water inlet (13) arranged between the ozone inlet (12) and the water inlet (14) and a return water outlet (9) arranged between the water outlet (7) and the catalyst filling layer (10), and the return water inlet (13) is connected with the return water outlet (9);
and/or the catalytic oxidation tower (5) further comprises a pall ring filling layer (8) arranged between the water outlet (7) and the catalyst filling layer (10), and the pall ring filling layer (8) is arranged above the return water outlet (9);
and/or the catalytic oxidation tower (5) is also provided with a tubular aerator (11) connected with the ozone inlet (12).
7. The device according to claim 6, wherein the pall ring packing layer (8) comprises polyvinyl chloride in the form of pall rings;
and/or the filling rate of the pall ring filling layer (8) is 10-30%.
8. The device according to claim 1, wherein the ozone exhaust port (6) is arranged at the top of the catalytic oxidation tower (5) and the water inlet port (14) is arranged at the bottom of the catalytic oxidation tower (5).
9. A method of treating wastewater, the method comprising: the wastewater to be treated is contacted with ozone in the presence of a catalyst for catalytic oxidation reaction, wherein the catalyst comprises the ozone catalyst in the form of a stepped ring according to any one of claims 1 to 5.
10. The method of claim 9, wherein the method is implemented in the device of any one of claims 1 to 8, the wastewater to be treated is introduced into the catalytic oxidation tower (5) from the water inlet (14) by an optional water inlet and outlet system, and the ozone is introduced into the catalytic oxidation tower (5) from the ozone inlet (12), so that the wastewater to be treated is contacted with the ozone for catalytic oxidation reaction; part of the treated wastewater leaves the catalytic oxidation tower (5) from a water outlet (7), and a gas phase after catalytic oxidation reaction leaves the catalytic oxidation tower (5) from an ozone exhaust port (6) and enters an optional ozone treatment system;
and/or the ozone is contacted with the wastewater to be treated in the form of micron-sized small bubbles;
and/or the dosage of the ozone is 50-200mg relative to each liter of wastewater to be treated;
and/or the total organic carbon of the wastewater to be treated is 40-50mg/L, the chemical oxygen demand is 110-130mg/L, and the chroma is 280-320.
11. The method according to claim 9, wherein the residence time of the wastewater to be treated in the catalytic oxidation tower (5) is 30-120 min;
and/or controlling the reflux ratio of the catalytic oxidation tower (5) to be 50-200%.
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