CN114436390A - Ozone catalytic oxidation reactor and application thereof in viscose waste water treatment - Google Patents

Ozone catalytic oxidation reactor and application thereof in viscose waste water treatment Download PDF

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Publication number
CN114436390A
CN114436390A CN202210041164.3A CN202210041164A CN114436390A CN 114436390 A CN114436390 A CN 114436390A CN 202210041164 A CN202210041164 A CN 202210041164A CN 114436390 A CN114436390 A CN 114436390A
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catalytic
conveying
ozone
catalyst
barrel
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CN114436390B (en
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吕路
郭志成
陈振
孙柏岩
张炜铭
潘丙才
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Enire Jiangsu Environmental Development Co ltd
Nanjing University
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Enire Jiangsu Environmental Development Co ltd
Nanjing University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/38—Polymers

Abstract

The invention discloses an ozone catalytic oxidation reactor and application thereof in viscose waste water treatment, wherein the ozone catalytic oxidation reactor comprises a cylinder, a jet aeration component, a catalytic reaction component and a backwashing component which are positioned in the cylinder, the catalytic reaction component is positioned at the upper part in the cylinder, the catalytic reaction component comprises a plurality of catalyst placing discs which can synchronously rotate, a plurality of through holes for water permeation are arranged on the bottom surface, the top surface and the side surface of each catalyst placing disc, and catalytic fillers are filled in each catalyst placing disc. The application is the application in the Lyocell wastewater containing the methylmorpholine oxide. The ozone catalytic oxidation reactor combines the strong oxidizing property of ozone with the adsorption and catalytic properties of the catalyst, and utilizes hydroxyl radicals generated by ozone molecules on the surface of the catalyst to remove organic matters which are difficult to biodegrade in sewage, thereby effectively solving the problem of incomplete degradation of the organic matters.

Description

Ozone catalytic oxidation reactor and application thereof in viscose waste water treatment
Technical Field
The invention relates to the technical field of industrial wastewater ozone treatment, in particular to an ozone catalytic oxidation reactor and application thereof in viscose fiber wastewater treatment.
Background
Lyocell fibers are called "green fibers of the 21 st century" which are distinguished from the rayon industry because they have all the comfort properties of natural fibers and also have the advantages of superior fiber strength compared to common synthetic fibers, etc. In recent years, the rapid development of lyocell fibers brings great economic benefits to the society, and simultaneously, a series of environmental problems are generated. The method is more remarkable in terms of a large amount of waste water generated in the generation process, and the direct discharge of the waste water can not only destroy the surrounding ecological environment, but also influence the living environment and the body health of surrounding residents. Therefore, more strict laws and regulations are continuously provided in China to limit the discharge of the wastewater. Therefore, the adoption of a proper method for treating the wastewater has important significance for adapting to new environmental regulations and promoting the development of the rayon industry.
Generally, the lyocell fiber is prepared by a cellulose organic solvent spinning method, and a new solvent, namely methylmorpholine oxide, is used for replacing (NMMO) for replacing carbon disulfide in the production process, so that the series of safety problems and environmental problems caused by the carbon disulfide are effectively solved, and the whole production process flow is reduced. However, because of the large amounts of NMMO used in the production process, NMMO inevitably enters the wastewater. NMMO is a typical nitrogen-containing heterocyclic compound and has the characteristics of stable chemical property, difficult biodegradation, high nitrogen content and the like. The lyocell fiber wastewater has the characteristics of high suspended matter, high chroma, high COD, BOD, high zinc and the like of the conventional viscose fiber wastewater, and also has the characteristic of containing a large amount of non-degradable NMMO. Therefore, if the lyocell fiber wastewater is treated by the traditional viscose fiber wastewater treatment process, NMMO in the wastewater is difficult to remove and seriously exceeds the standard. The catalytic ozonation technology combines the strong oxidizing property of ozone with the adsorption and catalysis properties of a catalyst, removes organic matters which are difficult to biodegrade in sewage and the like by utilizing hydroxyl radicals generated on the surface of the catalyst by ozone molecules, and effectively solves the problem of incomplete degradation of the organic matters. However, if such wastewater is treated by the catalytic ozonation process, the high suspended matter and high chroma species in the wastewater can cause poor catalytic ozonation effect on hydroxyl radicals generated by quenching ozone. Therefore, aiming at the characteristics of the lyocell fiber wastewater and combining the technical advantages of catalytic ozonation, the catalytic ozonation reactor suitable for treating the lyocell fiber wastewater is developed, and has good application prospect.
Disclosure of Invention
Aiming at the problems, the invention provides an ozone catalytic oxidation reactor and application thereof in viscose fiber wastewater treatment.
The technical scheme of the invention is as follows:
an ozone catalytic oxidation reactor comprises a cylinder body, a jet aeration component, a catalytic reaction component and a backwashing component which are positioned in the cylinder body,
the jet aeration component is positioned at the inner bottom of the barrel and comprises an ozone conveying pipe and a sewage conveying pipe which extend from the outside of the barrel to the inside of the barrel, and a plurality of aeration ejectors which are arranged at equal intervals and positioned between the ozone conveying pipe and the sewage conveying pipe, wherein the upper part of each group of aeration ejectors is connected with the ozone conveying pipe, and the lower part of each group of aeration ejectors is connected with the sewage conveying pipe;
the catalytic reaction assembly is positioned at the upper part in the cylinder body and comprises a plurality of catalyst placing discs capable of synchronously rotating, a plurality of water-permeable through holes are formed in the bottom surface, the top surface and the side surface of each catalyst placing disc, and catalytic fillers are filled in each catalyst placing disc;
the backwashing component is positioned in the middle of the cylinder, a bearing layer is arranged between the backwashing component and the catalytic reaction component, and the backwashing component comprises a backwashing water inlet pipe and a backwashing air inlet pipe which are arranged side by side up and down;
furthermore, the diameter of the catalytic filler is 3-5mm, and the bulk density is 0.6-0.8t/m3The specific surface area is 150-300m2Per g, the catalytic filler is Y2O3MgO and MnO2The height of the catalytic reaction component of the loaded activated carbon particles is 1.5-3 m. The catalyst is arranged in a mixed state, so that the catalyst is maximally utilized in elevation, the catalytic effect of the catalyst is favorable for enhancing the ozone oxidation effect and reducing the ozone reaction concentration, and meanwhile, the ozone oxidation is favorable for stabilizing the catalytic activity of the catalyst and delaying the inactivation period.
Furthermore, the catalyst placing discs are arranged in 6 groups at equal intervals, a group of conveying barrels for conveying catalytic fillers is arranged between every two adjacent groups of catalyst placing discs, the catalyst placing disc positioned at the lowermost part is additionally connected with the catalyst placing disc positioned at the uppermost part through a group of lengthened conveying barrels penetrating through the rest of the catalyst placing discs, and the conveying barrels and the lengthened conveying barrels are rotationally connected with each group of catalyst placing discs;
the supporting layer comprises a filter screen positioned at the lower part and a supporting plate positioned at the upper part, a group of limiting rods for limiting and fixing the catalyst placing discs up and down are arranged on the upper surface of the supporting plate, the limiting rods sequentially penetrate through each group of catalyst placing discs and then are connected with a fixed plate positioned at the upper part in the cylinder body, the limiting rods are rotatably connected with each group of catalyst placing discs, a rotating motor is arranged at one end of the fixed plate, a rotating wheel for driving the group of catalyst placing discs positioned at the top to rotate is arranged at the output end below the rotating motor, and the outer teeth of the rotating wheel are meshed with the teeth arranged on the outer wall of each catalyst placing disc and are rotatably connected;
the backup pad is equipped with a set of stand with the upper surface that rotates the motor and correspond one end, the stand is corresponding every two sets of catalysts and is placed a set of cowl in the clearance department, the cowl internal surface is equipped with the tooth's socket, and every group transfer drum and extension transfer drum outer wall middle part all are equipped with the rack, rotate to cowl position department when transfer drum and extension transfer drum the rack with the tooth's socket butt joint is used for controlling the transfer drum and extends the transfer drum and rotate, and the transfer drum outer wall that is located position department about the rack is equipped with the aperture. Through the area of contact to catalytic reaction subassembly's improvement increase waste water and catalytic filler, make catalytic filler no longer fix and place but ceaselessly through the rotation that the dish was placed to the catalyst and the rotation of conveying bucket accomplish and vertically upwards and transversely upwards replace, improve the catalytic effect, alleviateed catalytic filler's wearing and tearing, prolonged life.
Further, the position department that gag lever post upper portion is close to the fixed plate is scalable setting, and the spout sliding connection that cowl and the stand outside were equipped with all is equipped with a plurality of pulleys that are used for making cowl place the gliding of the surface from top to bottom along the catalyst on the cowl top edge. The catalytic reaction component is driven to move up and down through the up-down telescopic sliding arrangement of the limiting rod, so that the aim of further improving the catalytic oxidation effect is fulfilled.
Further, the conveying barrel and the lengthened conveying barrel are internally provided with transmission packing augers, the transmission packing augers inside the conveying barrel and the transmission packing augers inside the lengthened conveying barrel are opposite in direction, the conveying barrel is used for feeding materials upwards, the lengthened conveying barrel is used for feeding materials downwards, and the conveying barrel and the lengthened conveying barrel are longitudinally surrounded to form a circular ring and are the same in interval angle. The transmission auger is driven to rotate by the rotation of the material feeding barrel, so that the purpose of vertically conveying materials is realized.
Furthermore, a water outlet is formed in one side of the upper portion of the cylinder body, and access holes are formed in the top and the side wall of the cylinder body. The maintenance is convenient for the workers.
The application of the ozone catalytic oxidation reactor in viscose fiber wastewater treatment comprises the following steps:
s1: inputting viscose fiber wastewater to be treated from a sewage conveying pipe, inputting ozone with the mass concentration of 30-50mg/L from an ozone conveying pipe, and setting the air inlet flow rate to be 1-1.2L/min;
s2: sequentially passing the aerated wastewater through each group of catalyst placing discs, starting a rotating motor to enable the catalyst placing discs to rotate so as to improve the catalytic effect of the catalytic filler, wherein the catalytic reaction time is 1-1.5h, and discharging the wastewater after the catalytic reaction from a water outlet;
s3: cleaning the interior of the cylinder and the filter screen at intervals of 6h backwashing, injecting air through a backwashing air inlet pipe, and ensuring that the air washing strength is 10-15L/m2S, injecting clear water through a back washing water inlet pipe, wherein the washing strength is 5-7L/m2And/s, the backwashing time is 10-30 min.
Further, the main pollutant in the viscose fiber wastewater is methyl morpholine oxide. The methyl morpholine oxide is a nitrogen-containing heterocyclic compound, has undefined chemical property and is difficult to biodegrade, contains more organic nitrogen, cannot be effectively degraded and removed by a biochemical system, and can be effectively removed by the ozone catalytic oxidation reactor.
Further, the preparation method of the catalytic filler comprises the following steps:
soaking activated carbon particles in Mn (NO) with the mass concentration of 1mol/L3)2、Mg(NO3)2And Y (NO)3)3Stirring the solution for reaction for 6 hours, and then dropwise adding KMnO with the mass concentration of 1mol/L4And NaOH solution, standing for 6h, filtering to obtain a solid mixture, drying the solid mixture at the temperature of 105-110 ℃, and calcining at the temperature of 400-450 ℃ for 1-3h to obtain Y2O3MgO and MnO2The loaded activated carbon particles comprise 1.3-1.5% by mass of Y, 0.8-1% by mass of Mg and 4.7-5% by mass of Mn. The catalytic effect of the catalyst is beneficial to strengthening the ozone oxidation effect and reducing the reaction concentration of ozone, and meanwhile, the ozone oxidation is beneficial to stabilizing the catalytic activity of the catalyst and delaying the inactivation period.
Further, the Mn (NO)3)2、Mg(NO3)2And Y (NO)3)3Mixing the solution with dropwise added KMnO4And the volume ratio of the NaOH solution is 29: 1: 1, the maximum reaction rate and the adsorption effect are achieved by adjusting the solution ratio.
The invention has the beneficial effects that:
(1) the invention develops a novel ozone catalytic reactor aiming at the advantages that lyocell fiber wastewater has basic characteristics of high suspended matter, high chroma, high zinc ion concentration and the like of conventional viscose fiber wastewater and the characteristic of containing high-concentration non-degradable NMMO, and effectively solves the series problems of poor effect of the traditional viscose fiber wastewater treatment method, blockage of the reactor caused by the high suspended matter contained in the wastewater and quenching of hydroxyl radicals generated by ozone and the like of the traditional ozone catalytic reactor.
(2) The multi-metal catalytic filler directionally developed according to the chemical structure characteristics of the NMMO improves the degradation rate of the NMMO, increases the contact area of wastewater and the catalytic filler by improving the catalytic reaction component in the reactor, completes the replacement in the longitudinal direction and the transverse direction by the rotation of the catalyst placing disc and the rotation of the conveying barrel, improves the catalytic effect, reduces the abrasion of the catalytic filler and prolongs the service life.
(3) Effluent of the Lyocell wastewater treated by the ozone reactor is colorless and transparent, COD concentration is less than 40mg/L, total nitrogen concentration is less than 12mg/L, and ammonia nitrogen concentration is less than 4mg/L, so that the method meets the first-level A discharge standard of urban sewage, and solves the industrial problem that the Lyocell wastewater is difficult to treat and reaches the standard at present.
Drawings
FIG. 1 is a schematic view of the overall structure of an ozone catalytic oxidation reactor in example 2 of the present invention;
FIG. 2 is a top view of an ozone catalytic oxidation reactor in example 2 of the present invention;
FIG. 3 is a schematic view of the structure of the catalytic reaction unit in the catalytic ozonation reactor in example 2 of the present invention;
FIG. 4 is a schematic view of the internal structure of the transfer barrel and the elongated transfer barrel of the catalytic ozonation reactor in example 2 of the present invention;
FIG. 5 is a schematic view of the external structure of a transfer drum of the catalytic ozonation reactor in example 2 of the present invention;
FIG. 6 is a schematic view of the construction of an arc-shaped baffle plate of the catalytic ozonation reactor in example 2 of the present invention;
FIG. 7 is a schematic structural view of a jet aeration module of the catalytic ozonation reactor in example 2 of the present invention;
FIG. 8 is a schematic view of the overall structure of the catalytic ozonation reactor in example 1 of the present invention.
The device comprises a barrel body 1, a fixing plate 11, a water outlet 12, a maintenance opening 13, a 2-jet aeration component, an ozone conveying pipe 21, a sewage conveying pipe 22, an aeration jet ejector 23, a catalytic reaction component 3, a backwashing component 4, a backwashing water inlet pipe 41, a backwashing air inlet pipe 42, a catalyst placing disc 5, a through hole 51, a conveying barrel 52, a lengthened conveying barrel 53, a rack 54, a conveying auger 55, a small hole 56, a bearing layer 6, a filter screen 61, a support plate 62, a limiting rod 63, a rotating motor 7, a rotating wheel 71, an upright post 8, an arc baffle 81, a tooth groove 82, a sliding groove 83 and a pulley 84.
Detailed Description
Example 1
As shown in figure 1, the catalytic ozonation reactor comprises a cylinder body 1, a jet aeration component 2, a catalytic reaction component 3 and a backwashing component 4 which are positioned inside the cylinder body 1,
the jet aeration component 2 is positioned at the inner bottom of the cylinder 1, the jet aeration component 2 comprises an ozone conveying pipe 21 and a sewage conveying pipe 22 which extend from the outer part of the cylinder 1 to the inner part of the cylinder 1, and 3 groups of aeration jet devices 23 which are positioned between the ozone conveying pipe 21 and the sewage conveying pipe 22 and are arranged at equal intervals, the aeration jet devices 23 are commercially available koerting-hannover aeration jet devices, the upper part of each group of aeration jet devices 23 is connected with the ozone conveying pipe 21, and the lower part of each group of aeration jet devices 23 is connected with the sewage conveying pipe 22;
the catalytic reaction component 3 is positioned at the upper part in the cylinder 1, and catalytic fillers are uniformly filled in the catalytic reaction component 3;
as shown in fig. 1 and 2, the backwashing component 4 is positioned in the middle of the cylinder 1, a supporting layer 6 is arranged between the backwashing component 4 and the catalytic reaction component 3, and the backwashing component 4 comprises a backwashing water inlet pipe 41 and a backwashing air inlet pipe 42 which are arranged up and down side by side;
example 2
This example is a further improvement of the catalytic reaction module 3 over example 1.
As shown in fig. 1 and 2, an ozone catalytic oxidation reactor comprises a cylinder 1, a jet aeration component 2, a catalytic reaction component 3 and a backwashing component 4 which are positioned in the cylinder 1, wherein one side of the upper part of the cylinder 1 is provided with a water outlet 12, and the top and the side wall of the cylinder 1 are both provided with an access hole 13;
the jet aeration component 2 is positioned at the bottom in the barrel 1, the jet aeration component 2 comprises an ozone conveying pipe 21 and a sewage conveying pipe 22 which extend from the outside of the barrel 1 to the inside of the barrel 1, and 3 groups of aeration jet devices 23 which are arranged at equal intervals and positioned between the ozone conveying pipe 21 and the sewage conveying pipe 22, the upper part of each group of aeration jet devices 23 is connected with the ozone conveying pipe 21, and the lower part of each group of aeration jet devices 23 is connected with the sewage conveying pipe 22;
as shown in fig. 3-6, the catalytic reaction assembly 3 is located at the upper part of the cylinder 1, the catalytic reaction assembly 3 comprises 6 groups of catalyst placing discs 5 which can rotate synchronously, a plurality of through holes 51 for water permeation are arranged on the bottom surface, the top surface and the side surface of each catalyst placing disc 5, the inside of each catalyst placing disc 5 is filled with catalytic filler, the diameter of the catalytic filler is 4mm, and the stacking density is 0.7t/m3The specific surface area is 240m2The catalytic filler is activated carbon particles, and the height of the catalytic reaction component 3 is 2.2 m;
the catalyst placing discs 5 are arranged in 6 groups at equal intervals, a group of conveying barrels 52 for conveying catalytic fillers is arranged between every two adjacent groups of catalyst placing discs 5, the catalyst placing disc 5 positioned at the lowest part is additionally connected with the catalyst placing disc 5 positioned at the highest part through a group of lengthened conveying barrels 53 penetrating through the rest catalyst placing discs 5, the conveying barrels 52 and the lengthened conveying barrels 53 are rotatably connected with each group of catalyst placing discs 5, conveying packing augers 55 are arranged in the conveying barrels 52 and the lengthened conveying barrels 53, the directions of the conveying packing augers 55 in the conveying barrels 52 and the conveying augers 55 in the lengthened conveying barrels 53 are opposite, the conveying barrels 52 are used for feeding materials upwards, the lengthened conveying barrels 53 are used for feeding materials downwards, and the conveying barrels 52 and the lengthened conveying barrels 53 are enclosed into a circular ring in the longitudinal direction and have the same interval angle;
the supporting layer 6 comprises a filter screen 61 positioned at the lower part and a supporting plate 62 positioned at the upper part, the upper surface of the supporting plate 62 is provided with a group of limiting rods 63 for limiting and fixing the catalyst placing discs 5 up and down, the limiting rods 63 sequentially penetrate through each group of catalyst placing discs 5 and then are connected with a fixing plate 11 positioned at the upper part in the cylinder body 1, the limiting rods 63 are rotationally connected with each group of catalyst placing discs 5, one end of the fixing plate 11 is provided with a rotating motor 7, the rotating motor 7 is a commercially available gear reducing motor, the output end below the rotating motor 7 is provided with a rotating wheel 71 for driving the group of catalyst placing discs 5 positioned at the top to rotate, and the outer teeth of the rotating wheel 71 are rotationally connected with the teeth arranged on the outer walls of the group of catalyst placing discs 5 at the top in a meshing manner;
the upper surface of one end of the supporting plate 62 corresponding to the rotating motor 7 is provided with a group of upright posts 8, the upright posts 8 are provided with a group of arc baffles 81 at the gaps corresponding to each two groups of catalyst placing discs 5, the inner surfaces of the arc baffles 81 are provided with tooth grooves 82, the middle parts of the outer walls of each group of conveying barrels 52 and the lengthened conveying barrels 53 are provided with racks 54, when the conveying barrel 52 and the lengthened conveying barrel 53 rotate to the position of the arc-shaped baffle plate 81, the rack 54 is in butt joint with the toothed groove 82 to control the rotation of the conveying barrel 52 and the lengthened conveying barrel 53, small holes 56 are formed in the outer wall of the conveying barrel 53 at the upper position and the lower position of the rack 54, the position, close to the fixing plate 11, of the upper portion of the limiting rod 63 is in telescopic arrangement, the arc-shaped baffle plate 81 is in sliding connection with a sliding groove 83 formed in the outer side of the upright post 8, and 3 groups of pulleys 84 used for enabling the arc-shaped baffle plate 81 to slide along the upper surface and the lower surface of the catalyst placing plate 5 are arranged on the upper edge and the lower edge of the arc-shaped baffle plate 81;
as shown in figure 1, the backwashing component 4 is positioned in the middle of the cylinder 1, a supporting layer 6 is arranged between the backwashing component 4 and the catalytic reaction component 3, and the backwashing component 4 comprises a backwashing water inlet pipe 41 and a backwashing air inlet pipe 42 which are arranged side by side up and down.
The working principle of applying the catalytic reaction component 3 to carry out catalytic reaction is as follows:
the wastewater aerated by the ozone enters the catalytic reaction component 3, and is contacted with the catalytic filler in each catalyst containing disc 5 sequentially through the through holes 51 of each group of catalyst containing discs 5 to complete the catalysis, meanwhile, the rotating motor 7 is started to drive the rotating wheel 71 to rotate, so that the group of catalyst containing discs 5 at the top are driven to rotate, and each group of catalyst containing discs 5 synchronously rotate under the action of the limiting rod 63, so that the catalytic reaction of more efficient chlorine is realized;
in order to make the catalytic fillers in each group of catalyst placing discs 5 mutually circulate, when the catalyst placing discs 5 rotate, every time one group of conveying barrels 52 rotate to the position of the arc baffle 81, the tooth grooves 82 of the arc baffle 81 are correspondingly meshed with the racks 54 of the conveying barrels 52, after the meshing is finished, the conveying barrels 52 continuously rotate along with the catalyst placing discs 5 to finish the rotation of the conveying barrels 52, when the conveying barrels 52 are separated from the arc baffle 81, the conveying barrels 52 finish the rotation of 180 degrees, the feeding of the internal conveying augers 55 is finished through the rotation of the conveying barrels 52, a part of the catalytic fillers in the lower catalyst placing discs 5 is conveyed into the upper catalyst placing discs 5, each group of conveying barrels 52 finish the feeding once, meanwhile, the lengthened conveying barrels 53 finish the downward conveying of the catalytic fillers in the same method, and the amount of the lengthened conveying barrels 53 conveying the downward conveying of the catalytic fillers is equal to the amount of the upward conveying of the conveying barrels 52 of each group of the catalytic fillers The sum of the quantities of the materials to ensure the balance of the catalytic filler inside the catalytic reaction component 3;
in this process, catalytic reaction subassembly 3 can also be in the activity from top to bottom under the effect of rivers, and the position department that gag lever post 63 upper portion is close to fixed plate 11 is used for offsetting the surplus of activity from top to bottom for scalable setting, and cowl 81 slides along spout 83 synchronous from top to bottom simultaneously to place the dish 5 with the catalyst through pulley 84 and catalyst and contact the assurance catalyst and place that dish 5 can accomplish the rotation all the time, reaches the purpose that further improves the aeration effect.
Example 3
This embodiment is substantially the same as embodiment 2, except that: the catalytic packing structures inside the catalytic reaction assembly 3 are different in size.
The diameter of the catalytic filler is 5mm, and the bulk density is 0.6t/m3A specific surface area of 150m2/g。
Example 4
This embodiment is substantially the same as embodiment 2, except that: the catalytic packing structures inside the catalytic reaction assembly 3 are different in size.
The diameter of the catalytic filler is 3mm, and the bulk density is 0.8t/m3The specific surface area is 300m2/g。
Example 5
This embodiment is substantially the same as embodiment 2, except that: the catalytic reaction module 3 is different in overall size.
The height of the catalytic reaction assembly 3 is 1.5 m.
Example 6
This embodiment is substantially the same as embodiment 2, except that: the catalytic reaction module 3 is different in overall size.
The height of the catalytic reaction assembly 3 is 3 m.
Example 7
This example describes the use of the catalytic ozonation reactor of example 2 in viscose waste water treatment.
The application method comprises the following steps:
s1: inputting viscose fiber wastewater to be treated, wherein the main pollutant of the viscose fiber wastewater is methylmorpholine oxide, from a sewage conveying pipe 22, inputting ozone with the mass concentration of 40mg/L from an ozone conveying pipe 21, and the air inlet flow rate is 1.1L/min;
s2: the aerated wastewater sequentially passes through each group of catalyst placing discs 5, the rotating motor 7 is started to enable the catalyst placing discs 5 to rotate so as to improve the catalytic effect of the catalytic filler, the catalytic reaction time is 1.3h, and the wastewater after the catalytic reaction is discharged from a water outlet 12;
the preparation method of the catalytic filler comprises the following steps:
soaking activated carbon particles in Mn (NO) with the mass concentration of 1mol/L3)2、Mg(NO3)2And Y (NO)3)3Stirring the solution for reaction for 6 hours, and then dropwise adding KMnO with the mass concentration of 1mol/L4And NaOH solution, standing for 6h, Mn (NO)3)2、Mg(NO3)2And Y (NO)3)3Mixing the solution with dropwise added KMnO4And the volume ratio of the NaOH solution is 29: 1: filtering to obtain solid mixture, drying the solid mixture at 108 ℃, and calcining at 435 ℃ for 2h to obtain Y2O3MgO and MnO2The loaded activated carbon particles comprise 1.4% of Y, 0.9% of Mg and 4.8% of Mn by mass;
s3: cleaning the interior of the cylinder and the filter screen 61 by backwashing once every 6h, injecting air through a backwashing air inlet pipe 42, and ensuring that the air washing strength is 12L/m2S, injecting clear water through a back washing water inlet pipe 41, wherein the washing strength is 6L/m2And/s, backwashing time 20 min.
Example 8
This example is substantially the same as example 7 except that: the ozone injection parameters of step S1 are different.
S1: the viscose fiber wastewater with main pollutant of methyl morpholine oxide to be treated is input from a sewage conveying pipe 22, ozone with the mass concentration of 30mg/L is input from an ozone conveying pipe 21, and the air inlet flow rate is 1L/min.
Example 9
This example is substantially the same as example 7 except that: the ozone injection parameters of step S1 are different.
S1: the viscose fiber wastewater with main pollutant of methyl morpholine oxide to be treated is input from a sewage conveying pipe 22, ozone with the mass concentration of 50mg/L is input from an ozone conveying pipe 21, and the air inlet flow rate is 1.2L/min.
Example 10
This example is substantially the same as example 7 except that: step S2 differs in the method of preparation of the catalytic filler.
S2: the aerated wastewater sequentially passes through each group of catalyst placing discs 5, the rotating motor 7 is started to enable the catalyst placing discs 5 to rotate so as to improve the catalytic effect of the catalytic filler, the catalytic reaction time is 1h, and the wastewater after the catalytic reaction is discharged from a water outlet 12;
the preparation method of the catalytic filler comprises the following steps:
soaking activated carbon particles in Mn (NO) with the mass concentration of 1mol/L3)2、Mg(NO3)2And Y (NO)3)3Stirring the solution for reaction for 6 hours, and then dropwise adding KMnO with the mass concentration of 1mol/L4And NaOH solution, standing for 6h, Mn (NO)3)2、Mg(NO3)2And Y (NO)3)3Mixing the solution with dropwise added KMnO4And NaOH solution volume ratioIs 29: 1: filtering to obtain solid mixture, drying the solid mixture at 105 deg.C, and calcining at 400 deg.C for 1 hr to obtain Y2O3MgO and MnO2The supported activated carbon particles had a mass ratio of Y of 1.3%, a mass ratio of Mg of 0.8%, and a mass ratio of Mn of 4.7%.
Example 11
This example is substantially the same as example 7 except that: step S2 differs in the method of preparation of the catalytic filler.
S2: the aerated wastewater sequentially passes through each group of catalyst placing discs 5, the rotating motor 7 is started to enable the catalyst placing discs 5 to rotate so as to improve the catalytic effect of the catalytic filler, the catalytic reaction time is 1.5h, and the wastewater after the catalytic reaction is discharged from a water outlet 12;
the preparation method of the catalytic filler comprises the following steps:
soaking activated carbon particles in Mn (NO) with the mass concentration of 1mol/L3)2、Mg(NO3)2And Y (NO)3)3Stirring the solution for reaction for 6 hours, and then dropwise adding KMnO with the mass concentration of 1mol/L4And NaOH solution, standing for 6h, Mn (NO)3)2、Mg(NO3)2And Y (NO)3)3Mixing the solution with dropwise added KMnO4And the volume ratio of the NaOH solution is 29: 1: filtering to obtain solid mixture, drying the solid mixture at 110 deg.C, and calcining at 450 deg.C for 3 hr to obtain Y2O3MgO and MnO2The supported activated carbon particles had a mass ratio of Y of 1.5%, a mass ratio of Mg of 1%, and a mass ratio of Mn of 5%.
Example 12
This example is substantially the same as example 7 except that: the backwash parameters of step S3 are different.
S3: cleaning the interior of the cylinder and the filter screen 61 by backwashing once every 6h, injecting air through a backwashing air inlet pipe 42, and ensuring that the air washing strength is 10L/m2S, injecting clear water through a back washing water inlet pipe 41, wherein the washing strength is 5L/m2And/s, backwashing time 10 min.
Example 13
This example is substantially the same as example 7 except that: the backwash parameters of step S3 are different.
S3: cleaning the interior of the cylinder and the filter screen 61 by backwashing once every 6h, injecting air through a backwashing air inlet pipe 42, and ensuring that the air washing strength is 15L/m2S, injecting clear water through a back washing water inlet pipe 41, wherein the washing strength is 7L/m2And/s, backwashing time 30 min.
Examples of the experiments
The ozone catalytic oxidation reactors of examples 1 to 6 were subjected to wastewater treatment experiments, wherein the wastewater was nitrogen-containing wastewater, and the results of the experiments are shown in table 1.
TABLE 1 effect of treating wastewater from catalytic ozonation reactor of examples 1 to 6
Figure BDA0003470279020000121
As can be seen from the embodiment 1, the adoption of the ozone catalytic oxidation reactor can further improve the removal effect of ammonia nitrogen in wastewater; comparing the examples 1 and 2, the catalytic reaction assembly 3 of the present invention can further improve the ammonia nitrogen removal effect;
it can be seen from comparison of examples 2-4 that the catalytic filler selected with small size, high density and high specific surface area has the best catalytic reaction effect, wherein the treatment effect of example 2 is almost the same as that of example 4, while the manufacturing cost of the catalytic filler of example 4 is greatly increased, and the size of the catalytic filler of example 2 is selected in consideration of the manufacturing cost;
as can be seen from the comparison of examples 2, 5 and 6, the height of the catalytic reaction module 3 is not selected to be too high or too low, which affects the catalytic reaction effect, so that 2.2m of example 2 is selected as the optimum.
Experimental example 2
The ozone catalytic oxidation reactors of examples 7-13 were tested for their effectiveness in treating viscose waste water, and the results are shown in Table 2.
TABLE 2 effect of treating wastewater from catalytic ozonation reactor in examples 7 to 13
Figure BDA0003470279020000131
As can be seen from comparison of examples 7-9, the selection of appropriate ozone injection parameters has an effect on the treatment effect of wastewater, the treatment effect is not good when the ozone injection speed is low, and the waste to a certain extent can be caused when the ozone injection speed is high, so that the selection of the ozone injection parameters of example 7 is optimal;
compared with examples 7, 10 and 11, the change of the preparation method of the catalytic filler has little influence on the wastewater treatment effect of the ozone catalytic oxidation reactor, and the selection within the parameter range of the preparation method of the catalytic filler can achieve better effect;
experimental example 3
The treatment effect of the catalytic ozonation reactor in viscose wastewater treatment as seen in examples 7, 12 and 13 was tested, the wastewater treatment effect after backwashing for 3 times was observed, the treatment effects of the catalytic ozonation reactor in example 1 after the backwashing method in example 7 was applied were compared, and the test results are shown in table 3.
TABLE 3 effect of treating wastewater in catalytic ozonation reactor of examples 1, 7, 12 and 13
Figure BDA0003470279020000141
Comparing examples 7, 12 and 13, it can be seen that the backwashing parameters are different, the wastewater treatment and purification effects after backwashing are also different, and the backwashing parameters in example 7 should be selected to be the most reasonable, so that the maximum cleaning effect is achieved, the next wastewater purification rate is ensured, and the cost can be controlled;
comparing examples 1 and 7, it can be seen that the same backwashing method is used, the treatment effect of example 7 is much better than that of example 1, especially, example 7 can still maintain higher treatment efficiency after backwashing is carried out for a plurality of times, because the ozone catalytic oxidation reactor of the invention can reduce the abrasion of the catalytic filler after the catalytic reaction component 3 is applied, and prolong the service life of the ozone catalytic oxidation reactor.

Claims (9)

1. An ozone catalytic oxidation reactor is characterized by comprising a cylinder (1), a jet aeration component (2), a catalytic reaction component (3) and a backwashing component (4) which are positioned in the cylinder (1),
the jet aeration component (2) is positioned at the inner bottom of the barrel (1), the jet aeration component (2) comprises an ozone conveying pipe (21) and a sewage conveying pipe (22) which extend from the outside of the barrel (1) to the inside of the barrel (1), and a plurality of aeration jet devices (23) which are arranged at equal intervals between the ozone conveying pipe (21) and the sewage conveying pipe (22), the upper part of each group of aeration jet devices (23) is connected with the ozone conveying pipe (21), and the lower part of each group of aeration jet devices (23) is connected with the sewage conveying pipe (22);
the catalytic reaction assembly (3) is positioned at the upper part in the cylinder body (1), the catalytic reaction assembly (3) comprises a plurality of catalyst placing discs (5) which can synchronously rotate, a plurality of through holes (51) for water permeation are formed in the bottom surface, the top surface and the side surface of each catalyst placing disc (5), and catalytic filler is filled in each catalyst placing disc (5);
the backwashing component (4) is positioned in the middle of the inside of the cylinder body (1), a supporting layer (6) is arranged between the backwashing component (4) and the catalytic reaction component (3), and the backwashing component (4) comprises a backwashing water inlet pipe (41) and a backwashing air inlet pipe (42) which are arranged side by side from top to bottom.
2. The catalytic ozonation reactor of claim 1, wherein the catalytic packing has a diameter of 3-5mm and a bulk density of 0.6-0.8t/m3The specific surface area is 150-300m2Per g, the catalytic filler is Y2O3MgO and MnO2The height of the catalytic reaction component (3) of the loaded activated carbon particles is 1.5-3 m.
3. The catalytic ozonation reactor of claim 1, wherein the catalyst containing trays (5) are arranged in 6 groups and are arranged at equal intervals, a group of conveying barrels (52) for conveying catalytic fillers is arranged between every two adjacent groups of catalyst containing trays (5), the catalyst containing tray (5) positioned at the lowest position is additionally connected with the catalyst containing tray (5) positioned at the highest position through a group of lengthening conveying barrels (53) penetrating through the rest catalyst containing trays (5), and the conveying barrels (52) and the lengthening conveying barrels (53) are both rotatably connected with each group of catalyst containing trays (5);
the support layer (6) comprises a filter screen (61) positioned at the lower part and a support plate (62) positioned at the upper part, a group of limiting rods (63) used for limiting and fixing the catalyst placing discs (5) up and down are arranged on the upper surface of the support plate (62), the limiting rods (63) sequentially penetrate through each group of catalyst placing discs (5) and then are connected with a fixing plate (11) positioned at the upper part in the cylinder body (1), the limiting rods (63) are rotatably connected with each group of catalyst placing discs (5), a rotating motor (7) is arranged at one end of the fixing plate (11), a rotating wheel (71) used for driving the group of catalyst placing discs (5) positioned at the top to rotate is arranged at the output end below the rotating motor (7), and the outer teeth of the rotating wheel (71) are rotatably connected with the teeth arranged on the outer wall of the group of catalyst placing discs (5) at the top in a meshing manner;
the upper surface that backup pad (62) and rotation motor (7) correspond one end is equipped with a set of stand (8), stand (8) are corresponding every two sets of catalysts and are placed dish (5) clearance department and all are equipped with a set of cowl (81), cowl (81) internal surface is equipped with tooth's socket (82), and every group conveying barrel (52) and extension conveying barrel (53) outer wall middle part all are equipped with rack (54), when conveying barrel (52) and extension conveying barrel (53) rotate to cowl (81) position department rack (54) with tooth's socket (82) butt joint is used for controlling conveying barrel (52) and extension conveying barrel (53) to rotate, and conveying barrel (53) outer wall that is located rack (54) upper and lower position department is equipped with aperture (56).
4. The catalytic ozonation reactor according to claim 1, wherein the upper portion of the limiting rod (63) is telescopically arranged at a position close to the fixing plate (11), the arc-shaped baffle plate (81) is slidably connected with a sliding groove (83) arranged on the outer side of the upright post (8), and a plurality of pulleys (84) used for enabling the arc-shaped baffle plate (81) to slide along the upper and lower surfaces of the catalyst placing plate (5) are arranged on the upper and lower edges of the arc-shaped baffle plate (81).
5. The catalytic ozonation reactor according to claim 1, wherein the conveying barrel (52) and the lengthened conveying barrel (53) are internally provided with the conveying augers (55), the conveying augers (55) inside the conveying barrel (52) and the conveying augers (55) inside the lengthened conveying barrel (53) are arranged in opposite directions, the conveying barrel (52) is used for feeding upwards, the lengthened conveying barrel (53) is used for feeding downwards, and the conveying barrel (52) and the lengthened conveying barrel (53) are longitudinally encircled to form a circular ring and have the same interval angle.
6. The catalytic ozonation reactor of claim 1, wherein a water outlet (12) is formed in one side of the upper part of the cylinder (1), and the top and the side wall of the cylinder (1) are provided with access holes (13).
7. The use of the catalytic ozonation reactor of any of claims 1-6 in viscose waste water treatment, characterized in that the application method comprises the following steps:
s1: inputting viscose waste water to be treated from a sewage conveying pipe (22), inputting ozone with the mass concentration of 30-50mg/L from an ozone conveying pipe (21), and controlling the air inlet flow rate to be 1-1.2L/min;
s2: the aerated wastewater sequentially passes through each group of catalyst placing discs (5), a rotating motor (7) is started to enable the catalyst placing discs (5) to rotate to improve the catalytic effect of the catalytic filler, the catalytic reaction time is 1-1.5h, and the wastewater after the catalytic reaction is discharged from a water outlet (12);
s3: cleaning the interior of the cylinder and the filter screen (61) by backwashing once every 6h, injecting air through a backwashing air inlet pipe (42), wherein the air washing strength is 10-15L/m2S, clear water is injected through a back washing water inlet pipe (41), and the washing strength is 5-7L/m2And/s, the backwashing time is 10-30 min.
8. The application of the catalytic ozonation reactor in viscose waste water treatment according to claim 7, wherein the preparation method of the catalytic filler is as follows:
soaking activated carbon particles in Mn (NO) with the mass concentration of 1mol/L3)2、Mg(NO3)2And Y (NO)3)3Stirring the solution for reaction for 6 hours, and then dropwise adding KMnO with the mass concentration of 1mol/L4And NaOH solution, standing for 6h, filtering to obtain a solid mixture, drying the solid mixture at the temperature of 105-110 ℃, and calcining at the temperature of 400-450 ℃ for 1-3h to obtain Y2O3MgO and MnO2The loaded activated carbon particles comprise 1.3-1.5% of Y, 0.8-1% of Mg and 4.7-5% of Mn by mass.
9. Use of an ozone catalytic oxidation reactor according to claim 8 in viscose waste water treatment, characterized in that the Mn (NO) is3)2、Mg(NO3)2And Y (NO)3)3Mixing the solution with dropwise added KMnO4And the volume ratio of the NaOH solution is 29: 1: 1.
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