CN216662592U - Catalytic ozone oxidation system for treating membrane filtration concentrate by using reaction intermediate waste - Google Patents

Abstract

The utility model relates to a catalytic ozonation system for treating membrane filtration concentrated solution by using waste in a reaction process, wherein an activated carbon adsorption unit is used for adsorbing metal cations, heavy metal ions, metal acid radicals, miscellaneous salt ions and part of organic substances in the membrane filtration concentrated solution and comprises an adsorption reaction tank and a centrifugal machine; the first-stage active carbon modification unit prepares the active carbon with saturated adsorption into a first-stage catalyst, and comprises a first-stage dryer and a first-stage active carbon modifier; the secondary active carbon modification unit loads the primary catalyst again to prepare a secondary catalyst, and the secondary catalyst comprises a formula device, a secondary dryer and a secondary active carbon modifier; the primary catalytic ozonation unit is used for carrying out primary catalytic ozonation on wastewater to be treated and comprises an ozone generator and a primary reactor, and the secondary catalytic ozonation unit is used for carrying out secondary catalytic ozonation on the wastewater subjected to the primary catalytic ozonation treatment and comprises an ozone generator and a secondary reactor. Provides guarantee for realizing full-quantization and harmless treatment of membrane filtration concentrate in subsequent engineering.

Description

Catalytic ozone oxidation system for treating membrane filtration concentrate by using reaction intermediate waste

Technical Field

The utility model relates to a catalytic ozonation system for treating membrane filtration concentrate by using waste in a reaction process, and belongs to the technical field of treatment of membrane filtration concentrate of landfill leachate.

Background

Landfill leachate is refractory high-concentration organic wastewater with complex components and has the typical characteristics of high pollution load and comprehensive pollution: the odor is strong, the color is deep, the pH value is about 6-8, the COD load is high, the biodegradability is very poor, the ammonia nitrogen concentration is high, a large amount of soluble solids and heavy metals are contained, and the fluctuation range of the physicochemical properties is large. The landfill leachate treated by the membrane process at present in China accounts for more than 1/2 of the total treatment amount of the leachate, and the concentrated solution generated in China is about 500 ten thousand tons per year and accounts for 1/4 of the treated water output. The membrane filtration concentrated solution has complex components, poor biodegradability, high salt content, large peculiar smell, high organic matter content, brownish black color, high salt content (the conductivity is more than 15000 mu s/cm), large organic load (COD is more than 8000mg/L), high metal ion content, is usually difficult to carry out advanced oxidation and biochemical treatment, and has very small possibility of continuously degrading COD by adopting a microbial means because the high salt content of a water body influences the microbial activity.

The mainstream process method for treating the membrane filtration concentrated solution of the landfill leachate at home and abroad is a recharge method and an evaporation method: the recharge method is easy to cause the cyclic accumulation of the content of refractory organics and salts, the service life of a membrane system is reduced, and the aging of a landfill site is aggravated; the evaporation method has high energy consumption, easy scaling and high equipment cost, and particularly, the evaporation method has expensive treatment price and great popularization difficulty. Therefore, the research on the membrane filtration concentrated solution treatment process of the landfill leachate with economic and functional benefits is urgent.

CN110776196A "A landfill leachate treatment system and method in combination with advanced oxidation", the treatment system includes activated carbon filter, anaerobic reactor, aerobic reactor, advanced oxidation reactor and micro-nano bubble generator; the treatment method comprises the steps of removing insoluble impurities in percolate through an activated carbon filter, treating the percolate through an anaerobic reactor and an aerobic reactor sequentially by a biological method, carrying out advanced oxidation reaction in an advanced oxidation reactor, wherein an oxidant is ozone micro-nano bubbles, and finally discharging water meeting the discharge standard into a sewage discharge system. The treatment adopts a biological method and a physical and chemical method which are combined for treating the percolate, adds a process of advanced oxidation treatment of the percolate on the basis of anaerobic-aerobic combined treatment of the percolate, and utilizes the strong oxidizing property of ozone micro-nano bubbles generated OH to more efficiently and thoroughly remove pollutants.

However, in the catalytic ozonation process, the technical economy of the catalyst is poor, the use cost ratio is low, the fouling of the catalyst shortens the service life, and the granular activated carbon and gamma-Al are mostly used₂O₃The heterogeneous catalyst prepared by carrier-supported metal/precious metal/rare earth oxide has the problems of complex preparation process and high cost, and active components are lost in the treatment process, so that the balance of high performance and high cost performance is difficult to realize. A considerable amount of auxiliary agents are required to be added in the treatment process, part of the auxiliary agents become new substances to be treated, the cost of the agents is high, the amount of the agents is large, a large amount of waste substances in the reaction process such as sludge is generated, the waste disposal amount in the reaction process is large, and the treatment cost is high.

Disclosure of Invention

The utility model aims to provide a catalytic ozonation system for treating membrane filtration concentrate by using waste in the middle of reaction, which realizes high added value utilization of adsorption saturated activated carbon which is easy to be treated as hazardous waste and metal salt ions which are difficult to remove in the membrane filtration concentrate, realizes generation of a synergistic catalyst for sewage ozone treatment by modifying the adsorption saturated activated carbon, effectively solves the problems of high catalyst cost and large waste disposal amount of waste in the middle of reaction, and provides guarantee for realizing full-scale and harmless treatment of the membrane filtration concentrate in subsequent engineering.

The technical scheme for achieving the aim of the utility model is as follows: utilize catalytic ozonation system of reaction middling journey waste treatment membrane filtration concentrate, its characterized in that: comprises an activated carbon adsorption unit, a primary activated carbon modification unit, a secondary activated carbon modification unit, a primary catalytic ozonation unit and a secondary catalytic ozonation unit;

the activated carbon adsorption unit is used for adsorbing metal cations, heavy metal ions, metal acid radicals, miscellaneous salt ions and part of organic substances in the membrane filtration concentrated solution and comprises an adsorption reaction tank and a centrifugal machine, wherein a stirrer is arranged in the adsorption reaction tank and used for uniformly stirring filtrate and activated carbon, a discharge outlet at the bottom of the adsorption reaction tank is communicated with a feed inlet of the centrifugal machine, a liquid phase outlet of the centrifugal machine is communicated with the primary reactor through a liquid discharge pipe, and a first water inlet pump is arranged on the liquid discharge pipe;

the primary active carbon modification unit is used for preparing a primary catalyst from the adsorption saturated active carbon, and comprises a primary dryer and a primary active carbon modifier, wherein the primary dryer is used for receiving the adsorption saturated active carbon discharged by a centrifugal machine and the reacted primary catalyst and heating and drying the activated carbon and the reacted primary catalyst; the primary activated carbon modifier is used for receiving the activated carbon loaded with the active ingredients and dried by the primary dryer, roasting the activated carbon and fixedly loading the active oxides on the activated carbon;

the secondary active carbon modification unit is used for loading the primary catalyst again and preparing the primary catalyst into a secondary catalyst, and comprises a formula device, a secondary dryer and a secondary active carbon modifier, wherein the formula device is used for distributing, soaking and modifying the primary catalyst and the reacted secondary catalyst, and a plurality of independent ion impregnation tanks are arranged in the formula device; the secondary dryer is used for receiving the soaked catalyst and heating and drying the catalyst; the secondary activated carbon modifier is used for receiving the activated carbon loaded with the active ingredients and dried by the secondary dryer, roasting the activated carbon and fixedly loading the active oxides on the activated carbon;

the primary catalytic ozonation unit is used for primary catalytic ozonation of wastewater to be treated and comprises an ozone generator and a primary reactor, wherein the upper part of the primary reactor is provided with a first water inlet, the lower part of the primary reactor is provided with a first water outlet, a liquid discharge pipe is communicated with the first water inlet of the primary reactor, a first grid box which can be replaced and is provided with a primary catalyst is arranged in the primary reactor, the bottom of the primary reactor is provided with a first aerator, and the ozone generator is communicated with the first aerator through a first air pipe;

the secondary catalytic ozonation unit is used for carrying out secondary catalytic ozonation on the wastewater after the primary catalytic ozonation treatment, and comprises an ozone generator and a secondary reactor, wherein a second water inlet is formed in the upper part of the secondary reactor, a second water outlet is formed in the lower part of the secondary reactor, a first water outlet of the primary reactor is communicated with a second water inlet of the secondary reactor through a second water pipe, a third water inlet pump is installed on a second water inlet pipe, a second grid box capable of being replaced and provided with a secondary catalyst is installed in the secondary reactor, a second aerator is installed at the bottom of the secondary reactor, and the ozone generator is communicated with the second aerator through a second air pipe.

The technical scheme adopted by the utility model has the following advantages:

the utility model relates to a catalytic ozonation treatment process, which adopts an activated carbon adsorption unit, a primary activated carbon modification unit, a secondary activated carbon modification unit and a two-stage catalytic ozonation unit, creatively utilizes metal cations introduced by the activated carbon adsorption unit, metal ions which are usually difficult to remove and exist in a micro ionic state in membrane filtration concentrated liquid, metal acid radicals and miscellaneous salt ions, and oxides of the metal ions which are difficult to remove in sewage to be treated are used as main active ingredients of a catalyst of a subsequent catalytic reaction. The degradation degree and the biodegradability of subsequent treatment simultaneously creatively provide a multi-stage catalytic ozonation reaction system, the used catalysts are all in the system, newly introduced reaction intermediate waste is less, the catalysts can be repeatedly roasted for use, and the catalysts become ash loss in the process of repeatedly roasting and updating the catalysts, so the generated reaction intermediate waste is less. The utility model realizes the idea of 'treating waste by waste' by using the solid waste in the middle process of membrane filtration concentrated solution reaction, is beneficial to the field of landfill leachate which is difficult to degrade high-concentration organic wastewater to practice green production and circular economy development, and can give consideration to both technical and economic double-effect performance.

The utility model adopts catalysts with different active ingredients to carry out two-stage catalytic ozonation reaction, can obviously improve the degradation and mineralization degree of the membrane filtration concentrate, and can greatly improve BOD (biochemical oxygen demand)₅The COD value further improves the degradation, chain scission or mineralization degree of the membrane filtration concentrated solution. The utility model effectively destroys the structure of macromolecular organic matters in the membrane filtration concentrated solution through two-stage catalytic ozonation reaction so as to convert the macromolecular organic matters into micromolecular organic matters, even part of the macromolecular organic matters are mineralized into carbon dioxide and water; the method breaks the part of the cyclic molecules or long chain molecules of the organic matters difficult to biodegrade, can convert part of the macromolecular organic matters difficult to degrade in the membrane filtration concentrated solution into micromolecular organic matters easy to degrade by oxidation open bonds, and converts part of the organic matters with unsaturated molecular structures in the humic acid difficult to degrade into organic matter micromolecules with good biodegradability, so that the biodegradability of the membrane filtration concentrated solution can be improved, the salt content of the concentrated solution can be properly reduced, stable and safe water quality is provided for subsequent biochemical treatment, and the reduction of biochemical performance caused by microbial poisoning is avoided. The membrane filtration concentrated solution treated by the method has the removal rate of organic matter COD (chemical oxygen demand) up to 70-90 percent and BOD (biochemical oxygen demand)₅The COD value is increased from 0.01-0.05 to 0.20-0.50. The catalytic ozonation method can realize the effect of humic acid and other macromolecular organic matters, silicate, polymeric aluminum iron or polypropylene in the membrane filtration concentrated solutionAnd due to the removal of high-molecular polymer substances such as enamine and the like, the chromaticity and viscosity of the sewage are effectively reduced, the operation cost is reduced, and the economic benefit of the process is further improved.

The catalytic ozone-oxygen system adopts 'adsorption-roasting-catalysis', the activated carbon is used for preparing the catalyst, the activated carbon which is easy to be treated as hazardous waste and is subjected to adsorption saturation and metal salt ions which are difficult to remove in membrane filtration concentrated solution are utilized with high added value, the activated carbon is modified by the catalyst preparation unit, the generation of the wastewater ozone treatment synergistic catalyst is realized, ozone is used for carrying out micro-aeration treatment on wastewater, and the mass transfer effect between the ozone-catalyst and organic pollutants is enhanced by adopting a filler reaction tower for sequencing batch treatment and ozone aeration.

By adopting the catalytic ozonation system, the treatment process route is simple, the treatment cost is lower than that of other processes, the treatment effect is better, substances which are difficult to biodegrade in the wastewater can be effectively degraded through catalytic ozonation reaction, meanwhile, the ozone and organic pollutants react to form oxygen and carbon dioxide, secondary pollution of an oxidant is not generated, and the problems that a membrane filtration concentrated solution is difficult to biodegrade, the waste disposal amount in the middle of reaction is large, and a catalyst is easy to scale are solved. The catalytic ozonation method is favorable for realizing the combination of pre-coagulation sedimentation and post-biochemical treatment methods to form a substance and energy efficient utilization network in the degradation-resistant high-concentration sewage treatment process, provides guarantee for realizing full-quantification and harmless treatment of the membrane filtration concentrated solution and finally realizing full up-to-standard discharge of the membrane filtration concentrated solution in subsequent engineering, and provides a new idea for membrane filtration concentrated solution treatment.

Drawings

Embodiments of the present invention are described in further detail below with reference to the accompanying drawings.

FIG. 1 is a schematic diagram of a catalytic ozonation system of the present invention utilizing a mid-range waste treatment membrane filtration concentrate.

FIG. 2 is a schematic view of a first-stage reactor according to the present invention.

Wherein: 1-an adsorption reaction tank, 1-a stirrer, 2-a centrifuge, 2-1-a liquid discharge pipe, 3-a first water inlet pump, 4-a filter, 5-a liquid storage tank, 5-1-a first water inlet pipe, 6-a second water inlet pump, 7-a first-stage reactor, 7-1-a second water inlet pipe, 7-2-a first grid box, 7-3-a first aerator, 7-4-a first back-off port, 7-5-a first water inlet, 7-6-a first box frame, 7-a first access door, 7-8-a first emergency evacuation port, 7-9-a first water outlet, 8-a third water inlet pump, 9-a second-stage reactor, 9-1-a second aerator, 9-2-a second grid box, 10-an ozone recoverer, 11-a first-stage dryer, 12-a first-stage active carbon modifier, 13-first-stage catalyst storage tank, 14-formula device, 15-second-stage dryer, 16-second-stage activated carbon modifier, 17-second-stage catalyst storage tank, 18-ozone generator, 18-1-first air pipe, 18-2-second air pipe

Detailed Description

As shown in fig. 1, the catalytic ozonation system using the membrane filtration concentrate for medium-range waste treatment in the reaction according to the present invention includes an activated carbon adsorption unit, a primary activated carbon modification unit, a secondary activated carbon modification unit, and a primary catalytic ozonation unit and a secondary catalytic ozonation unit.

As shown in figure 1, the activated carbon adsorption unit is used for adsorbing metal cations, heavy metal ions, metal acid radicals, miscellaneous salt ions and partial organic substances in membrane filtration concentrated solution and comprises an adsorption reaction tank 1 and a centrifugal machine 2, a stirrer 1-1 arranged in the adsorption reaction tank 1 is used for uniformly stirring filtrate and activated carbon to ensure that the activated carbon is fully adsorbed and saturated, the stirrer 1-1 is used for slowly stirring at the speed of 20-80 revolutions per minute, and the specific surface area of the activated carbon selected by the system is 500-1100 m²The iodine value is 800-1000, and the particle density of the active carbon is 0.6-1.1 g/cm³The particle size of the particles is 30-80 mm, the sphericity is 60-80%, and the adding amount of the active carbon accounts for 1/10-3/10 of the volume of the adsorption reaction tank 1.

As shown in figure 1, a discharge outlet at the bottom of an adsorption reaction tank 1 is communicated with a feed inlet of a centrifuge 2, a liquid phase outlet of the centrifuge 2 is communicated with a first-stage reactor 7 through a liquid discharge pipe 2-13, a first water inlet pump 3 is arranged on the liquid discharge pipe 2-13, a separated liquid phase is used as a main water sample for catalyzing ozone oxidation reaction, and adsorption saturated activated carbon separated by the centrifuge 2 is used as a catalyst precursor and enters a next-stage first-stage activated carbon modification unit.

The utility model has a large amount of metal cation Fe which has obvious influence on advanced oxidation reaction and biochemical reaction in an activated carbon adsorption unit³⁺/Fe²⁺、Ca²⁺、Mg²⁺、Na⁺Metallate hetero-salt ions such as AlO₂ ^-TiO titanate (II)₃ ^2-Other acid radical ions such as Cl^-、SO₄ ^2-The method has the advantages that trace heavy metal elements such as Cu, Mn, Ni, Sr, Ti, Pd and the like and partial organic substances such as humus and the like are effectively adsorbed, heavy metal salt ions which are difficult to remove in membrane filtration concentrated solution can be removed, particularly excessive metal ions which are introduced during coagulating sedimentation treatment are removed, adsorption saturated activated carbon which is easy to discard after being used is used as a catalyst precursor, adsorbed waste is used as an active ingredient, the catalyst is roasted to form a catalyst suitable for a subsequent catalytic ozone oxidation reaction section, and the activated carbon which is treated as waste substances in the middle process of reaction is subjected to high value-added utilization. The utility model reduces the content of salt ions in the wastewater to be treated through adsorption, and the removed salt ions are not simply discarded in the adsorption process but are fully utilized as the active components of the catalyst reaction, thereby realizing the treatment of wastes with processes of wastes against one another. The utility model reduces the interference of miscellaneous salt ions in the wastewater through the adsorption of the activated carbon, is beneficial to the subsequent two-stage catalytic ozone oxidation reaction, can prolong the service life of the catalyst in the subsequent treatment, and improves the degradation degree of pollutants in the membrane filtration concentrated solution and the biodegradability of the subsequent treatment.

As shown in figure 1, a filter 4 and a liquid storage tank 5 are further connected to a liquid discharge pipe 2-13, solid-liquid separation is carried out again through the filter 4 to separate out residual activated carbon fine particles in a liquid phase, the filter 4 can adopt a plate frame filter, clarified filtrate is used as a main water sample for catalyzing ozone oxidation reaction and sent into the liquid storage tank 5 for standby, the liquid storage tank 5 is communicated with a first water inlet 7-5 on a first-stage reactor 7 through a first water inlet pipe 5-1, and a second water inlet pump 6 is installed on the first water inlet pipe 5-1.

As shown in fig. 1, the primary activated carbon modification unit of the present invention is used for preparing a primary catalyst from activated carbon saturated by adsorption, and includes a primary dryer 11 and a primary activated carbon modifier 12, where the primary dryer and the activated carbon modifier of the present invention are existing devices, the primary dryer 11 is used for receiving activated carbon saturated by adsorption and discharged from a centrifuge 2 and a reacted primary catalyst and performing heating and drying, and the primary activated carbon modifier 12 is used for receiving activated carbon loaded with an active ingredient and dried by the primary dryer 11 and performing calcination, and fixing and loading an active oxide on the activated carbon. The utility model also comprises a first-stage catalyst storage tank 13, and the prepared first-stage catalyst is stored in the first-stage catalyst storage tank 13 for later use. According to the utility model, before each round of catalytic ozonation reaction, a primary catalyst is filled in a primary reactor 7 in advance, after each round of catalytic ozonation reaction is finished, the reacted primary catalyst is discharged and then is sent to a primary dryer 11 for drying, and then roasting regeneration is carried out to realize recycling until ash is converted by high-temperature roasting in the recycling process and is cleaned out.

The utility model discloses pass through high temperature calcination with the active carbon after the absorption saturation in one-level active carbon modified unit, with the adsorbed metal ion among the adsorption process, including main catalyst active ingredient's polyvalent attitude metallic iron, the metal ion that is of great variety, content rare but ubiquitous becomes the reaction active component of oxide as catalyst effect reinforcing, silicon element that difficult getting rid of is simultaneously strained at the membrane in concentrate processing procedure as catalyst structure auxiliary agent, as the beneficial component to follow-up catalytic ozonation reaction, like Fe₃O₄、Al₂O₃、SiO₂And the oxide of the metal cation comprises Na₂O、CaO、TiO₂The heavy metal oxide includes oxide containing Cu, Mn, Ni, Sr, Pd and Zn elements, and the chlorine, nitrogen and sulfur elements on the active carbon are generally removed in gaseous state in the high-temperature roasting process, so that the waste in the middle stage of reaction is greatly reduced, the degradation degree is improved, and the biodegradability of subsequent treatment is improved。

As shown in fig. 1, the secondary activated carbon modification unit of the present invention is used for loading the primary catalyst again and preparing a secondary catalyst, and includes a formula 14, a secondary dryer 15 and a secondary activated carbon modifier 16, wherein the formula 14 is used for distributing and modifying the primary catalyst and the reacted secondary catalyst, a plurality of independent ion impregnation tanks are arranged in the formula 14, and predetermined ions such as cobalt ions, copper ions, cerium ions, etc. are added into the impregnation tanks. The secondary dryer 15 is used for receiving the soaked catalyst and heating and drying the catalyst, the secondary activated carbon modifier 16 is used for receiving the activated carbon loaded with active ingredients and dried by the secondary dryer 15 and roasting the activated carbon, the activated oxides are fixedly loaded on the activated carbon, a more efficient catalytic ozonation catalyst is formed through secondary energization, and the secondary catalyst is stored in the secondary catalyst storage tank 17 for later use. According to the utility model, before each round of catalytic ozonation reaction, a secondary catalyst is filled in a secondary reactor 9 in advance, after each round of catalytic ozonation reaction is finished, the discharged secondary catalyst after reaction is taken out and sent to a formula device 14 for regeneration, so that cyclic utilization is realized until the ash is converted by high-temperature roasting in the cyclic utilization process and is swept out.

The utility model enables the secondary catalyst to comprise Fe by secondarily energizing the primary catalyst₃O₄、Co_xO_y、Cu_xO_y、CeO₂、Al₂O₃、SiO₂And Na₂O、CaO、TiO₂The oxide of metal cations and the oxide containing heavy metal containing Mn, Ni, Sr, Pd and Zn can meet the complicated and variable water quality requirement of the membrane filtration concentrated solution, further enhance the mass transfer and reaction among the catalyst, ozone and organic pollutants in the secondary catalytic ozonation reaction process, and secondarily improve the catalytic reaction effect.

As shown in the figures 1 and 2, the primary catalytic ozonation unit of the utility model is used for primary catalytic ozonation of wastewater to be treated, and comprises an ozone generator 18 and a primary reactor 7, the ozone generator 18 adopts an air source ozone generator, can save the electric energy consumption of air oxygen enrichment, the concentration of the generated ozone is not high, the utility model can arrange one ozone generator 18 to provide ozone for the primary reactor 7 and the secondary reactor 9, or two ozone generators 18 are arranged to respectively provide ozone for the primary reactor 7 and the secondary reactor 9, the primary reactor 7 is a packed bed type reaction tower body, the upper part of the primary reactor 7 is provided with a first water inlet 7-5, the lower part of the primary reactor 7 is provided with a first water outlet 7-9, a liquid discharge pipe 2-13 is communicated with the first water inlet 7-5 of the primary reactor 7, and wastewater can be pumped into the primary reactor 7 through a liquid storage tank and a first water inlet pipe. A first grid box 7-2 which can be replaced and is provided with a first-stage catalyst is arranged in a first-stage reactor 7, a first aerator 7-3 is arranged at the bottom of the first-stage reactor 7, an ozone generator 18 is communicated with the first aerator 7-3 through a first air pipe 18-1, wastewater enters from the upper end of a tower body, the whole tower body is filled, then a reaction is started, a sequential catalytic ozone oxidation reaction is carried out, and water is discharged from the lower end after the reaction is finished, the first grid box 7-2 adopts a metal grid box, the grid of the first grid box 7-2 is 50-100 meshes, the first-stage catalyst is arranged in the first grid box 7-2, the first aerator 7-3 is an ozone microbubble aeration disc, can realize supply of 1-100 mu m ozone microbubbles, and under the common carrying effect of ascending flow containing ozone gas and the catalyst, the full contact between the ozone and the organic pollutants in the water and the catalyst is realized, and the rapid mass transfer and the surface reaction of the catalyst are realized.

As shown in the figures 1 and 2, a first emergency evacuation port 7-8 is arranged at the bottom of the primary reactor 7, and the primary catalyst is removed out of the first grid box 7-2 or becomes fine powder due to abrasion, is removed and deposited at the bottom of the tower, or needs to stop reaction in case of emergency, and is evacuated through the first emergency evacuation port 7-8 of the primary reactor 7 after the ozone generator 18 is turned off.

As shown in fig. 1 and 2, the first frame 7-6 with a frame structure is arranged in the first-stage reactor 7, at least two first grid boxes 7-2 are arranged on the first frame 7-6, the first-stage reactor 7 is provided with filling openings corresponding to the first grid boxes 7-2, and the first access door 7-7 is hermetically arranged on the first-stage reactor 7 and covers the corresponding filling openings, so that the rapid catalyst filling and the timed reaction tower body maintenance are conveniently completed.

As shown in figure 1, the secondary catalytic ozonation unit is used for carrying out secondary catalytic ozonation on wastewater treated by primary catalytic ozonation and comprises an ozone generator 18 and a secondary reactor 9, wherein the secondary reactor 9 is a packed bed type reaction tower body, and the structure of the secondary reactor 9 is basically the same as that of the primary reactor 7. The upper part of a secondary reactor 9 of the utility model is provided with a second water inlet, the lower part is provided with a second water outlet, a first water outlet 7-9 of a primary reactor 7 is communicated with the second water inlet of the secondary reactor 9 through a second water inlet pipe 7-1, a third water inlet pump 8 is arranged on the second water inlet pipe 7-1, the water outlet of the primary reactor 7 is fed from the upper end of a tower body through the third water inlet pump 8, the whole tower body is filled, then the reaction is started for carrying out the sequential catalytic ozone oxidation reaction, and the water is discharged from the lower end after the reaction is finished and is sent to a subsequent biochemical treatment system. A second grid box 9-2 which can be replaced and is provided with a second catalyst is arranged in a second-stage reactor 9, a second aerator 9-1 is arranged at the bottom of the second-stage reactor 9, and an ozone generator 18 is communicated with the second aerator 9-1 through a second air pipe 18-2. The second grid box 9-2 adopts a metal grid box, a secondary catalyst is placed in the second grid box 9-2, the second aerator 9-1 is an ozone microbubble aeration disc, 1-100 mu m ozone microbubble supply can be realized, under the common carrying effect of the upflow ozone-containing gas and the catalyst, the full contact between the ozone, the organic pollutants in the water and the catalyst is realized, and the rapid mass transfer and the surface reaction of the catalyst are realized.

As shown in figure 1, the bottom of the secondary reactor 9 of the utility model is provided with a second emergency evacuation port, the secondary catalyst falls out of the second grid box 9-2 or becomes fine powder due to abrasion and is removed and deposited on the bottom of the tower, or the reaction needs to be stopped in case of emergency, and after the ozone generator 18 is closed, the secondary catalyst is evacuated by the second emergency evacuation port of the secondary reactor 9.

Similarly, the second reactor 9 of the utility model is internally provided with a second box frame with a frame structure, at least two second grid boxes 9-2 are arranged on the second box frame, the second reactor 9 is provided with filling openings corresponding to the second grid boxes 9-2, and a second access door is hermetically arranged on the second reactor 9 and covers the corresponding filling openings, thus being convenient for finishing the rapid filling of the catalyst and the timing maintenance of the reaction tower body.

As shown in figure 1, the utility model also comprises an ozone recoverer 10, wherein the tops of the primary reactor 7 and the secondary reactor 9 are respectively provided with a first recovery port 7-4 and a second recovery port for recovering redundant ozone, the first recovery port and the second recovery port are communicated with a recovery gas port of the ozone recoverer 10, and a gas outlet of the ozone recoverer 10 is communicated with a first gas pipe 18-1 or/and a second gas pipe 18-2. Can further reduce the ozone consumption and the treatment cost.

Claims (7)

1. A catalytic ozonation system for membrane filtration concentrate treatment by using reaction intermediate waste is characterized in that: comprises an activated carbon adsorption unit, a primary activated carbon modification unit, a secondary activated carbon modification unit, a primary catalytic ozonation unit and a secondary catalytic ozonation unit;

the activated carbon adsorption unit is used for adsorbing metal cations, heavy metal ions, metal acid radicals, miscellaneous salt ions and part of organic substances in the membrane filtration concentrated solution and comprises an adsorption reaction tank and a centrifugal machine, wherein a stirrer is arranged in the adsorption reaction tank and used for uniformly stirring filtrate and activated carbon, a discharge outlet at the bottom of the adsorption reaction tank is communicated with a feed inlet of the centrifugal machine, a liquid phase outlet of the centrifugal machine is communicated with the primary reactor through a liquid discharge pipe, and a first water inlet pump is arranged on the liquid discharge pipe;

the primary active carbon modification unit is used for preparing a primary catalyst from the adsorption saturated active carbon, and comprises a primary dryer and a primary active carbon modifier, wherein the primary dryer is used for receiving the adsorption saturated active carbon discharged by a centrifugal machine and the reacted primary catalyst and heating and drying the activated carbon and the reacted primary catalyst; the primary activated carbon modifier is used for receiving the activated carbon loaded with the active ingredients and dried by the primary dryer, roasting the activated carbon and fixedly loading the active oxides on the activated carbon;

the secondary active carbon modification unit is used for loading the primary catalyst again and preparing the primary catalyst into a secondary catalyst, and comprises a formula device, a secondary dryer and a secondary active carbon modifier, wherein the formula device is used for distributing, soaking and modifying the primary catalyst and the reacted secondary catalyst, and a plurality of independent ion impregnation tanks are arranged in the formula device; the secondary dryer is used for receiving the soaked catalyst and heating and drying the catalyst; the secondary activated carbon modifier is used for receiving the activated carbon loaded with the active ingredients and dried by the secondary dryer, roasting the activated carbon and fixedly loading the active oxides on the activated carbon;

the primary catalytic ozonation unit is used for primary catalytic ozonation of wastewater to be treated and comprises an ozone generator and a primary reactor, wherein the upper part of the primary reactor is provided with a first water inlet, the lower part of the primary reactor is provided with a first water outlet, a liquid discharge pipe is communicated with the first water inlet of the primary reactor, a first grid box which can be replaced and is provided with a primary catalyst is arranged in the primary reactor, the bottom of the primary reactor is provided with a first aerator, and the ozone generator is communicated with the first aerator through a first air pipe;

the secondary catalytic ozonation unit is used for carrying out secondary catalytic ozonation on the wastewater after the primary catalytic ozonation treatment, and comprises an ozone generator and a secondary reactor, wherein a second water inlet is formed in the upper part of the secondary reactor, a second water outlet is formed in the lower part of the secondary reactor, a first water outlet of the primary reactor is communicated with a second water inlet of the secondary reactor through a second water pipe, a third water inlet pump is installed on a second water inlet pipe, a second grid box capable of being replaced and provided with a secondary catalyst is installed in the secondary reactor, a second aerator is installed at the bottom of the secondary reactor, and the ozone generator is communicated with the second aerator through a second air pipe.

2. The catalytic ozonation system according to claim 1, wherein the catalytic ozonation system comprises: the liquid discharge pipe is also connected with a filter and a liquid storage tank, the liquid storage tank is communicated with a first water inlet on the first-stage reactor through a first water inlet pipe, and the first water inlet pipe is provided with a second water inlet pump.

3. The catalytic ozonation system according to claim 1, wherein the catalytic ozonation system comprises: the first-stage reactor is internally provided with a first box frame with a frame structure, at least two first grid boxes are arranged on the first box frame, filling openings corresponding to the first grid boxes are arranged on the first-stage reactor, and a first access door is hermetically arranged on the first-stage reactor and covers the corresponding filling openings.

4. The catalytic ozonation system according to claim 2, wherein the catalytic ozonation system comprises: the second reactor is internally provided with a second box frame with a frame structure, at least two second grid boxes are arranged on the second box frame, filling openings corresponding to the second grid boxes are arranged on the second reactor, and a second access door is hermetically arranged on the second reactor and covers the corresponding filling openings.

5. The catalytic ozonation system according to claim 1, wherein the catalytic ozonation system comprises: the bottom of the first-stage reactor is provided with a first emergency evacuation port, and the bottom of the second-stage reactor is provided with a second emergency evacuation port.

6. The catalytic ozonation system according to claim 1, wherein the catalytic ozonation system comprises: the ozone recovery device is also provided, the top parts of the primary reactor and the secondary reactor are respectively provided with a first recovery port and a second recovery port for recovering redundant ozone, the first recovery port and the second recovery port are connected and communicated with a recovery gas port of the ozone recovery device, and a gas outlet of the ozone recovery device is connected and communicated with a first gas pipe or/and a second gas pipe.

7. The catalytic ozonation system according to claim 1, wherein the catalytic ozonation system comprises: the first aerator and the second aerator are ozone microbubble aeration disks.

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