CN106830457B - Electrode coupling ozone oxidation integrated reactor - Google Patents
Electrode coupling ozone oxidation integrated reactor Download PDFInfo
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- CN106830457B CN106830457B CN201710177803.8A CN201710177803A CN106830457B CN 106830457 B CN106830457 B CN 106830457B CN 201710177803 A CN201710177803 A CN 201710177803A CN 106830457 B CN106830457 B CN 106830457B
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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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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Abstract
The invention relates to a sewage treatment device, in particular to a reactor for treating sewage by coupling an electrode technology and an ozone oxidation technology. The electrode technology and the ozone oxidation technology are coupled in the same reactor, so that the electrode coupling ozone oxidation integrated reactor which has the advantages of low equipment cost, less consumption of parts and components, capability of avoiding the defect of ozone oxidation selectivity, greatly improving ozone oxidation efficiency, reducing ozone consumption, shortening ozone reaction time and achieving the purposes of effectively treating biochemical effluent and improving treatment efficiency is provided.
Description
Technical Field
The invention relates to a sewage treatment device, in particular to a reactor for treating sewage by coupling an electrode technology and an ozone oxidation technology.
Background
Ozone oxidation technology is widely used in the field of water treatment, such as sterilization and disinfection of urban water supply, advanced treatment of industrial wastewater and the like. At present, the technology is more and more paid attention to a method for treating organic wastewater, particularly organic wastewater difficult to biodegrade. However, the popularization and application of the ozone oxidation technology are severely limited due to the problems of low oxidation selectivity, low ozone utilization rate, high running cost and the like. Ozone can directly oxidize and decompose organic matters as a strong oxidant, but has strong selectivity in the reaction with the organic matters, so that only macromolecular organic matters in wastewater can be converted into micromolecular organic matters, and the efficiency of generating hydroxyl free radicals is low.
The electrochemical method for treating the wastewater generally does not need to add an oxidant, and has the advantages of simple equipment, small volume, small sludge amount and simple post-treatment, and is commonly called as an environment-friendly green oxidation technology. Meanwhile, the traditional three-dimensional electrode reaction is used for treating the organic wastewater which is difficult to biodegrade, and electrochemical degradation of the organic wastewater is carried out mostly under the action of a simple external electric field, so that the conversion and removal efficiency of organic pollutants in the wastewater are low, and the conversion of the organic matters in the wastewater cannot be realized.
The combination of the ozone oxidation technology and the electrode technology can improve the wastewater treatment effect, but the prior art simply combines electrolysis and ozone oxidation, and has low treatment efficiency and high cost. The Chinese patent application No. 201510816139.8, which is a wastewater treatment device and a method for treating wastewater by the device, comprises an ozone generator, a three-dimensional electrode reactor and a direct-current regulated power supply, wherein an ozone gas distribution bottom support is arranged in the three-dimensional electrode reactor, an ozone aeration head is arranged below the ozone gas distribution bottom support, a particle electrode and a main electrode are arranged above the ozone aeration head, and a waste liquid feeding port and a sampling port are arranged on the cavity wall of the three-dimensional electrode reactor in a penetrating way. According to the technical scheme, ozone is directly introduced into the electrode reactor, so that the treatment efficiency of wastewater is low, the respective effects cannot be fully exerted, and unpredictable interference exists.
The system comprises an ozone catalytic oxidation reactor, an ozone generator, an oxygen tank, a gas-liquid separation device, a filter, an electric adsorption device, a reuse water tank, a concentrate water tank, a water production valve, a concentrate water valve and a connecting pipeline; wherein, the outlet of the coking wastewater after biochemical treatment and coagulating sedimentation is connected with the water inlet of the ozone catalytic oxidation reactor; the water outlet of the ozone catalytic oxidation reactor is connected with the gas-liquid separation device; the water outlet of the gas-liquid separation device is connected with the water inlet of the filter; the water outlet of the filter is connected with the water inlet of the electro-adsorption device, the water outlet of the electro-adsorption device is connected with the reuse water tank through a water generating valve and is connected with the concentrate water tank through a concentrate electromagnetic valve. In the technical scheme, the ozone catalytic oxidation reactor and the electro-adsorption device are in a simple series connection mode and can only respectively and successively play roles, and do not play a real synergistic effect, so that the defects existing in the independent treatment of the ozone catalytic oxidation reactor and the electro-adsorption device cannot be overcome.
The treatment device comprises a pre-electrolysis unit and an ozone oxidation unit which are communicated, wherein a tail gas outlet of the ozone oxidation unit is connected into the pre-electrolysis unit. The method comprises the steps that wastewater firstly enters a pre-electrolysis unit to carry out electrolytic reaction, the wastewater after the electrolytic reaction flows into an ozone oxidation unit, ozone is introduced into the ozone oxidation unit to carry out reaction, and ozone tail gas generated by the ozone oxidation unit is introduced into the pre-electrolysis unit to be aerated. According to the technical scheme, the pre-electrolysis unit and the ozone oxidation unit are connected in series, and meanwhile, ozone tail gas is led into the pre-electrolysis unit, but the pre-electrolysis unit and the ozone oxidation unit are still two relatively independent devices, so that the equipment cost is high.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides the electrode coupling ozone oxidation integrated reactor which has low equipment cost and less consumption of parts, can avoid the defect of ozone oxidation selectivity, greatly improves ozone oxidation efficiency, reduces ozone consumption, shortens ozone reaction time, and achieves the aims of effectively treating biochemical effluent and improving treatment efficiency.
In order to achieve the aim, the electrode coupling ozone oxidation integrated reactor is designed in the invention, the reactor main body is of a cavity structure with a hollow inside and a closed outside, the inside of the reactor main body is divided into an electrolysis reaction chamber and an ozone reaction chamber by a partition plate, a space is reserved between the partition plate and a top plate and a bottom plate of the reactor, and the height of the top plate of the reactor above the partition plate is lower than that of the top plate of the electrolysis reaction chamber and the top plate of the ozone reaction chamber; an upper water inlet baffle is arranged at the joint of the top plate of the reactor above the partition plate and the side wall of the electrolytic reaction chamber, and the upper water inlet baffle is inclined towards the direction of the electrolytic reaction chamber; the top of the electrolytic reaction chamber is provided with a water inlet, a plurality of groups of electrode plates are arranged in the electrolytic reaction chamber, and the electrode plates are connected with an external power supply through wires arranged in a wire conduit; the bottom of the partition plate is provided with a lower water inlet baffle plate which is inclined towards the ozone reaction chamber; an aeration system is arranged at the bottom of the ozone reaction chamber and comprises an air inlet pipe and a micropore aeration disc, wherein the air inlet pipe is communicated with an ozone source, and the micropore aeration disc is arranged on the air inlet pipe; the top of the ozone reaction chamber is provided with a gas collecting cover which is in an inverted funnel shape, and the top end of the gas collecting cover is connected with the tail gas destruction device through an exhaust pipe; a water outlet is arranged on the side wall of the ozone reaction chamber below the gas collection cover, and the water outlet is in the form of a water outlet weir.
Preferably, the included angle between the upper water inlet baffle plate and the horizontal plane is 20-80 degrees.
Preferably, the included angle between the lower water inlet baffle and the horizontal plane is 90-165 degrees.
Preferably, the electrode plate is fixed in the electrolytic reaction chamber through a clamping groove; in order to insulate the reactor and avoid corrosion in the electrolytic process, the clamping groove is made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC; the anode plate of the electrode plate adopts a titanium plate with a rare earth element plating layer of ruthenium, iridium, tantalum and the like, and the cathode plate can adopt materials of a titanium plate, a graphite plate, a stainless steel plate and the like.
Preferably, the distance between the electrode plates is 1-500cm, the thickness of the electrode plates is 1-5mm, and the number of the electrode groups is 1-10.
Preferably, the water outlet is 10-100cm below the bottom of the gas collection housing.
Preferably, a powdery catalytic material is introduced into the reactor to perform electrode coupling ozone catalytic oxidation reaction, and the catalytic material can be in a fixed bed form or a fluidized bed form; the active components of the powdery catalytic material have catalytic performance on ozone oxidation and electrolytic reaction, and belong to multi-effect catalysts.
The reactor in the form of a fixed bed is designed as follows: the top plate of the electrolytic reaction chamber is also provided with a water inlet stirrer, the bottom of the electrolytic reaction chamber is also provided with a diving stirrer, and the side wall of the top of the electrolytic reaction chamber is provided with a water inlet; the bottom of the electrode plate is also provided with a supporting net, and a catalyst solid bed is placed on the supporting net; the gas collecting cover at the top of the ozone reaction chamber is changed into a three-phase separator which is in an inverted funnel shape, and the top end of the three-phase separator is connected with the tail gas destruction device through an exhaust pipe; a supporting net is arranged above the microporous aeration disc, a catalyst solid bed is placed on the supporting net, the lower layer of the fixed bed is large-particle-size gravel, and the upper layer of the fixed bed is catalyst; a water outlet is arranged on the side wall of the ozone reaction chamber above the bottom of the three-phase separator, and the water outlet is in the form of a water outlet weir.
As a further preferable mode, the distance between the electrode plates is 100-500cm, the thickness of the electrode plates is 1-5mm, and the number of the electrode groups is 1-2; the diameter of the mesh of the supporting net in the electrolytic reaction chamber is 1-2mm, the catalyst in the fixed bed is spherical, the particle diameter is 3-5mm, and the filling degree of the catalyst fixed bed is 30% -80%; the stirring speed of the water inlet stirrer is 60-500rad/min, and the stirring strength of the submersible stirrer is 1-10w/m < 3 >; the supporting net in the ozone reaction chamber is made of titanium alloy, the diameter of the net holes is 5-10mm, the particle size of the gravel is 12-30mm, the catalyst is spherical, and the particle size is 3-5mm; the height of the bottom of the water outlet weir crest is 5-50cm higher than that of the bottom of the three-phase separator; the catalyst is a catalytic material taking gamma-Al 2O3 as a carrier and taking one or more oxides in a load Zn, ti, mn, sn, fe, bi as active components; preferably, the gamma-Al 2O3 is a sphere with the diameter of 3-5mm, the active components are oxides of Ti, sn and Mn, and the molar ratio of the active components is Ti: sn: mn= (10-200): (1-30): (5-100).
The fluidized bed type reactor is improved as follows: the top plate of the electrolytic reaction chamber is also provided with a water inlet stirrer, the side wall of the bottom of the electrolytic reaction chamber is also provided with a diving stirrer, and the side wall of the top of the electrolytic reaction chamber is provided with a water inlet and a catalyst feeding port; the gas collecting cover at the top of the ozone reaction chamber is changed into a three-phase separator which is in an inverted funnel shape, inverted scale-shaped blades are arranged outside the three-phase separator, and the top end of the three-phase separator is connected with the tail gas breaking device through an exhaust pipe; the upper part of the bottom of the three-phase separator is also provided with an inclined tube sedimentation device, the side wall of the ozone reaction chamber which is positioned at the same horizontal position with the bottom of the inclined tube sedimentation device is provided with a water outlet, and the water outlet is in the form of an effluent weir.
As a further preference, the partition plate is in a parallelogram shape, and the included angle gamma of the acute angle of the parallelogram is 45 degrees to 85 degrees; the spacing of the electrode plates is 2-20cm, more preferably 2-6cm, the thickness of the electrode plates is 1-5mm, and the number of electrode groups is 2-5; the stirring speed of the water inlet stirrer is 60-500rad/min, and the stirring strength of the submersible stirrer is 1-10w/m < 3 >; the bottom of the water outlet is 5-50cm higher than the bottom of the three-phase separator; the inclined tube inclination angle is 50-70 degrees; the added catalyst is a catalytic material taking powdered activated carbon as a carrier and carrying one or more oxides in Zn, ti, mn, sn, fe, bi as active components; preferably, the powder activated carbon particles are 80-100 meshes, the active components are oxides of Ti, sn and Mn, and the molar ratio of the active components is Ti: sn: mn= (10-200): (1-30): (5-100).
The invention realizes the coupling of the electrode technology and the ozone oxidation technology in the same reactor, and the working principle is as follows: the wastewater enters the reactor, is guided by the upper water inlet baffle plate and firstly enters the electrolytic chamber for electrode electrolytic oxidation-reduction reaction, and ring-opening and chain breakage are carried out on annular and long-chain macromolecular organic matters in the wastewater, so that the chemical energy required by oxidation of pollutants is effectively reduced, the oxidation efficiency of the subsequent ozone oxidation is improved, the ozone consumption is reduced, and the defect of selectivity of the ozone oxidation technology is overcome; the wastewater after primary electrolysis reaction enters an ozone reaction chamber through the space between the baffle plate and the bottom plate of the reactor through the lower water inlet baffle plate, the wastewater fully dissolves ozone in the ozone reaction chamber and carries out oxidation reaction, the wastewater containing saturated ozone enters the electrolysis reaction chamber through the space between the baffle plate and the top plate of the reactor under the flow guide of the upper water inlet baffle plate, and the dissolved saturated ozone loses electrons at the electrode to quickly carry out coupling reaction of electrode electrolysis and ozone oxidation, and the wastewater enters the ozone reaction chamber again through the flow guide of the lower water inlet baffle plate to dissolve ozone, so that the gas-liquid mass transfer rate is accelerated, a stable internal circulation mode is formed, and the ozone utilization efficiency is greatly improved; after a plurality of cycles, the gas is discharged out of the reactor after being destroyed by the gas collecting cover and the tail gas destroying device, and the waste water is discharged out of the reactor through the water outlet weir. The technology mainly comprises the following reaction mechanisms: (1) In the ozone reaction chamber, gaseous ozone is dissolved in the wastewater, and ozone molecules directly oxidize pollutants under the acid-base condition of the wastewater; (2) electrode system: the high oxidation potential at the anode plate directly oxidizes pollutants, and the high reduction potential at the cathode plate directly reduces pollutants; (3) an ozone electrode coupling reaction system: the acidic environment around the anode plate promotes ozone molecules to directly oxidize pollutants, and the alkaline environment around the cathode plate promotes ozone to generate OH to indirectly oxidize pollutants; ozone molecules are used for generating intermediate products such as O, O3-and the like at a cathode to indirectly oxidize pollutants; the electrons obtained by the oxygen molecules at the cathode react with water to generate H2O2, and the H2O2 can directly oxidize pollutants; H2O2 and ozone molecules have synergistic effect, and the reaction can generate OH.
The reactor in the form of the fixed bed combines the three-dimensional electrode technology and the ozone catalytic oxidation technology in the same reactor, and synchronously realizes the series application and the coupling application of the two technologies in the form of the fixed bed; the working principle is as follows: the wastewater enters the reactor, is guided by the upper water inlet baffle and the water inlet stirrer, firstly enters the electrolysis chamber, and is matched with the catalyst in the fixed bed to carry out three-dimensional electrode electrolytic oxidation-reduction reaction, so that ring-opening and chain breaking are carried out on the annular and long-chain macromolecular organic matters in the wastewater, the chemical energy required by oxidation of pollutants is effectively reduced, the oxidation efficiency of the subsequent ozone oxidation is improved, the ozone consumption is reduced, and the defect that the ozone oxidation technology has selectivity is overcome; under the action of the pushing flow of the submersible stirrer, the wastewater after the primary electrolytic reaction is guided into an ozone reaction chamber through a space between a baffle plate and a bottom plate of a reactor by a lower water inlet baffle plate, the wastewater and a catalyst in a fixed bed fully dissolve ozone in the ozone reaction chamber and perform catalytic oxidation reaction, the wastewater containing saturated ozone enters the electrolytic reaction chamber through the space between the baffle plate and a top plate of the reactor under the guide of the upper water inlet baffle plate, electrons are lost from the dissolved saturated ozone at a three-dimensional electrode, the coupling reaction of the three-dimensional electrode and the catalytic oxidation of the ozone is rapidly performed, the wastewater is guided by the lower water inlet baffle plate and then enters the ozone reaction chamber again to dissolve the ozone, the gas-liquid mass transfer rate is accelerated, a stable internal circulation mode is formed, and the ozone utilization efficiency is greatly improved; the waste water is separated by a three-phase separator after circulating for several times, the gas is discharged out of the reactor by a tail gas destruction device, the catalyst is remained in the reactor for circulating reaction, and the waste water is discharged out of the reactor by a water outlet weir. The catalyst is added in the reactor in a fixed bed form, compared with a two-dimensional electrode, the specific surface area of ozone contacted with pollutants and the surface-to-body ratio of an electrode system are greatly improved, and the catalytic efficiency of active components is cooperated, so that the reaction efficiency is greatly improved; the following reaction mechanisms mainly exist: (1) The ozone catalytic oxidation system is characterized in that gaseous ozone is dissolved in wastewater, ozone molecules directly oxidize pollutants in the wastewater, the pollutants and the ozone molecules are adsorbed on the surface of a catalyst, active sites on the surface of the catalyst participate in ozone decomposition reaction in the water, and the rate of generating OH by ozone decomposition is accelerated; forming a complex which is easy to react with ozone molecules on the surface of the metal oxide by the pollutant; (2) three-dimensional electrode system: the high oxidation potential at the anode plate directly oxidizes pollutants, the high reduction potential at the cathode plate directly reduces the pollutants, the catalyst is electrified in an electric field due to electrostatic induction, each catalyst particle forms a tiny primary cell, the pollutants are adsorbed on the surface of the catalyst and are electrolyzed and degraded, the electrolytic surface-to-surface ratio is greatly improved, the current efficiency is improved, and the reaction energy consumption is reduced; (3) a three-dimensional electrode coupling ozone catalytic oxidation reaction system: the acidic environment around the anode plate promotes ozone molecules to directly oxidize pollutants, and the alkaline environment around the cathode plate promotes ozone to generate OH to indirectly oxidize pollutants; ozone molecules are subjected to electron generation on the surfaces of a cathode and a catalyst to indirectly oxidize pollutants through intermediate products such as O, O3-and the like; the electrons obtained by the oxygen molecules at the cathode react with water to generate H2O2, and the H2O2 can directly oxidize pollutants; H2O2 and ozone molecules have synergistic effect, and OH can be generated by the reaction; the catalyst forms a primary cell under the electrostatic induction condition of an electric field, metal oxide loaded by the catalyst reacts with O2 under the electrifying condition to generate OH, pollutants and ozone molecules are adsorbed on the surface of the catalyst and are rapidly contacted with the nascent state OH, and the reaction efficiency is greatly improved (4) the catalyst system: the Sn and Ti metal oxides have synergistic effect, ozone molecules and an electric field can both utilize the characteristic that the energy levels of conduction bands of SnO2 and TiO2 differ by 0.5V, electrons on the surface of TiO2 move to SnO2 under the oxidation effect of ozone and intermediate products thereof or the effect of the electric field, electron holes are formed on the surface of TiO2, the probability of recombination of electrons and holes on the surface of TiO2 can be reduced by SnO2, and the holes have extremely strong oxidizing property and are easy to generate OH with water and oxygen.
The three-dimensional electrode technology and the ozone catalytic oxidation technology are combined in the same reactor, and the serial application and the coupling application of the two technologies are synchronously realized in the fluidized bed mode; the working principle is as follows: the wastewater enters a reactor, then a powder catalyst is added, the mixture of the wastewater and the catalyst is guided by an upper water inlet baffle plate, and is pushed to be homogenized by a water inlet stirrer, and then enters an electrolytic reaction chamber for three-dimensional electrolytic oxidation-reduction reaction, so that ring-opening and chain breaking of annular and long-chain macromolecular organic matters in the wastewater are carried out, the chemical energy required by oxidation of pollutants is effectively reduced, the oxidation efficiency of the subsequent ozone oxidation is improved, the ozone consumption is reduced, and the defect that an ozone oxidation technology has selectivity is overcome; after primary electrolytic reaction, under the action of the push flow of a submersible stirrer, the wastewater and the powder catalyst are guided into an ozone reaction chamber through a lower water inlet baffle plate by a space between a baffle plate and a bottom plate of the reactor, the wastewater and the catalyst fully dissolve ozone in the ozone reaction chamber and perform catalytic oxidation reaction, the wastewater and the catalyst containing saturated ozone enter the electrolytic reaction chamber through the space between the baffle plate and a top plate of the reactor under the guide of the upper water inlet baffle plate, the dissolved saturated ozone loses electrons at a three-dimensional electrode, the coupling reaction of the three-dimensional electrode and ozone catalytic oxidation is rapidly performed, and then the wastewater and the catalyst are guided by a lower water inlet baffle plate to reenter the ozone reaction chamber to dissolve ozone, so that the gas-liquid mass transfer rate is accelerated, a stable internal circulation mode is formed, and the ozone utilization efficiency is greatly improved; the waste water after circulation for several times realizes the separation of powder catalyst, waste water and gas under the action of a three-phase separator, the gas is discharged out of the reactor through a tail gas destruction device, the powder catalyst is left in the reactor for circulation reaction, the waste water is precipitated through an inclined tube precipitation device and then discharged out of the reactor through an effluent weir, the powder catalyst which is not separated by the three-phase separator in water is subjected to secondary solid-liquid separation in the inclined tube precipitation device, and the effluent SS is ensured to reach the standard while the loss of the catalyst is avoided. The powder catalyst circulates in the reactor in a fluidized state, so that compared with a fixed bed, the specific surface area contacted with ozone and pollutants is greatly improved, and the catalytic efficiency is higher; the following reaction mechanisms mainly exist: (1) The ozone catalytic oxidation system is characterized in that gaseous ozone is dissolved in wastewater, ozone molecules directly oxidize pollutants in the wastewater, the pollutants and the ozone molecules are adsorbed on the surface of a catalyst, active sites on the surface of the catalyst participate in ozone decomposition reaction in the water, and the rate of ozone decomposition to generate OH is accelerated; forming a complex which is easy to react with ozone molecules on the surface of the metal oxide by the pollutant; (2) three-dimensional electrode system: the high oxidation potential at the anode plate directly oxidizes pollutants, the high reduction potential at the cathode plate directly reduces the pollutants, the catalyst is electrified in an electric field due to electrostatic induction, each catalyst particle forms a tiny primary cell, the pollutants are adsorbed on the surface of the catalyst and are electrolyzed and degraded, the electrolytic surface-to-surface ratio is greatly improved, the current efficiency is improved, and the reaction energy consumption is reduced; (3) a three-dimensional electrode coupling ozone catalytic oxidation reaction system: the acidic environment around the anode plate promotes ozone molecules to directly oxidize pollutants, and the alkaline environment around the cathode plate promotes ozone to generate OH to indirectly oxidize pollutants; ozone molecules obtain intermediate products such as electron production O, O3-and the like at a cathode, and indirectly oxidize pollutants; the electrons obtained by the oxygen molecules at the cathode react with water to generate H2O2, and the H2O2 can directly oxidize pollutants; H2O2 and ozone molecules have synergistic effect, and OH can be generated by the reaction; the catalyst forms a primary cell under the electrostatic induction condition of an electric field, the metal oxide loaded by the catalyst reacts with O2 under the electrifying condition to generate OH, pollutants and ozone molecules are adsorbed on the surface of the catalyst, and the pollutants and ozone molecules are quickly contacted with nascent state OH, so that the reaction efficiency is greatly improved.
Drawings
Fig. 1 is a schematic structural diagram of embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of embodiment 2 of the present invention.
Fig. 3 is a schematic structural diagram of embodiment 3 of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings.
Example 1
As shown in fig. 1, in the electrode coupling ozone oxidation integrated reactor described in this embodiment, the reactor main body is of a cavity structure with a hollow inside and a closed outside, the inside of the reactor main body is divided into an electrolytic reaction chamber 2 and an ozone reaction chamber 3 by a partition board 1, a space is reserved between the partition board and a top plate of the reactor and a bottom plate of the reactor, and the height of the top plate of the reactor above the partition board is lower than that of the top plate of the electrolytic reaction chamber and that of the top plate of the ozone reaction chamber; an upper water inlet baffle 4 is arranged at the joint of the top plate of the reactor above the partition plate and the side wall of the electrolytic reaction chamber, the upper water inlet baffle inclines towards the direction of the electrolytic reaction chamber, and the included angle between the upper water inlet baffle and the horizontal plane is 20-80 degrees; a water inlet 5 is arranged at the top of the electrolytic reaction chamber, a plurality of groups of electrode plates 6 are arranged in the electrolytic reaction chamber, the electrode plates are fixed in the electrolytic reaction chamber through clamping grooves, and the clamping grooves are made of glass fiber reinforced plastics, polytetrafluoroethylene or UPVC materials; the electrode plate is connected with an external power supply through a lead arranged in the conduit, the anode plate of the electrode plate adopts a titanium plate with a rare earth element plating layer of ruthenium, iridium, tantalum and the like, and the cathode plate adopts a material of a titanium plate, a graphite plate or a stainless steel plate and the like; the distance between the electrode plates is 1-500cm, the thickness of the electrode plates is 1-5mm, and the number of the electrode groups is 1-10; the bottom of the partition plate is provided with a lower water inlet baffle 7, the lower water inlet baffle is inclined towards the ozone reaction chamber, and the included angle between the lower water inlet baffle and the horizontal plane is 90-165 degrees; an aeration system 8 is arranged at the bottom of the ozone reaction chamber, the aeration system comprises an air inlet pipe and a micropore aeration disc, the air inlet pipe is communicated with an ozone source, and the micropore aeration disc is arranged on the air inlet pipe; the top of the ozone reaction chamber is provided with a gas collecting cover 9 which is in an inverted funnel shape, and the top end of the gas collecting cover is connected with a tail gas destruction device 10 through an exhaust pipe; the side wall of the ozone reaction chamber below the gas collection cover is provided with a water outlet 11 which is in the form of an effluent weir, and the effluent weir is 10-100cm lower than the bottom of the gas collection cover.
Example 2
As shown in fig. 2, in the electrode coupling ozone oxidation integrated fixed bed reactor described in this embodiment, the reactor body is of a hollow interior and a closed exterior chamber structure, the interior of the reactor body is divided into an electrolytic reaction chamber 2a and an ozone reaction chamber 3a by a partition plate 1a, a space is reserved between the partition plate and a top plate and a bottom plate of the reactor, and the height of the top plate of the reactor above the partition plate is lower than the heights of the top plate of the electrolytic reaction chamber and the top plate of the ozone reaction chamber; an upper water inlet baffle 4a is arranged at the joint of the top plate of the reactor above the partition plate and the side wall of the electrolytic reaction chamber, the upper water inlet baffle is inclined towards the direction of the electrolytic reaction chamber, and the included angle between the upper water inlet baffle and the horizontal plane is 20-80 degrees; a water inlet 5a is formed in the side wall of the top of the electrolytic reaction chamber, a water inlet stirrer 6a is arranged on the top plate of the electrolytic reaction chamber, a submerged stirrer 7a is arranged on the side wall of the bottom of the electrolytic reaction chamber, the stirring speed of the water inlet stirrer is 60-500rad/min, and the stirring strength of the submerged stirrer is 1-10w/m < 3 >; a plurality of groups of electrode plates 8a are arranged in the electrolytic reaction chamber, the electrode plates are fixed in the electrolytic reaction chamber through clamping grooves, and the clamping grooves are made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC materials; the electrode plate is connected with an external power supply through a lead arranged in a conduit, the anode plate of the electrode plate adopts a titanium plate with a rare earth element plating layer of ruthenium, iridium, tantalum and the like, the cathode plate adopts a titanium plate, a graphite plate or a stainless steel plate and other materials, the distance between the electrode plates is 100-500cm, the thickness of the electrode plates is 1-5mm, and the number of electrode groups is 1-2; the bottom of the electrode plate is provided with a supporting net, a catalyst solid bed 9a is placed on the supporting net, the diameter of a mesh hole of the supporting net is 1-2mm, the catalyst in the fixed bed is spherical, the particle size of the catalyst in the fixed bed is 3-5mm, and the filling degree of the catalyst fixed bed is 30% -80%; the bottom of the partition plate is provided with a lower water inlet baffle plate 10a, the lower water inlet baffle plate is inclined towards the ozone reaction chamber, and the included angle between the lower water inlet baffle plate and the horizontal plane is 90-165 degrees; an aeration system 11a is arranged at the bottom of the ozone reaction chamber, the aeration system comprises an air inlet pipe and a micropore aeration disc, the air inlet pipe is communicated with an ozone source, and the micropore aeration disc is arranged on the air inlet pipe; a supporting net is arranged above the microporous aeration disc, a catalyst fixed bed 12a is placed on the supporting net, the lower layer of the fixed bed is large-particle-size gravel 13a, the upper layer of the fixed bed is catalyst, the supporting net is made of titanium alloy, the diameter of a mesh is 5-10mm, the particle size of the gravel is 12-30mm, and the catalyst is spherical and has the particle size of 3-5mm; the top of the ozone reaction chamber is provided with a three-phase separator 14a which is in an inverted funnel shape, and the top end of the three-phase separator is connected with a tail gas destruction device 15a through an exhaust pipe; a water outlet 16a is arranged on the side wall of the ozone reaction chamber above the bottom of the three-phase separator, the water outlet is in the form of an effluent weir, and the bottom of the effluent weir is 5-50cm higher than the bottom of the three-phase separator. The catalyst in the electrolytic reaction chamber and the ozone reaction chamber is a catalytic material taking spherical gamma-Al 2O3 with the diameter of 3-5mm as a carrier and taking supported Ti, sn and Mn oxides as active components, wherein the molar ratio of the active components is as follows: sn: mn= (10-200): (1-30): (5-100).
Example 3
As shown in fig. 3, in the electrode coupling ozone oxidation integrated fluidized bed reactor described in this embodiment, the reactor body is of a hollow cavity structure with an enclosed outside, the inside of the reactor body is divided into an electrolysis reaction chamber 2b and an ozone reaction chamber 3b by a partition board 1b, spaces are formed between the partition board and a top plate and a bottom plate of the reactor, the partition board is in a parallelogram shape, and an acute included angle gamma of the parallelogram is 45 ° -85 °; the height of the top plate of the reactor above the partition plate is lower than the heights of the top plate of the electrolytic reaction chamber and the top plate of the ozone reaction chamber; an upper water inlet baffle 4b is arranged at the joint of the top plate of the reactor above the partition plate and the side wall of the electrolytic reaction chamber, the upper water inlet baffle is inclined towards the direction of the electrolytic reaction chamber, and the included angle between the upper water inlet baffle and the horizontal plane is 20-80 degrees; a water inlet 5b and a catalyst feeding port 15b are arranged on the side wall of the top of the electrolytic reaction chamber, a water inlet stirrer 6b is arranged on the top plate of the electrolytic reaction chamber, a submerged stirrer 7b is arranged on the side wall of the bottom of the electrolytic reaction chamber, the stirring speed of the water inlet stirrer is 60-500rad/min, and the stirring strength of the submerged stirrer is 1-10w/m3; a plurality of groups of electrode plates 8b are arranged in the electrolytic reaction chamber, the electrode plates are fixed in the electrolytic reaction chamber through clamping grooves, and the clamping grooves are made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC materials; the electrode plate is connected with an external power supply through a lead arranged in a conduit, the anode plate of the electrode plate adopts a titanium plate with a rare earth element plating layer of ruthenium, iridium, tantalum and the like, the cathode plate adopts a material of a titanium plate, a graphite plate or a stainless steel plate and the like, the distance between the electrode plates is 2-6cm, the thickness of the electrode plates is 1-5mm, and the number of electrode groups is 2-5; the bottom of the partition plate is provided with a lower water inlet baffle plate 9b which is inclined towards the ozone reaction chamber, and the included angle between the lower water inlet baffle plate and the horizontal plane is 90-165 degrees; an aeration system 10b is arranged at the bottom of the ozone reaction chamber, the aeration system comprises an air inlet pipe and a micropore aeration disc, the air inlet pipe is communicated with an ozone source, and the micropore aeration disc is arranged on the air inlet pipe; the top of the ozone reaction chamber is provided with a three-phase separator 11b which is in an inverted funnel shape, an inverted scale-shaped blade is arranged outside the ozone reaction chamber, and the top end of the three-phase separator is connected with a tail gas destruction device 12b through an exhaust pipe; an inclined tube sedimentation device 13b is arranged above the bottom of the three-phase separator, and the inclined tube inclination angle is 50-70 degrees; the side wall of the ozone reaction chamber which is positioned at the same horizontal position with the bottom of the inclined tube sedimentation device is provided with a water outlet 14b which is in the form of an effluent weir, and the bottom of the effluent weir is 5-50cm higher than the bottom of the three-phase separator. The added catalyst is a catalytic material taking 80-100 meshes of powder active carbon as a carrier and taking oxides of Ti, sn and Mn as active components, wherein the molar ratio of the active components is as follows: sn: mn= (10-200): (1-30): (5-100).
Claims (2)
1. An electrode coupling ozone oxidation integrated reactor is characterized in that: the reactor main body is of a cavity structure with a hollow inside and a closed outside, the inside of the reactor main body is divided into an electrolytic reaction chamber and an ozone reaction chamber by a partition board, a space is reserved between the partition board and a top plate and a bottom plate of the reactor, and the height of the top plate of the reactor above the partition board is lower than that of the top plate of the electrolytic reaction chamber and that of the top plate of the ozone reaction chamber; an upper water inlet baffle plate is arranged at the joint of the top plate of the reactor above the partition plate and the side wall of the electrolytic reaction chamber, the upper water inlet baffle plate is inclined towards the direction of the electrolytic reaction chamber, and the included angle between the upper water inlet baffle plate and the horizontal plane is 20-80 degrees; a water inlet is formed in the side wall of the top of the electrolytic reaction chamber, a water inlet stirrer is arranged on the top plate of the electrolytic reaction chamber, a submerged stirrer is arranged on the side wall of the bottom of the electrolytic reaction chamber, the stirring speed of the water inlet stirrer is 60-500rad/min, and the stirring strength of the submerged stirrer is 1-10w/m < 3 >; a plurality of groups of electrode plates are arranged in the electrolytic reaction chamber, the electrode plates are fixed in the electrolytic reaction chamber through clamping grooves, and the clamping grooves are made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC materials; the electrode plate is connected with an external power supply through a lead arranged in a conduit, the anode plate of the electrode plate adopts a titanium plate with ruthenium, iridium or tantalum rare earth element plating, the cathode plate adopts a titanium plate, a graphite plate or a stainless steel plate, the distance between the electrode plates is 100-500cm, the thickness of the electrode plates is 1-5mm, and the number of electrode groups is 1-2; the bottom of the electrode plate is provided with a supporting net, a catalyst solid bed is placed on the supporting net, the diameter of a mesh hole of the supporting net is 1-2mm, the catalyst in the fixed bed is spherical, the particle size of the catalyst in the fixed bed is 3-5mm, and the filling degree of the catalyst fixed bed is 30% -80%; the bottom of the partition plate is provided with a lower water inlet baffle plate, the lower water inlet baffle plate is inclined towards the ozone reaction chamber, and the included angle between the lower water inlet baffle plate and the horizontal plane is 90-165 degrees; an aeration system is arranged at the bottom of the ozone reaction chamber and comprises an air inlet pipe and a micropore aeration disc, wherein the air inlet pipe is communicated with an ozone source, and the micropore aeration disc is arranged on the air inlet pipe; a supporting net is arranged above the microporous aeration disc, a catalyst fixed bed is placed on the supporting net, the lower layer of the fixed bed is gravel with large particle size, the upper layer of the fixed bed is catalyst, the supporting net is made of titanium alloy, the diameter of a mesh is 5-10mm, and the particle size of the gravel is 12-30mm; the top of the ozone reaction chamber is provided with a three-phase separator which is in an inverted funnel shape, and the top end of the three-phase separator is connected with a tail gas destruction device through an exhaust pipe; a water outlet is formed in the side wall of the ozone reaction chamber above the bottom of the three-phase separator, the water outlet is in a water outlet weir form, and the bottom of a water outlet weir is 5-50cm higher than the bottom of the three-phase separator; the catalyst in the electrolytic reaction chamber and the ozone reaction chamber is a catalytic material taking a sphere gamma-Al 2O3 with the diameter of 3-5mm as a carrier and carrying active components of Ti oxide, sn oxide and Mn oxide, wherein the molar ratio of the active components is Ti: sn: mn= (10-200): (1-30): (5-100).
2. An electrode coupling ozone oxidation integrated reactor is characterized in that: the reactor main body is of a cavity structure with a hollow inside and a closed outside, the inside of the reactor main body is divided into an electrolysis reaction chamber and an ozone reaction chamber by a baffle plate, the baffle plate and the top plate and the bottom plate of the reactor are all provided with intervals, the baffle plate is in a parallelogram shape, and the included angle gamma of the parallelogram acute angle is 45-85 degrees; the height of the top plate of the reactor above the partition plate is lower than the heights of the top plate of the electrolytic reaction chamber and the top plate of the ozone reaction chamber; an upper water inlet baffle plate is arranged at the joint of the top plate of the reactor above the partition plate and the side wall of the electrolytic reaction chamber, the upper water inlet baffle plate is inclined towards the direction of the electrolytic reaction chamber, and the included angle between the upper water inlet baffle plate and the horizontal plane is 20-80 degrees; a water inlet and a catalyst feeding port are arranged on the side wall of the top of the electrolytic reaction chamber, a water inlet stirrer is arranged on the top plate of the electrolytic reaction chamber, a submerged stirrer is arranged on the side wall of the bottom of the electrolytic reaction chamber, the stirring speed of the water inlet stirrer is 60-500rad/min, and the stirring strength of the submerged stirrer is 1-10w/m < 3 >; a plurality of groups of electrode plates are arranged in the electrolytic reaction chamber, the electrode plates are fixed in the electrolytic reaction chamber through clamping grooves, and the clamping grooves are made of glass fiber reinforced plastic, polytetrafluoroethylene or UPVC materials; the electrode plate is connected with an external power supply through a lead arranged in a conduit, the anode plate of the electrode plate adopts a titanium plate with ruthenium, iridium or tantalum rare earth element plating, the cathode plate adopts a titanium plate, a graphite plate or a stainless steel plate, the distance between the electrode plates is 2-6cm, the thickness of the electrode plates is 1-5mm, and the number of electrode groups is 2-5; the bottom of the partition plate is provided with a lower water inlet baffle plate, the lower water inlet baffle plate is inclined towards the ozone reaction chamber, and the included angle between the lower water inlet baffle plate and the horizontal plane is 90-165 degrees; an aeration system is arranged at the bottom of the ozone reaction chamber and comprises an air inlet pipe and a micropore aeration disc, wherein the air inlet pipe is communicated with an ozone source, and the micropore aeration disc is arranged on the air inlet pipe; the top of the ozone reaction chamber is provided with a three-phase separator which is in an inverted funnel shape, an inverted scale-shaped blade is arranged outside the ozone reaction chamber, and the top end of the three-phase separator is connected with a tail gas destruction device through an exhaust pipe; an inclined tube sedimentation device is arranged above the bottom of the three-phase separator, and the inclined tube inclination angle is 50-70 degrees; a water outlet is arranged on the side wall of the ozone reaction chamber which is positioned at the same horizontal position with the bottom of the inclined tube sedimentation device, the water outlet is in the form of an effluent weir, and the bottom of the effluent weir is 5-50cm higher than the bottom of the three-phase separator; the added catalyst is a catalytic material which takes 80-100 meshes of powder active carbon as a carrier and loads active components of Ti oxide, sn oxide and Mn oxide, wherein the molar ratio of the active components is as follows: sn: mn= (10-200): (1-30): (5-100).
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| CN109775896B (en) * | 2019-03-20 | 2024-03-15 | 南京大学 | Device and method for deeply purifying biochemical tail water by coupling ozone catalytic oxidation and coagulating sedimentation |
| CN111995133B (en) * | 2020-08-31 | 2022-09-16 | 常州昱道电子有限公司 | Ozone electrode coupling oxidation purification equipment for water pollution and purification process thereof |
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| JP2009034625A (en) * | 2007-08-02 | 2009-02-19 | Mhi Environment Engineering Co Ltd | Wastewater treatment apparatus and method |
| CN102040262A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Electrolytic and catalytic oxidation reaction device and processing method based fluidized bed |
| CN203159290U (en) * | 2012-10-23 | 2013-08-28 | 中国石油化工股份有限公司 | A fixed bed electrolytic catalytic oxidation device |
| CN103304018A (en) * | 2013-06-14 | 2013-09-18 | 北京赛科康仑环保科技有限公司 | Method and device for enhanced ozone oxidation wastewater treatment of ozone tail gas |
| CN105502764A (en) * | 2016-01-26 | 2016-04-20 | 清华大学 | Coking wastewater deep treatment system combing ozone catalytic oxidation and electro-adsorption |
| CN206858331U (en) * | 2017-03-23 | 2018-01-09 | 博瑞德环境集团股份有限公司 | Electrode couples ozone oxidation integral reactor |
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| JP2009034625A (en) * | 2007-08-02 | 2009-02-19 | Mhi Environment Engineering Co Ltd | Wastewater treatment apparatus and method |
| CN102040262A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Electrolytic and catalytic oxidation reaction device and processing method based fluidized bed |
| CN203159290U (en) * | 2012-10-23 | 2013-08-28 | 中国石油化工股份有限公司 | A fixed bed electrolytic catalytic oxidation device |
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