阅读说明：本技术 一种多级膜组件催化臭氧氧化的连续流装置 (Continuous flow device for catalyzing ozone oxidation by multistage membrane module ) 是由 陈忠林 刘山 孙婧怡 祝鑫炜 郭玉浩 蔡李铭 沈吉敏 王斌远 李响 赵晟锌 康晶 于 2021-07-09 设计创作，主要内容包括：一种多级膜组件催化臭氧氧化的连续流装置,本发明涉及高级氧化水处理领域。本发明要解决现有水处理装置存在单一臭氧对难降解有机物处理效率较低,且催化剂难以回收的问题。该装置包括臭氧水生成罐、混合器、压力表-平板膜单元和尾气吸收装置,臭氧水生成罐顶盖设有进水管、进气管、出气管和出水管,其中进气管出气口与曝气盘连通,曝气盘出气口靠近臭氧水生成罐的底部。本发明运用膜片自身的过渡态金属非均相催化臭氧氧化,利用膜片自身的碱性缓冲性质,提供膜孔内的碱性环境,加速臭氧分解生成自由基,催化臭氧氧化有机污染物。本发明原理简单易操作,可以作为预处理或者深度处理的工艺使用。本发明装置可用于饮用水和废水处理领域。(The invention discloses a continuous flow device for catalyzing ozone oxidation by a multistage membrane module, and relates to the field of advanced oxidation water treatment. The invention aims to solve the problems that the existing water treatment device has low treatment efficiency of single ozone on refractory organic matters and is difficult to recover a catalyst. The device comprises an ozone water generating tank, a mixer, a pressure gauge-flat membrane unit and a tail gas absorption device, wherein a top cover of the ozone water generating tank is provided with a water inlet pipe, an air outlet pipe and a water outlet pipe, an air outlet of the air inlet pipe is communicated with an aeration disc, and an air outlet of the aeration disc is close to the bottom of the ozone water generating tank. The invention utilizes the transition metal of the membrane to catalyze the ozone oxidation in a heterogeneous mode, provides an alkaline environment in membrane holes by utilizing the alkaline buffer property of the membrane, accelerates the decomposition of ozone to generate free radicals, and catalyzes the ozone to oxidize organic pollutants. The method has simple and easy operation principle, and can be used as a pretreatment or advanced treatment process. The device can be used in the field of drinking water and wastewater treatment.)

1. A continuous flow device for catalyzing ozone oxidation by a multi-stage membrane module is characterized in that: the device comprises an ozone water generating tank (4), a mixer (11), a pressure gauge-flat membrane unit and a tail gas absorption device (7), wherein a top cover of the ozone water generating tank (4) is provided with a water inlet pipe (4-1), an air inlet pipe (4-2), an air outlet pipe (4-3) and a water outlet pipe (4-4), an air outlet of the air inlet pipe (4-2) is communicated with an aeration disc (5), an air outlet of the aeration disc (5) is close to the bottom of the ozone water generating tank (4), and a water inlet of the water outlet pipe (4-4) is close to the bottom of the ozone water generating tank (4); the water outlet of the water outlet pipe (4-4) is communicated with the water inlet of the mixer (11), the raw water tank (10) is also communicated with the mixer (11) through a pipeline, a reactor (14) is arranged above the mixer (11), the reactor (14) comprises a plurality of groups of pressure gauge-flat membrane units which are connected in series, each group of pressure gauge-flat membrane unit consists of a reaction section and a pressure measuring section, a flat membrane (13) is arranged at the bottom of the reaction section, a pressure gauge (12) is arranged on the pressure measuring section, and an oxidation water outlet (16) and an exhaust port (17) are arranged at the top of the reactor (14); the gas outlet of the gas outlet pipe (4-3) is communicated with a tail gas absorption device (7), the gas outlet (17) is also communicated with the tail gas absorption device (7) through a pipeline, and the tail gas outlet pipe (7-1) is arranged at the top end of the tail gas absorption device (7).

2. The continuous flow device for catalytic ozonation by the multi-stage membrane module according to claim 1, wherein an air outlet of the oxygen cylinder (1) is communicated with an air inlet of the ozone generator (3), and an air outlet of the ozone generator (3) is communicated with an air inlet pipe (4-2) of the ozone water generation tank (4).

3. The continuous flow device for catalytic ozonation by a multi-stage membrane module according to claim 2, wherein a drying pipe (2) is arranged between the oxygen cylinder (1) and the ozone generator (3).

4. The continuous flow device for catalytic ozonation by a multi-stage membrane module according to claim 1, wherein the first suck-back prevention device (6) is arranged on the gas outlet pipe (4-3).

5. The continuous flow device for catalytic ozonation by a multi-stage membrane module according to claim 1, wherein an ozone water pump (8) is arranged on the water outlet pipe (4-4).

6. The continuous flow device for catalytic ozonation by a multi-stage membrane module according to claim 1, wherein a raw water pump (9) is disposed on a pipeline connecting the raw water tank (10) and the mixer (11).

7. The continuous flow device for catalytic ozonation by a multi-stage membrane module according to claim 1, wherein the flat membrane in the pressure gauge-flat membrane unit is assembled at the joint by a flange.

8. The continuous flow device for catalytic ozonation by a multi-stage membrane module according to claim 1, wherein a second anti-back suction device (15) is arranged on a pipeline connecting the exhaust port (17) and the tail gas absorption device (7).

9. The continuous flow device for catalytic ozonation by using the multi-stage membrane module according to claim 1, wherein the flat membrane (13) is prepared by mixing and tabletting Portland cement and a non-metal framework material, and the mass ratio of the Portland cement to the non-metal framework material is (1-10): 1; the flat membrane has a membrane pore structure and an average pore diameter of 0.1-10 microns.

10. The continuous flow device for catalytic ozonation by multi-stage membrane modules according to claim 1, wherein the wall of the reaction section in the reactor (14) is made of glass, and the wall of the pressure measurement section is made of food-grade 304 stainless steel.

Technical Field

The invention relates to the field of advanced oxidation water treatment.

Background

Endocrine disruptors and refractory organic matters are the key problems in the treatment of drinking water at present, and accumulation can be generated after long-term drinking, and especially, the long-life influence on the development of fetuses in the abdomen of pregnant women can be generated. The organic matter which is difficult to degrade is weak in the conventional drinking water treatment unit, the removal rate in the advanced treatment unit is low, the oxidation capacity of single ozone molecule is weak, the oxidation is selective, and the organic matter is difficult to degrade and mineralize. Advanced oxidation technology is based on the excitation of ozone molecules to generate free radicals, thereby further removing organic contaminants. The advanced oxidation of ozone often requires an activator and a catalyst, such as photocatalysis and catalytic ozonation. However, the existing water treatment device has the technical problems of complex structure, difficult regeneration and utilization of the catalyst and low treatment efficiency.

Disclosure of Invention

The invention aims to solve the problems that the existing water treatment device has low treatment efficiency of single ozone on refractory organic matters and the catalyst is difficult to recover, and provides a continuous flow device for catalyzing ozone oxidation by a multi-stage membrane module, which simulates an actual water treatment process and provides technical guidance and theoretical basis for the actual application of scale expansion to ozone advanced water treatment.

A continuous flow device for catalytic ozonation by a multi-stage membrane assembly comprises an ozone water generation tank, a mixer, a pressure gauge, a flat membrane unit and a tail gas absorption device, wherein a top cover of the ozone water generation tank is provided with a water inlet pipe, an air outlet pipe and a water outlet pipe; the water outlet of the water outlet pipe is communicated with the water inlet of the mixer, the raw water pool is also communicated with the mixer through a pipeline, a reactor is arranged above the mixer and comprises a plurality of groups of pressure gauge-flat membrane units which are connected in series, each group of pressure gauge-flat membrane unit consists of a reaction section and a pressure measuring section, the bottom of the reaction section is provided with a flat membrane, the pressure measuring section is provided with a pressure gauge, and the top of the reactor is provided with an oxidation water outlet and an exhaust port; the gas outlet of the gas outlet pipe is communicated with a tail gas absorption device, the gas outlet is also communicated with the tail gas absorption device through a pipeline, and the top end of the tail gas absorption device is provided with a tail gas exhaust pipe.

Furthermore, the water inlet pipe is externally connected with a clean water source.

Further, an air outlet of the oxygen cylinder is communicated with an air inlet of the ozone generator, and an air outlet of the ozone generator is communicated with an air inlet pipe of the ozone water generating tank.

Further, a drying tube is arranged between the oxygen cylinder and the ozone generator.

Furthermore, a first anti-suck-back device is arranged on the air outlet pipe.

Further, an ozone water pump is arranged on the water outlet pipe.

Furthermore, a raw water pump is arranged on a pipeline which is communicated with the raw water pool and the mixer.

Further, the flat membrane in the pressure gauge-flat membrane unit is assembled at the joint by adopting a flange.

Furthermore, the joint of the pressure gauge and the flat membrane unit is sealed by a rubber ring and a rubber pad.

Furthermore, a second anti-back suction device is arranged on a pipeline for communicating the exhaust port with the tail gas absorption device.

Further, the flat sheet membrane is prepared by mixing and tabletting ordinary portland cement and a non-metal framework material, wherein the mass ratio of the ordinary portland cement to the non-metal framework material is (1-10): 1; the non-metal framework material comprises silicon dioxide, fly ash, kaolin or activated carbon powder. The thickness of the flat membrane is 0.5-3mm, and the average pore diameter is 0.1-10 microns.

Furthermore, the wall of the reaction section in the reactor is made of glass, and the wall of the pressure measuring section is made of stainless steel.

The top of the ozone water generating tank is sealed by a rubber plug, and a glass tube penetrates through the middle of the rubber plug without a gap, so that ozone gas can be prevented from leaking, and the safety of a user can be ensured; the ozone water pump and the raw water pump use a peristaltic pump or an anti-corrosion water pump, the whole pipeline is resistant to ozone corrosion, and potassium iodide or other solutions reacting with ozone are filled in the tail gas absorption device.

The device adopts oxygen and ozone generator to prepare ozone and then leads the ozone into an ozone water generating tank, and ozone gas in the tank continuously passes through water to ensure that the concentration of ozone in the water is stabilized in a certain range.

The device is characterized in that oxygen is provided by an oxygen cylinder, a gas drying pipe dries moisture in the oxygen, the dried oxygen generates high-concentration ozone through ionization of an ozone generator, the ozone is introduced into an ozone water generation tank and then fully contacts with a water body, the ozone water is continuously introduced all the time to generate saturated ozone water, a tail gas outlet can be closed by a high-pressure valve, and the air pressure in the cylinder is maintained, so that the ozone concentration is increased.

The front end of the reactor is provided with a mixer for mixing ozone water and raw water, liquid flows from bottom to top, water flows into the lower end, water flows out of the upper end, a pressure gauge can observe transmembrane pressure difference of the membrane, and whether the membrane is damaged or blocked is judged; if the device blocks up, can reverse operation or wash, water inlet and delivery port exchange, the flip-chip returns after wasing, does not have the influence to the device operation.

The flat plate membrane is formed by mixing and tabletting common portland cement and other materials, the portland cement contains metal elements in various transition regions, can catalyze ozone oxidation in a heterogeneous mode, can catalyze ozone oxidation continuously in a continuous flow device (reactor), and has an alkaline buffer property, and the alkaline environment in membrane pores can catalyze ozone decomposition to generate free radicals. The ion precipitation amount is low in the water treatment process, and the effluent meets GB 5749-.

The mixer can be a tubular static mixer or a water jet.

The working principle of the invention is as follows: oxygen and ozone generator are adopted to prepare ozone, then the ozone is led into an ozone water generating tank, a clean water source is connected outside a water inlet pipe, and ozone gas in the tank continuously passes through a water body to enable the concentration of the ozone in the water body to be stable in a certain range. Ozone saturated water in the ozone water generating tank is pumped into the mixer through the water outlet pipe and the ozone water pump, meanwhile, polluted raw water is pumped into the mixer through the raw water pump from the raw water pool, the water mixed by the mixer passes through membrane pores of the flat membrane, the ozone molecules catalyze to generate non-selective strong-oxidizing free radicals, and the non-selective strong-oxidizing free radicals are rapidly combined with pollutants in the membrane pores and on the surface of the membrane, so that the pollutants are degraded. Meanwhile, the membrane pores of the microfiltration membrane can retain macromolecules such as Bovine Serum Albumin (BSA), the retention rate is above 68% under the transmembrane pressure difference (TMP) of 100kPa, the TMP is low (less than 40kPa), and the retention rate of the BSA can reach 100%. The treated water is discharged from the oxidation water outlet, and the waste gas is introduced into the tail gas absorption device through the exhaust port and the second anti-back suction device. Ozone tail gas of the ozone water generating tank passes through the gas outlet pipe and is led to the tail gas absorption device through the first anti-suck-back device. Liquid (such as potassium iodide) in the tail gas absorption device can react with the ozone tail gas to achieve the purpose of absorbing the tail gas.

The invention adopts catalytic ozone (O)₃) Generate free radicals to oxidize organic substances to effectively treat water and catalyze ozone (O)₃) Oxidation is divided into homogeneous and heterogeneous catalysis, which combine differencesThe function is as follows: direct or indirect ozone oxidation, with catalysis of O₃Generating more hydroxyl radicals, O₃And heterogeneous material surface groups can lead to the generation of hydroxyl radicals, singlet oxygen, superoxide radicals. The free radicals have high oxidizability, can degrade various organic pollutants and endocrine disruptors in water, and can greatly improve the quality of drinking water.

The invention has the beneficial effects that:

the invention provides an advanced oxidation treatment continuous flow device capable of being applied in engineering, which comprises three major parts of ozone generation, ozone and pollutant water mixing and membrane catalytic ozone oxidation, and also comprises a power system of a pump, a tail gas absorption system and a water source. It can run automatically and continuously, combines the homogeneous phase and heterogeneous phase catalytic ozonation functions into one, improves the efficiency of pollutants, and can use multistage series connection to increase the contact time of the membrane.

The invention uses transition metal heterogeneous catalysis ozone oxidation, uses alkaline environment in membrane pores and on membrane surface homogeneous catalysis ozone oxidation, has simple principle and easy operation, is suitable for treatment of drinking water and sewage wastewater, and can be used as a pretreatment or advanced treatment process.

The verification proves that the removal rate of nitrobenzene and p-chloronitrobenzene in the water treated by the device reaches 88-95%, the removal rate of atrazine reaches 95%, and the removal rate of chlorpyrifos is more than 90%. The device of the invention is proved to have the effect of deeply removing the organic matters which are difficult to degrade in the wastewater.

The device can be used in the field of drinking water and wastewater treatment.

Drawings

FIG. 1 is a schematic diagram of a multi-stage membrane module catalytic ozonation continuous flow apparatus according to one embodiment;

FIG. 2 is a surface electron micrograph of the flat sheet membrane according to the first example.

Detailed Description

The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.

The first embodiment is as follows: the continuous flow device for catalyzing ozone oxidation by using the multistage membrane module is characterized in that: the device comprises an ozone water generating tank 4, a mixer 11, a pressure gauge-flat membrane unit and a tail gas absorption device 7, wherein a top cover of the ozone water generating tank 4 is provided with a water inlet pipe 4-1, an air inlet pipe 4-2, an air outlet pipe 4-3 and a water outlet pipe 4-4, wherein an air outlet of the air inlet pipe 4-2 is communicated with an aeration disc 5, an air outlet of the aeration disc 5 is close to the bottom of the ozone water generating tank 4, and a water inlet of the water outlet pipe 4-4 is close to the bottom of the ozone water generating tank 4; the water outlet of a water outlet pipe 4-4 is communicated with the water inlet of a mixer 11, a raw water pool 10 is also communicated with the mixer 11 through a pipeline, a reactor 14 is arranged above the mixer 11, the reactor 14 comprises a plurality of groups of pressure gauge-flat membrane units which are connected in series, each group of pressure gauge-flat membrane unit consists of a reaction section and a pressure measuring section, a flat membrane 13 is arranged at the bottom of the reaction section, a pressure gauge 12 is arranged on the pressure measuring section, and an oxidation water outlet 16 and an exhaust port 17 are arranged at the top of the reactor 14; the gas outlet of the gas outlet pipe 4-3 is communicated with a tail gas absorption device 7, the gas outlet 17 is also communicated with the tail gas absorption device 7 through a pipeline, and the tail gas outlet pipe 7-1 is arranged at the top end of the tail gas absorption device 7.

The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the air outlet of the oxygen bottle 1 is communicated with the air inlet of the ozone generator 3, and the air outlet of the ozone generator 3 is communicated with the air inlet pipe 4-2 of the ozone water generating tank 4. The rest is the same as the first embodiment.

The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the water inlet pipe is externally connected with a clean water source. The others are the same as in the first or second embodiment.

The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: a drying tube 2 is arranged between the oxygen cylinder 1 and the ozone generator 3. The rest is the same as one of the first to third embodiments.

The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the air outlet pipe 4-3 is provided with a first suck-back prevention device 6. The rest is the same as one of the first to fourth embodiments.

The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: an ozone water pump 8 is arranged on the water outlet pipe 4-4. The rest is the same as one of the first to fifth embodiments.

The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: a raw water pump 9 is provided in a pipe connecting the raw water tank 10 and the mixer 11. The rest is the same as one of the first to sixth embodiments.

The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: and the flat membrane in the pressure gauge-flat membrane unit is assembled at the joint by adopting a flange. The rest is the same as one of the first to seventh embodiments.

The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and a second anti-back suction device 15 is arranged on a pipeline for communicating the exhaust port 17 with the tail gas absorption device 7. The rest is the same as the first to eighth embodiments.

The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the flat sheet membrane 13 is prepared by mixing and tabletting ordinary portland cement and a non-metal framework material, wherein the mass ratio of the ordinary portland cement to the non-metal framework material is (1-10): 1; the flat membrane has a membrane pore structure and an average pore diameter of 0.1-10 microns. The rest is the same as one of the first to ninth embodiments.

The concrete implementation mode eleven: the present embodiment differs from one of the first to tenth embodiments in that: the non-metal framework material comprises silicon dioxide, fly ash, kaolin or activated carbon powder. The rest is the same as one of the first to tenth embodiments.

The specific implementation mode twelve: this embodiment is different from one of the first to eleventh embodiments in that: the wall of the reaction section in the reactor 14 is made of glass, and the wall of the pressure measuring section is made of food-grade 304 stainless steel. The rest is the same as in one of the first to eleventh embodiments.

The following examples were used to demonstrate the beneficial effects of the present invention:

the first embodiment is as follows:

the continuous flow device for catalytic ozonation by the multi-stage membrane module comprises an ozone water generation tank 4, a mixer 11, a pressure gauge-flat membrane unit and a tail gas absorption device 7, wherein a top cover of the ozone water generation tank 4 is provided with a water inlet pipe 4-1, an air inlet pipe 4-2, an air outlet pipe 4-3 and a water outlet pipe 4-4, an air outlet of the air inlet pipe 4-2 is communicated with an aeration disc 5, an air outlet of the aeration disc 5 is close to the bottom of the ozone water generation tank 4, and a water inlet of the water outlet pipe 4-4 is close to the bottom of the ozone water generation tank 4; the water outlet of a water outlet pipe 4-4 is communicated with the water inlet of a mixer 11, a raw water pool 10 is also communicated with the mixer (11) through a pipeline, a reactor 14 is arranged above the mixer 11, the reactor 14 comprises a plurality of groups of pressure gauge-flat membrane units which are connected in series, each group of pressure gauge-flat membrane unit consists of a reaction section and a pressure measuring section, a flat membrane 13 is arranged at the bottom of the reaction section, a pressure gauge 12 is arranged on the pressure measuring section, and an oxidation water outlet 16 and an exhaust port 17 are arranged at the top of the reactor 14; the gas outlet of the gas outlet pipe 4-3 is communicated with a tail gas absorption device 7, the gas outlet 17 is also communicated with the tail gas absorption device 7 through a pipeline, and the tail gas outlet pipe 7-1 is arranged at the top end of the tail gas absorption device 7.

The water inlet pipe is externally connected with a clean water source.

The air outlet of the oxygen bottle 1 is communicated with the air inlet of the ozone generator 3, and the air outlet of the ozone generator 3 is communicated with the air inlet pipe 4-2 of the ozone water generating tank 4.

A drying tube 2 is arranged between the oxygen cylinder 1 and the ozone generator 3.

The air outlet pipe 4-3 is provided with a first suck-back prevention device 6.

An ozone water pump 8 is arranged on the water outlet pipe 4-4.

A raw water pump 9 is provided in a pipe connecting the raw water tank 10 and the mixer 11.

And the flat membrane in the pressure gauge-flat membrane unit is assembled at the joint by adopting a flange.

And a second anti-back suction device 15 is arranged on a pipeline for communicating the exhaust port 17 with the tail gas absorption device 7.

The flat sheet membrane 13 is prepared from ordinary portland cement and silicon dioxide powder according to a mass ratio of 1: 5 mixing and tabletting, the thickness is 2mm, and the tablet contains a plurality of metal elements and alkaline substances.

FIG. 2 is a surface electron microscope image of the flat membrane of the first embodiment, wherein the flat membrane has a membrane pore structure and an average pore diameter of 0.1-10 μm.

The wall of the reaction section in the reactor 14 is made of glass, and the wall of the pressure measuring section is made of stainless steel. The device of the embodiment is detected, the concentration of nitrobenzene in raw water is controlled to be 100ug/L, the concentration of p-chloronitrobenzene is controlled to be 100ug/L, the initial concentration of atrazine is 30ug/L, the concentration of chlorpyrifos is 50ug/L, the current of an ozone generator is 10A, the concentration of ozone water in a water outlet pipe of an ozone water generation tank is actually measured to be 0.5mg/L, the flow is 90mL/min, 2 groups of pressure gauge-flat membrane units which are connected in series are arranged in a reactor, the removal rate of p-chloronitrobenzene and nitrobenzene in water after the discharge treatment of an oxidation water outlet is detected to reach 88-95%, the removal rate of atrazine reaches 95%, and the removal rate of chlorpyrifos is more than 90%. The device of the invention is proved to have the effect of deeply removing the organic matters which are difficult to degrade in water. And the device can further improve the treatment efficiency of the device on organic pollutants by increasing the reaction stages and increasing the current and the power.

Example two:

the difference between the present embodiment and the first embodiment is: the flat membrane 13 is formed by mixing and pressing activated carbon powder and portland cement.

The test proves that the embodiment achieves the water treatment effect equivalent to that of the embodiment I.