TWI726799B - Wastewater purification system having catalytic membrane tube - Google Patents

Abstract

The present invention relates to a wastewater purification system having a catalytic membrane tube. It comprises an oxygen supply device, an ozone production machine, a membrane tube tank including a membrane tube module, a water storage tank and a pump. The membrane tube module has a first end connected to the ozone production machine and the pump, a second end opposite to the first end for connecting the water storage tank, and a plurality of porous membrane tubes. Each of the plurality of porous membrane tubes has a hollow channel, a braided layer wrapped around the hollow channel, a coating layer wrapped around the braided layer, and a plurality of catalysts distributed in the coating layer. Accordingly, the present invention can effectively reduce the content of organic matter and metal in waste water.

Description

Wastewater purification system with catalyst membrane tube

The present invention relates to a waste water purification system containing catalyst membrane tubes, in particular to a waste water purification system capable of carrying out high-efficiency catalytic oxidation reactions, so as to effectively reduce chemical pollutants in the waste water.

According to this, industrial wastewater contains high concentrations of chemical pollutants. If it is directly discharged into underground waterways or rivers, it will seriously pollute the environmental water body. Therefore, careful treatment and purification before the discharge of wastewater has become an important measure. According to the Environmental Protection of the Executive Yuan The agency stipulates that the organic content or metal content in waste water must be treated below a certain level before it can be discharged to ensure the safety of environmental water resources.

At present, there are various methods or systems for treating wastewater. For example, the Republic of China Patent Publication No. M592436 discloses a membrane tube electrodialysis desalination system, which mainly includes a membrane tube group and an isolation net, which can effectively desalinate the salt in the water. In addition, the Republic of China Patent Publication No. I606994 discloses a method for preparing a ceramic catalyst membrane tube, which is mainly to mix sinterable powder, metal salts and binders, and then use The mixed sinterable powder, metal salt, and binder form a film tube, which is then sintered to form a ceramic catalyst membrane tube. By this, when the ceramic catalyst membrane tube is applied to the catalyst catalytic oxidation system, it can oxidize and degrade the containing In the case of phenol wastewater, the pollutants in the phenol wastewater can be effectively converted and the total organic carbon can be effectively removed.

Due to the large demand for different wastewater treatment equipment in Taiwan's industries, how to develop various wastewater treatment or purification systems to reduce the content of chemical pollutants in wastewater is still an important direction that inventors in related fields think.

The main purpose of the present invention is to provide a waste water purification system containing a catalyst membrane tube, especially a waste water purification system that can carry out high-efficiency catalytic oxidation reaction, so as to effectively reduce the chemical pollutants in the waste water.

In order to achieve the above-mentioned implementation objectives, the present invention provides a catalyst-containing membrane tube wastewater purification system, which includes: an oxygen supply device; an ozone generator connected to the oxygen supply device; a membrane tube tank with a water inlet and a The opposite water outlet end contains a membrane tube module. The membrane tube module has a first end connected to the ozone generator, an opposite second end, and a plurality of porous membrane tubes, each of which includes A hollow channel, a braided layer looped around the hollow channel, a coating covering the braided layer, and a plurality of catalysts arranged in the coating; a water storage tank having a water inlet and a water outlet, in which The water port is connected to the water outlet of the membrane tube tank by a pipeline; and a pump with an input end connected to the water outlet of the water storage tank, and an output end connected to the water inlet end of the membrane tube tank.

Therefore, the present invention can effectively reduce the organic content and metal content in wastewater (such as chemical chelate wastewater, wastewater containing polyvinyl alcohol (PVA), phenol wastewater, dyeing wastewater, etc.).

The purpose of the present invention and its structural and functional advantages will be described based on the structure shown in the following drawings and specific embodiments, so that the review committee can have a deeper and specific understanding of the present invention.

Please refer to the first figure. The present invention provides a waste water purification system containing a catalyst membrane tube, which mainly includes an oxygen supply device (1), an ozone generator (2), a membrane tube tank (3) with a membrane tube Module (31), a water storage tank (4) and a pump (5). The ozone generator (2) is connected to an oxygen supply device (1), so that the oxygen supply device (1) provides oxygen to the ozone generator (2) to produce ozone. The membrane tube tank (3) has a water inlet (3a) and an opposite water outlet (3b), and contains a membrane tube module (31); the water storage tank (4) has a water inlet (41) and a water outlet (3b). The water outlet (42), the water outlet (3b) of the membrane tube tank (3) is connected to the water inlet (41) of the water storage tank (4) with a pipeline (43); the pump (5) has an input end (51) Connect the water outlet (42) of the water storage tank (4), and an output end (52) connected to the water inlet (3a) of the membrane tube tank (3); and also connected to the water outlet (3b) of the membrane tube tank (3) A pH meter (6) can be further provided on the pipeline (43) of the water storage tank (4) to facilitate adjustment of the pH value of the wastewater.

As shown in the second figure, the membrane tube module (31) has a first end (31a), a second end (31b) opposite to the first end (31a), and a plurality of porous membrane tubes (311).

Also, please refer to the third figure again. Each porous membrane tube (311) includes a hollow channel (3111), a braided layer (3112) arranged around the hollow channel (3111), and a braided layer (3112). ) Coating (3113), and a plurality of catalysts (3114) arranged in the coating (3113). Preferably, the diameter of the hollow channel (3111) of each porous membrane tube (311) can be, for example, 1~1.2 mm, the thickness of the braided layer (3112) is 0.4-0.6 mm, and the thickness of the coating (3113) It is 0.1-0.2 mm. The braided layer (3112) may be, for example, a polyester yarn layer, and the coating (3113) may be selected from, for example, polyvinylidene fluoride (PVDF) film, polysulfide (PSF) film, and cellulose acetate (cellulose acetate). A group of films.

Preferably, the catalyst (3114) can be selected from manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), nickel (Ni), titanium ( Ti) or cerium (Ce) oxide.

Preferably, the catalyst (3114) can be, for example, composed of an active component and a carrier, the active component is selected from manganese (Mn), iron (Fe), cobalt (Co), copper ( The oxide of Cu), zinc (Zn), nickel (Ni), titanium (Ti) or cerium (Ce), and the support is selected from activated alumina pellets, activated carbon, ceramsite, porous zeolite or graphene, Especially activated carbon or graphene has more surface area, which can make organic matter decompose more effectively.

In addition, the following specific examples can further prove the scope of practical application of the present invention, but it is not intended to limit the scope of the present invention in any form.

Example one

When the waste water purification system with catalyst-containing membrane tube of the present invention is actually used, please refer to the first figure. The oxygen supply device (1) is connected to the ozone generator (2), and the ozone generator (2) produces ozone by the membrane tube module The first end (31a) of (31) enters the membrane tube module (31) for catalytic oxidation reaction. The water outlet (3b) of the membrane tube tank (3) is connected to the inlet of the water storage tank (4) by a pipeline (43). Water outlet (41), connected to the outlet (42) of the water storage tank (4), connected to the input end (51) of the pump (5), and the output end (52) of the pump (5) connected to the membrane tube tank (3) Inlet end (3a). Thereby, the whole system forms a loop, and the waste water to be treated is stored in the water storage tank (4). When the pump (5) starts to pump, the waste water passes through the water outlet (42) of the water storage tank (4) through the pump ( 5) Go into the membrane tube tank (3), and pass through the membrane tube module (31) filled with ozone (8) for purification (as shown in the fourth picture), and then the treated wastewater will be treated by the membrane tube module (31) The water outlet (3b) of the water outlet (3b) flows into the water inlet (41) of the water storage tank (4) through the pipeline (43) and returns to the water storage tank (4) again. In this way, the purpose of repeatedly treating and purifying wastewater can be achieved. In addition, in order to enhance the convenience of use of the system, a control panel (7) can also be provided to connect and control the oxygen supply device (1), the ozone generator (2), and the pump (5).

Please refer to the second and third figures, the upper ring of the membrane tube module (31) is provided with a plurality of porous membrane tubes (311), and each of the porous membrane tubes (311) has a hollow channel (3111) and a braided layer The (3112) ring is arranged in the hollow channel (3111), and the coating (3113) is covered on the braided layer (3112). The braided layer (3112) is a polyester yarn layer, and the coating (3113) is mixed with a plurality of catalysts (3114). The catalyst (3114) can be, for example, a metal oxide or a metal oxide with a carrier. , To enhance the catalytic oxidation reaction. Please refer to the fourth figure, the ozone (8) will be distributed in the membrane tube module (31) after entering the membrane tube groove (3), so the catalyst (3114) on the coating (3113) of the porous membrane tube (311) Contact with ozone (8) and jointly carry out the catalytic oxidation reaction of wastewater. The reaction catalyzed by ozone (8) and metal catalyst (3114) is that ozone (8) generates oxygen free radicals through the catalyst (3114), and the oxygen free radicals follow The water forms hydroxyl radicals, and finally the hydroxyl radicals destroy the organic matter and decompose the organic matter into carbon dioxide and water.

Example two

Please refer to Table 1, the fifth figure and the sixth figure. The porous membrane tube (311) has multiple filter holes (3115) with a particle size of 0.22~10 μm, and the porous membrane tube (311) can be adjusted to different filter holes. The pore size and operating pressure of (3115) reach the situation of controlling the movement of ozone (8). As shown in Table 1, the operation mode is to make ozone (8) appear to be saturated and stay in the porous membrane tube (311) without escaping. Porous membrane tube (311); The second operation mode is to make ozone (8) escape from the porous membrane tube (311) as fine bubbles.

Table 1: The operating pressure of filter holes with different pore sizes Aperture (μm) Operation mode one Operation mode two 0.22 ＜0.35~0.4 (Mpa) ＞0.35~0.4 (Mpa) 0.30 ＜0.3 (Mpa) ＞0.3 (Mpa) 0.45 ＜0.23 (Mpa) ＞0.23 (Mpa) 0.65 ＜0.14 (Mpa) ＞0.14 (Mpa) 0.80 ＜0.11 (Mpa) ＞0.11 (Mpa) 1.2 ＜0.08 (Mpa) ＞0.08 (Mpa) 3.0 ＜0.07 (Mpa) ＞0.07 (Mpa) 5.0 ＜0.04 (Mpa) ＞0.04 (Mpa) 8.0 ＜0.03 (Mpa) ＞0.03 (Mpa) 10.0 ＜0.01 (Mpa) ＞0.01 (Mpa)

The double arrow in the hollow channel (3111) in the fifth figure represents the path of ozone (8) into the porous membrane tube (311). Due to the use of operation mode 1 to control the pore size and pressure, the ozone (8) fills the porous membrane tube (311) The hollow channel (3111) for catalytic oxidation reaction. In addition, the double arrow in the hollow channel (3111) in the sixth figure represents the path of ozone (8) entering the porous membrane tube (311). Due to the use of operation mode two to control the pore size and pressure, the ozone entering the porous membrane tube (311) (8) Escape from the porous membrane tube (311). Ozone (8) generates oxygen free radicals through the catalyst (3114), and the oxygen free radicals form hydroxyl free radicals with water. Finally, the hydroxyl free radicals destroy organic matter, so the organic matter in the wastewater can be decomposed into carbon dioxide and water.

Example three

The type of waste water that can be treated by the present invention is not limited, such as chemical chelate waste water, polyvinyl alcohol (PVA)-containing waste water, phenol waste water, dyeing and finishing waste water, etc., all of which can be used to decompose the organic matter or metal content in the waste water, etc. , Its efficacy verification results are as follows:

(1) Use the catalyst-containing membrane tube waste water purification system of the present invention to treat Sinopec Green Energy's phenol-containing waste water. Please refer to the seventh figure for the result, which shows that the color of the waste water can be decomposed and the Chemical Oxygen Demand (COD) value can be reduced. , The COD value of the original solution is 18125 after treatment and it is reduced to 7650, and the color is almost removed. If the COD value is 17925 only by filtration (no ozone provided), it means that the system in this case can be used to treat phenol-containing wastewater.

(2) Use the catalyst-containing membrane tube waste water purification system of the present invention to treat molybdenum (Mo)-containing waste water. The test results show that the initial waste water contains about 68 ppm of molybdenum. The use of sodium diethyldithiocarbamate (Sodium diethyldithiocarbamate) , SDDC) (heavy metal trapping agent) treatment, the molybdenum concentration is reduced to about 1~2 ppm; if the wastewater is treated with this system and ozone before adding SDDC, the molybdenum concentration can be reduced to 0.4, which is less than the current EPA emission standard 0.6 ppm, which means that the system in this case can be used to treat wastewater containing molybdenum (Mo).

(3) Use the catalyst-containing membrane tube waste water purification system of the present invention to treat TSMC's cobalt (Co) waste water, where the Co concentration department commissioned Professor Lai Zhenli from Jianan University of Pharmacology to use inductively coupled plasma (ICP) measuring. The test data showed that the concentration of Co in untreated raw water was 4.387 ppm; (a) After the ozone-treated water sample was adjusted to pH 13, the water sample filtered through the catalyst-containing membrane tube of the present invention was 0.692 ppm; (b) The ozone-treated water sample is adjusted to pH 13, and 300 ppm SDDC is added. The water sample filtered by the catalyst-containing membrane tube of the present invention is ND (<0.1 ppm) (detection concentration) The value is 0.1 ppm), which means that the system in this case can be used to treat wastewater containing cobalt (Co).

As can be seen from the above implementation description, compared with the prior art, the present invention has the following advantages:

1. In the present invention, the porous membrane tube is directly provided with a catalyst on the coating, so when ozone contacts the catalyst on the porous membrane tube, the oxidation catalytic reaction can be directly carried out.

2. The present invention can be used to treat different types of waste water to reduce chemical pollutants in the waste water and remove color, so as to achieve the purpose of purifying waste water.

3. The present invention can control the content or residence time of ozone in the membrane tube module by adjusting the aperture of the filter holes and different operating pressures, thereby controlling the catalytic oxidation reaction.

In summary, the waste water purification system of the present invention containing the catalyst membrane tube can indeed achieve the expected use effect through the above-disclosed embodiments, and the present invention has not been disclosed before the application. The provisions and requirements of the Patent Law. If you file an application for a patent for invention in accordance with the law, you are kindly requested to review it and grant a quasi-patent, it will be more virtuous.

However, the above-mentioned illustrations and descriptions are only preferred embodiments of the present invention, and are not intended to limit the scope of protection of the present invention. Anyone familiar with the art will do other things based on the characteristic scope of the present invention. Equivalent changes or modifications should be regarded as not departing from the design scope of the present invention.

1: Oxygen supply device

2: Ozone production machine

3: Membrane tube groove

3a: Water inlet

3b: Water outlet

31: Membrane tube module

31a: first end

31b: second end

311: Porous membrane tube

3111: Hollow channel

3112: Braid

3113: Coating

3114: Catalyst

3115: filter hole

4: Water storage tank

41: Water inlet

42: water outlet

43: Pipeline

5: Pump

51: Input

52: output

6: pH meter

7: Control Panel

8: Ozone

9: Water flow

The first figure: the schematic diagram of the preferred implementation of the waste water purification system containing the catalyst membrane tube of the present invention.

Figure 2: A perspective view of a preferred implementation of the membrane tube module of the present invention.

Figure 3: A cross-sectional view of a preferred implementation of the porous membrane tube of the present invention.

Figure 4: A schematic diagram of ozone aeration through the porous membrane tube of the membrane tube module in the preferred embodiment of the present invention.

Figure 5: A schematic diagram of the first mode of operation in the preferred embodiment of the present invention to make ozone stay in the porous membrane tube.

Figure 6: A schematic diagram of the second mode of operation in the preferred embodiment of the present invention to cause ozone to escape from the porous membrane tube (dashed arrow).

Figure 7: Photographs of specific embodiments of the present invention before and after wastewater treatment.

1: Oxygen supply device

2: Ozone production machine

3: Membrane tube groove

3a: Water inlet

3b: Water outlet

31: Membrane tube module

31a: first end

31b: second end

311: Porous membrane tube

4: Water storage tank

41: Water inlet

42: water outlet

43: Pipeline

5: Pump

51: Input

52: output

6: pH meter

7: Control Panel

Claims (9)

A waste water purification system containing a catalyst membrane tube, which includes: An ozone generator; A membrane tube tank has a water inlet end and an opposite water outlet end, and contains a membrane tube module. The membrane tube module has a first end connected to the ozone generator, an opposite second end, and a plurality of Porous membrane tubes, wherein each porous membrane tube includes a hollow channel, a braided layer around the hollow channel, a coating covering the braided layer, and a plurality of catalysts arranged in the coating ； A water storage tank having a water inlet and a water outlet, wherein the water inlet is connected to the water outlet of the membrane tube tank by a pipeline; and A pump has an input end connected to the water outlet of the water storage tank, and an output end connected to the water inlet end of the membrane tube tank. The wastewater purification system containing catalyst membrane tube according to claim 1, wherein a pH meter is provided on the pipeline connecting the outlet end of the membrane tube tank to the water storage tank. The waste water purification system containing catalyst membrane tubes according to claim 1, wherein each of the porous membrane tubes has a plurality of filter holes with a particle size of 0.22-10 μm. The waste water purification system with a catalyst-containing membrane tube according to claim 1, wherein the plurality of catalysts are selected from manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn) ), nickel (Ni), titanium (Ti) or cerium (Ce) oxides. The waste water purification system with a catalyst-containing membrane tube according to claim 1, wherein the plurality of catalysts are composed of an active component and a carrier. The waste water purification system containing catalyst membrane tube according to claim 5, wherein the active component is selected from manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn) , Nickel (Ni), titanium (Ti) or cerium (Ce) oxide, and the support is selected from activated alumina pellets, activated carbon, ceramsite, porous zeolite or graphene. The waste water purification system containing the catalyst film tube according to claim 1, wherein the braided layer is a polyester yarn layer, and the coating is selected from the group consisting of polyvinylidene fluoride (PVDF) membrane, polysulfide (PSF) ) A group consisting of a film and a cellulose acetate film. The waste water purification system containing the catalyst membrane tube according to claim 7, wherein the diameter of the hollow channel is 1~1.2 mm, the thickness of the braided layer is 0.4-0.6 mm, and the thickness of the coating is 0.1-0.2 mm. The waste water purification system with a catalytic membrane tube as described in claim 1, further comprising an oxygen supply device connected to the ozone generator to provide oxygen to produce ozone.

Images