• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:

    公开号:NL1041422A
    申请号:NL1041422
    申请日:2015-08-11
    公开日:2016-07-12
    发明作者:Jozef Jacques Mayer Mateo；Engelaar Antoine
    申请人:Pure Green Tech B V；
    IPC主号:
    专利说明:

    Method and device for disinfecting hospital waste water
    The present invention relates to a method and device for disinfecting water in general and hospital waste water in particular, characterized by a tubular reactor containing red LEDs that emit light in the wavelength range of 600 nm to 700 nm, the presence of methylene blue in the tubular reactor as a photo-mediator and an ozone generator to increase the efficiency of the tubular reactor and / or to selectively decompose the excess methylene blue after the disinfection step.
    Description of the present invention
    Domestic waste water, waste water from care institutions such as hospitals and waste water from the bio-industry contain resistant bacteria and medicine residues that ultimately end up in relevant quantities at sewage treatment plants (STPs). The STPs are insufficiently equipped to effectively remove all pathogens and the many thousands of types of medicines from the wastewater. The result is a real risk that bacteria that are resistant to various types of antibiotics, as well as significant amounts of drug residues, will end up in our surface water.
    The technology according to the present invention makes it possible to disinfect waste water and at the same time to oxidize drug residues in the waste water in an environmentally friendly manner and at low energy costs.
    In a first aspect, the technology according to the present invention relates to the use of an ozone generator with a new type of energy-efficient flat corona electrode. This electrode is characterized by very accurately adjustable geometry, good scalability, good heat dissipation, low pressure drop across the electrode at high air flows through the electrode and good manufacturability of the electrode with simple means of production and little labor. The characteristic features of the first aspect of the technology according to the present invention, the corana electrode, are now further explained. According to the state of the art, a corana electrode consists of a surface of a first conductor with a first insulator layer arranged thereon, which usually consists of ceramic material or glass. Furthermore, a second conductor whose surface is at a fixed distance from the first conductor, with the result that a first gap is created. By now applying a high voltage to the first and the second conductor, it is possible to get gas discharge in the first gap, if there is air or oxygen there. A corona then forms and the plasma thus formed contains atomic oxygen and oxygen that react to ozone. The electrodes made according to the prior art usually consist of a cylindrical first electrode and a cylindrical second electrode with a cylindrical first insulator layer arranged therein which occupies only partially the space between the inner cylinder and the outer cylinder so that an air gap is created. The advantage of such a cylindrical electrode is a large specific surface area of the electrode, i.e. a large surface area per cubic meter of electrode. Since the ozone production in principle increases proportionally with the electrode surface, this is an advantage of the cylindrical electrode design. A disadvantage of a cylindrical electrode design, however, is that special (construction) measures are required to properly dissipate the heat that arises in the electrode and that it is not technically easy to construct the air gap between the electrodes in which the corona forms, to be exactly the same size everywhere. This requires precision tubes from both the inner conductor, the outer conductor and the insulating material, as well as a good alignment of the electrode. The technology according to the present invention relates to a flat electrode. This flat electrode is established by taking a preferably first stainless steel plate (stainless steel 316) as the starting material for the first conductor. On this plate, as the first insulator, a glass plate is arranged which is preferably sandblasted on one side, i.e. the side which is not arranged on the first stainless steel plate. A first gasket is then applied to the glass plate which is preferably made from ozone-resistant material, such as Teflon. The gasket has a thickness that determines the size of the first air gap in the flat electrode. A second electrode is placed on top of the first gasket which, like the first electrode, is preferably a stainless steel 316 flat plate. However, in the second electrode, a hole is provided at each end of the rectangle on which a preferably stainless steel 316 hose grommet is mounted. The hose nozzles serve as a supply for the air / oxygen to the corona electrode and as a discharge for the ozone-rich reaction product. The air gap between the two electrodes is selected such that the air resistance between the electrodes is limited, so that the pressure drop across the electrode is also limited with large air flows. In practice, this means that an air gap is preferably larger than 0.5 millimeters. Furthermore, air gaps are in practice preferably smaller than 2 millimeters due to the relatively high voltage that is otherwise required to get a corona. The thickness of the glass plate (the first insulator) is preferably larger than 0.5 millimeter and preferably smaller than 2.5 millimeter. After the flat electrode system has been established by stacking the first electrode, the first insulator, the first gasket and the second electrode, the whole is cast in an ozone-resistant resin. This is preferably a polyurethane resin that is used in electrical engineering to cast electronic circuits (so-called "potting agent"). It is clear to a person skilled in the art that other polymers can also be used as casting resin. The use of the casting resin is expressly part of the technology according to the present invention since said casting resin well immobilizes the electrode and the method of obtaining a housing for the electrode in this way is very reliable, so that mass production can be realized quickly and with simple production means. In addition to the advantages already mentioned, the technology according to the present invention also offers an additional degree of freedom with regard to the wall thickness of the housing into which the electrode is cast (the thickness of the layer of casting resin). This degree of freedom offers the additional possibility of increasing the pressure resistance of the electrode by choosing a larger wall thickness of casting resin. As explained later in this application, this property is essential to make the technology according to the present invention suitable for use in pressure systems, i.e., in systems where the air pressure or oxygen pressure is greater than approximately 0.5 bar and can rise to approximately 15 bar.
    Now that the basic technology according to the present invention has been explained, a first variant follows the flat corona electrode already described, wherein use is made of PCB (printed circuit board) technology. In short, in the first variant, the first electrode is replaced by a PCB, i.e. a printed circuit board produced according to the state of the art. This printed circuit board is preferably made of FR4 material, i.e. glass-fiber reinforced epoxy laminate and contains a, preferably gold-plated, copper layer on one side. The (gold-plated) copper layer is the first electrode. The FR4 material of the PCB acts as the first insulator. The gasket used is preferably a PCB with the same dimensions as the first conductor but then without a copper layer and with a rectangular hole in the middle that ultimately forms the air gap. On top of the gasket, the second conductor, with the hose connectors fitted therein, is then placed again. If desired, the FR4 material that forms the first insulator can be provided with a layer of Teflon or another gas-impermeable polymer. In this way it can be prevented that oxygen and / or ozone eventually end up as a result of diffusion at the copper layer on the PCB and subsequently oxidize it. For the record, it is stated that in practice the diffusion of gas through the FR4 material is so low that oxidation of the copper layer on the PCB is negligible. It is further noted that it is convenient in practice not to provide the entire surface of the PCB with a copper layer but to maintain an edge of about 5 mm around the PCB that is free of the copper layer. In this way breakdown at the edges between the first electrode and the second electrode is prevented at all times. It is also noted that the application of the PCB technology makes it possible to provide the PCB on which the first conductor is located, the PCB that acts as a gasket, and the stainless steel 316 second conductor with holes so that the whole can be bolted, preferably plastic. assembled before casting. In a second variant of the flat corona electrode already described, use is made of a gas discharge plate. By a gas discharge plate is meant a plate-shaped embodiment of a cylindrical gas discharge lamp as described in patents NL1039186, NL1038161 and NL1038162. In short, a gas discharge plate is understood to mean a cylindrical gas discharge lamp with 1 electrode as described in NL1038161 and NL1038162, one side of which is made flat. Another construction consists of 2 glass plates between which there is an electrode and a noble gas mixture under low pressure. The gas discharge plate according to the definition in this invention functions at the same time as the first conductor (this is the gas as soon as gas discharge has taken place therein) and as a dielectric (the glass of the gas discharge plate). In this second variant of the flat corona electrode, a first gasket is also processed which is applied to the gas discharge plate. On top of the first gasket, the second conductor is then provided, which is again preferably made of stainless steel 316 and in which holes are provided to which hose connectors can be connected.
    According to a second aspect, the technology according to the present invention relates to a vertically arranged cylindrical reactor with preferably a liquid inlet at the bottom and a liquid outlet at the top. It is explicitly stated that in this application a cylindrical reactor is understood to mean a reactor whose length is at least twice as long as the width (or diameter or other characteristic radial coordinate) and that the reactor is therefore also a geometry of a beam or other geometric figure can have. In addition to a liquid inlet, there is also a gas inlet, preferably at the bottom of the reactor, and preferably a gas outlet at the top of the reactor. In order to ensure a good distribution of the gas in the reactor, a layer of glass marbles is preferably poured into the cylindrical reactor. The total length of the cylindrical reactor is preferably approximately 2 meters and the height of the column with marbles is preferably approximately 30 cm. The liquid inlet and the gas inlet of the reactor are located at the bottom of the cylindrical reactor so that the liquid and the gas entering the reactor are effectively distributed in a radial direction thanks to the bed of glass marbles. The cylindrical reactor is preferably provided with a first induction coil which is wound around the reactor. This first induction coil is operatively connected to a high-frequency current source which preferably operates in the frequency range of approximately 5 Hz to 10 MHz. Disinfection elements are preferably arranged in the column which are supplied with electrical energy by means of induction, i.e. the alternating magnetic field generated by the first induction coil. The disinfection elements preferably consist of metal particles in which eddy currents start to run and / or induction coils with UVC light sources and / or UVB light sources and / or UVA light sources and / or light sources for visible light and / or electrodes and / or diodes series with electrodes. The liquid to be disinfected is added to the liquid inlet of the vertically arranged cylindrical reactor. To the gas inlet is added a mixture of air and ozone produced in an ozone generator equipped with a corona electrode according to the first aspect of the present invention. Due to the constitution of the corona electrode with the technology according to the present invention, it is technically possible to pump large airflows through the electrode and in this way provide the reactor with a large excess of air and a relatively low concentration of ozone.
    For illustration, the basic construction of the corona electrode is explained with reference to Figure 1. See also the indications in the figure. Designation 1 relates to a first conductor with both hose tubes mounted thereon and shown as designation 2. Designation 6 represents a second conductor. Indicators 7 and 3 represent both electrode connections. Designation 5 represents an insulating insulator. Designation 4 indicates a gasket. Designation 8 shows the casting resin. It is noted that, in contrast to Figure 1, the casting resin can also partially or completely enclose the electrode to give it additional strength and pressure resistance.
    According to a third aspect, the technology according to the present invention consists of a column with activated carbon which is preferably connected in series with the cylindrical reactor. Preferably, the liquid leaving the ozone reactor is pumped through the activated carbon column. In this case, drug residues that have not yet been decomposed by ozone in the reactor are adsorbed to the activated carbon and at the same time the water is stripped of the excess ozone. Regeneration of the activated carbon column can be easily carried out by operating the reactor system and the column in series with an excess of ozone.
    Now that the three aspects of the technology according to the present invention have been explained, a number of preferred embodiments of the technology follow.
    In a first embodiment, a portion of the liquid is pumped into the vertical cylindrical reactor into a first pressure vessel. The first pressure vessel is preferably operated at a pressure between 0.5 bar and 15 bar, more preferably at a pressure between 2 and 6 bar and most preferably at a pressure of 4 bar and preferably pressurized by the product of the pump the ozone generator (air plus ozone) into the first pressure vessel. As a result, that amount of gas will dissolve in the liquid associated with the absolute pressure in the first pressure vessel and the gas composition. Subsequently, the liquid in the first pressure vessel is supplied to the cylindrical reactor which is preferably operated at a lower pressure than the pressure in the first pressure vessel, more preferably operated at atmospheric pressure and most preferably operated at a pressure which is at least 1 bar lower than the pressure in the first pressure vessel. Since the pressure in the first pressure vessel is higher than in the first cylindrical reactor, liquid pumped from the pressure vessel into the reactor will become oversaturated with air and ozone. The result is that microbubbles arise with a very large specific surface area, which ensures an exceptionally good transfer of dust from ozone gas to the liquid to be disinfected. The process described in the first embodiment is emphatically part of the technology according to the present invention. It is clear to a person skilled in the art that the new corona electrode according to the technology in this application is extremely suitable for use in combination with the first pressure vessel since the electrode can be constructed in such a way that it operates reliably at pressures up to approximately 15 bar .
    In a second embodiment, the technology of the present invention is combined with the use of a photocatalyst such as methylene blue. To this end, a low concentration of methylene blue (order of 1 mg methylene blue per liter of water to be disinfected) is introduced into the water to be disinfected. In combination with visible light and / or UVA radiation and ozone, radicals are formed in this way, with the result that the decomposition of medicine residues and disinfection of hospital waste water run efficiently. It will be clear to a person skilled in the art that the technology according to the present invention is generally applicable for disinfecting both drinking water and waste water. Furthermore, the technology according to the present invention is suitable for partially purifying water that is present in different biotopes. Pond water or water from ditches and lakes is mentioned as a non-limiting example. In such a case, it is often not necessary or even desirable that the technology according to the present invention kills all microorganisms present in the water. In such cases, the technology according to the present invention can be used to reduce the infection pressure of the water by killing (preferably partially selectively) microorganisms in the water and / or removing organic contaminants including nutrients or medicine residues present in the water.
    Finally, it is noted that in a number of cases it is efficient to first subject water with a very high concentration of impurities, bacteria, inorganic and organic nutrients to a pre-treatment before applying the technology according to the present invention. Non-limiting examples of such pre-treatment are the use of a membrane bioreactor (MBR), a moving bed biofilm reactor (MBBR) and a digester. Combinations of these pre-purification techniques and the technology described in this application explicitly form part of the technology according to the present invention. An unexpected additional advantage of applying said pre-purification techniques is that the biodiversity of the microorganisms in the pre-treated water is greatly reduced by the pre-purification technique used, which allows extensive optimization of the steps with the technology according to the present invention since this optimization can be aimed at killing a limited number of microorganisms and / or removing a limited number of microorganisms.
    Finally, a final embodiment of the technology according to the present invention is mentioned for the disinfection of hospital waste water. For this purpose a liquid is introduced into a tubular reactor which is provided with at least LEDs that produce light in the visible range, preferably in the range between 600 nm and 700 nm and most preferably in the range between 650 nm and 690 nm. To the liquid entering the reactor is preferably added an amount of methylene blue in the range of 0.01 mg / l to 100 mg / l, more preferably 0.1 mg / l to 10 mg / l and most preferably about 1 mg / l . By adding the methylene blue, the efficiency of the reactor appears to increase considerably with regard to disinfection of the water (killing of bacteria), the inactivation of viruses, DNA fragments and RNA fragments and the selective oxidation and inactivation of traces of drugs such as antibiotics. . By applying this latter embodiment of the technology according to the present invention, it appears possible to have disinfection and selective oxidation of drug residues carried out against a very high background concentration of approximately 130 mg / l COD (chemical oxygen demand). Without introducing any limitation in the scope of the technology according to the present invention, this surprisingly high efficiency and selectivity is attributed to the formation of methylene blue radicals under the influence of the red light, which is then after energy transfer (where methylene blue is a mediator) to oxygen, to single state oxygen or superoxide formation. These molecules are reactive and can cause disinfection and decomposition of drug residues but are unable to react with all organic components in the liquid. As a result, selectivity is obtained with respect to, for example, advanced oxidation with hydrogen peroxide or ozone whereby OH radicals are formed. It is noted that in addition to methylene blue, other dyes can also act as a photo mediator. These substances can also be naturally present in waste water. The use of a photo-mediator as described in the last embodiment to increase disinfection efficiency and the efficiency with which medicine residues can be removed is emphatically part of the technology according to the present invention.
    Example 1
    Finely filtered mixed hospital waste water on a 0.5 mm screen obtained on the demo site of the Antonius Hospital in Sneek is fed to an active sludge reactor with a volume of 1 m3. The feed flow to the reactor is 50 liters per hour, the liquid leaving the reactor goes to a settling The bottom of the settling is returned to the active sludge reactor and the clear overflow of the settling is the starting material for the disinfection tests. The COD from the feed to the activated sludge reactor appears to be 1600 mg / l. The clear overflow of the settler has a COD content of approximately 130 mg / l. The number of CFU (colony forming units) in the feed to the activated sludge reactor is approximately 5 * 106 / ml and that in the clear overflow of the settler approximately 5 * 104 / ml.
    50 liters of the clear overflow of the settler are added to a vessel. The liquid in the vessel is recirculated through a tubular reactor equipped with red LEDs with a maximum radiation production at 660 nm. Approximately 1 mg of methylene blue per liter of water is added to the reaction mixture. It appears that after 1 hour of reaction time a 1 log reduction of the total number of bacteria has occurred and specific tests on E. coli yield a 2 log reduction, specific tests on KESC a 3 log reduction for KESC and specific tests on ESBL Klebsiella a 1 log reduction for ESBL Klebsiella.
    Example 2
    As examples 1 and 2. However, the reactor from example 1 is provided with LEDs that are operatively connected to an induction coil in the reactor. The LEDs are supplied with electrical energy through induction.
    The advantage is that the LEDs are in constant motion and remain clean due to an abrasive effect, which benefits the light output. Furthermore, plug flow is obtained by means of the fluidized bed, which improves the conversion rate in the reactor.
    Example 3
    At the end of the reaction, the excess methylene blue is decomposed with ozone. This decomposition of methylene blue is a very selective process in which additional disinfection and decomposition of medicine residues occurs because of the radical avalanche that arises.
    After these examples, it is clear to the skilled person that the technology according to the present invention is extremely suitable for applications in markets other than the disinfection of hospital waste water. Examples of non-limiting examples are the horticultural sector for reducing water infection pressure and for removing micro-pollutants such as pesticides from the water, the pond sector for reducing water infection pressure, the swimming pool sector and the bulb sector.
    权利要求:
    Claims (18)
    [1]
    Device for disinfecting and / or purifying water characterized by • a tubular reactor with a liquid inlet and a liquid outlet • provided with red LEDs that emit light in the wavelength range between 600 nm and 700 nm • means for dosing methylene blue to the reactor • methylene blue in the reactor dissolved in the water and exposed to light emitted by the red LEDs.
    [2]
    Device as claimed in claim 1, wherein the LEDs in the reactor are operatively connected to an induction coil and are supplied with electrical energy by means of induction.
    [3]
    Device as claimed in any of the foregoing claims 1 and 2 plus an active sludge reactor and a settler in series as pre-purification.
    [4]
    Device according to one of the preceding claims 1 to 3, plus an ozone generator.
    [5]
    Device according to claim 4, wherein the ozone generator is fed with an excess of air to produce a mixture of air and ozone, characterized in that the resulting mixture of air and ozone is added to the tubular reactor.
    [6]
    Device according to one of the preceding claims 1 to 4 plus an activated carbon column.
    [7]
    The device of claim 6 plus means for dosing ozone to the activated carbon column to regenerate it.
    [8]
    Device according to one of the preceding claims 1 to 7, wherein less than 100 mg of methylene blue per liter of water to be purified is added to the purification process (less than 100 ppm).
    [9]
    Device according to one of the preceding claims 1 to 7, wherein less than 10 mg of methylene blue per liter of water to be purified is added to the purification process (less than 10 ppm).
    [10]
    Device according to one of the preceding claims 1 to 7, wherein less than 1 mg of methylene blue per liter of water to be purified is added to the purification process (less than 1 ppm) and more than 0.1 mg of methylene blue per liter of water to be purified (more than 0.1 ppm).
    [11]
    Device according to one of the preceding claims 1 to 7 for disinfection of hospital waste water and / or the removal of medicine residues from hospital waste water.
    [12]
    Device according to one of the preceding claims 1 to 7 for removing pesticides from water.
    [13]
    Device according to one of the preceding claims 1 to 7 for reducing the infection pressure of water in the pond sector.
    [14]
    Device according to one of the preceding claims 1 to 7 for reducing the infection pressure of water in the bulb sector.
    [15]
    Device according to one of the preceding claims 1 to 7 for reducing the infection pressure of water in the swimming pool sector.
    [16]
    Device according to one of the preceding claims 1 to 7 for purifying hospital waste water.
    [17]
    Device according to one of the preceding claims 1 to 7 for purifying waste water.
    [18]
    A method for disinfecting and / or purifying water characterized by a device according to any one of the preceding claims 1 to 17.
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    同族专利:
    公开号 | 公开日
    NL1041422B1|2016-08-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2019-04-24| PD| Change of ownership|Owner name: STICHTING WETSUS, EUROPEAN CENTRE OF EXCELLENCE FO Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: PURE GREEN TECHNOLOGIES B.V. Effective date: 20190215 |
    优先权:
    申请号 | 申请日 | 专利标题
    NL1040930|2014-08-30|
    NL1041221A|NL1041221B1|2015-03-10|2015-03-10|Method and device for disinfecting hospital waste water.|
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