KR100256547B1 - Apparatus for purifying organic waste water - Google Patents

Abstract

PURPOSE: A purifying equipment of organic wastewater is provided, which can oxidize, react at low temperature and pressure and separation effectively by adding hydrogen peroxide to air, by bubbling to increase oxidation efficiency and by passing through a catalyst of ceramic material coated with transition metal or metal oxides, so that the system can treat organic wastewater completely. The system can also save heating cost and can change the catalyst according to the kind of wastewater. CONSTITUTION: The system comprises the followings: (i) a reactor(1) that consists of gas injection chamber(11), a bubbling chamber(12) and a reaction chamber(13); (ii) a distributing member(5) that is porous and is set between gas injection chamber(11) and the bubbling chamber(12) for distributing gas; (iii) a honey comb catalyst member(3) that is fixed in the reaction chamber(13) for decomposing organic matter to water and carbon dioxide by oxidation of bubbled wastewater of bubbling chamber(12); (iv) a heating member(43) that is set around the reaction chamber(13) for heating honey comb catalyst member(3); (v) a separator(2) that has a liquid outlet(21) at the bottom and a gas discharge line(22) at the top and is installed down stream of reactor(1) for separating water and carbon dioxide; and (vi) a condenser(45) that is set on the gas discharge line(22) for condensing moisture in the discharge gas and for recovering through a recovery ling(24).

Description

Organic wastewater purifier

The present invention relates to a purification apparatus for treating wastewater, and more particularly, to an organic wastewater purification apparatus capable of treating various high concentration organic wastewater such as dyeing industrial wastewater or chemical industrial wastewater at low temperature and low pressure.

Generally, as a device for purifying dyeing industrial wastewater or chemical industrial wastewater, a high temperature reaction of 150 ° C to 325 ° C and a high pressure of 20atm to 200atm using a packed bed reactor or a slurry bed fluidized bed reactor having a catalyst layer using a wet oxidation concept. Apparatuses are provided for purifying organic wastewater by obtaining oxidation efficiency under conditions.

In the high pressure packed-bed reactor, which is one of the apparatuses of the wet oxidation process, waste water supplied from the liquid tank 84 containing the wastewater and gas supplied from the gas cylinder 86 pass through the evaporator 85 as shown in FIG. While the sprayed wastewater passes through the main reaction portion, which is the catalyst layer 81 filled in the fixed tank surrounded by the heating mantle 82, the oxidation reaction is continuously performed. After passing through the condenser 83 for purification, the flow path of the atomized wastewater passing through the portion providing the immobilized catalyst layer 81 is irregular, so that the dispersion of the liquid phase is poor and the reaction rate is low. In addition, the pressure drop between the upper and lower tanks of the reaction part easily causes a pressure drop, resulting in an irregular flow flow. It takes place, whereby gas and significant blockage of liquid flow occurs as part of the catalyst is a problem that can not be effectively used. In addition, the reactor of the packed bed catalyst bed has difficulty in temperature control, and it is very difficult to replace the catalyst packed in the fixed tank.

In addition, the slurry-phase fluidized bed reactor, which is one of the apparatuses of the wet oxidation process, receives wastewater in a reactor enclosure 90 in which a heating mantle 91 is disposed around the inside, as shown in FIG. 5, and a gas cylinder ( 93) and the gas supplied to the gas inlet (94) to purify by mixing the stirrer (92) to have a reaction in a batch type, such a fluidized bed reactor is to receive a certain amount of waste water in one reactor chamber and to purify The purified water is limited in the amount of purification because it is repeated to discharge to the outside, and since the sludge or sediment is inevitably generated after the reaction because the purification process is not a continuous process, a subsequent treatment step for treating this is added. It is very inefficient and uneconomical.

The present invention has been proposed to solve the above problems, and an object of the present invention is to oxidize and remove contaminants without generation of by-products as well as easily decompose into water and carbon dioxide under the condition of low temperature and low pressure. The present invention provides an organic wastewater purification apparatus which can obtain economical efficiency and can efficiently process high concentration or hardly decomposable organic wastewater without generating secondary treatment cost such as slurry treatment.

In addition, the present invention increases the purification efficiency by coating a transition metal or metal oxide on the catalyst member for oxidizing and decomposing wastewater, and easy replacement, appropriate for the cost reduction of the catalyst recovery step in the industrial process and the characteristics of each wastewater The present invention provides an organic wastewater purification apparatus that can easily replace and use a catalyst member.

In another aspect, the present invention is to provide an organic wastewater purification apparatus that can further improve the oxidation efficiency by mixing together with the oxidizing agent of air or pure oxygen oxidizing waste water and hydrogen peroxide as an auxiliary oxidant.

In addition, the present invention is to provide an organic wastewater purification apparatus to be discharged through the activated carbon filter to further improve the treatment efficiency of the gas and liquid components that are purified while passing through the catalyst member and separated in the separator.

1 is an exploded perspective view schematically showing a purification apparatus of the present invention,

2 is a schematic cross-sectional view of an essential part of the purification apparatus of the present invention;

3 is an explanatory view showing the operation of the catalyst member of the purification device of the present invention,

4 is a schematic view of a conventional high pressure packed bed reactor,

5 is a schematic diagram of a conventional high pressure fluidized bed reactor.

* Explanation of symbols for main parts of the drawings

1: reactor 2: separator

21: liquid outflow pipe 22: gas outflow pipe

23 exhaust pipe 24 recovery pipe

3: catalyst member 41: air cylinder

42: wastewater storage tank 43: heating member

44: back pressure valve 45; Condenser

46,47: activated carbon filter 48: hydrogen peroxide tank

5: Distribution member 61: Gas inlet

62: liquid inlet 63: discharge pipe

64,65: preheater

In order to achieve the above object, the present invention provides a gas injection chamber for injecting pure air, a bubble chamber for aeration and bubbled at the same time as the injection of the air distributed through the distribution member of the porous material and the incoming waste water, and the upper portion of the bubble chamber And a honeycomb catalyst member disposed therein to decompose organic matter into water and carbon dioxide while oxidizing the bubbled wastewater supplied from the bubble chamber and discharging the separated water and carbon dioxide into the upper discharge pipe, respectively. A reactor formed by separating and easily separating and assembling; A heating member installed to be wrapped around the reaction chamber to provide heat to promote the oxidation reaction to the honeycomb catalyst member; The gas outlet pipe communicating with the discharge pipe installed in the upper part of the reaction chamber, re-separated the separated water and carbon dioxide by gravity, and the liquid discharge pipe for discharging the separated water to discharge the gas of carbon dioxide at the bottom Separators installed in communication with each other; A condenser connected to one end of the gas outlet pipe of the separator and in communication with an exhaust pipe at the other end, the condenser condensing the gas discharged from the gas outlet pipe; And a recovery pipe communicating with the lower side of the exhaust pipe and collecting a small amount of water contained in the gas discharged from the gas outlet pipe while collecting the condensed liquid into the liquid outlet pipe while passing through the condenser. .

In addition, the present invention is characterized in that the honeycomb catalyst member disposed in the reaction chamber is formed of a ceramic material, the transition metal or metal oxide is coated on the surface of the catalyst member.

In another aspect, the present invention is characterized in that the activated carbon filter is disposed in the exhaust pipe communicating with the condenser and the liquid outflow pipe communicating with the lower part of the separator.

In another aspect, the present invention is characterized in that the hydrogen peroxide tank is installed so that one end is connected to the bubble chamber of the reactor and the other end is supplied between the waste water inlet pipe connected to the waste water storage tank.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

1 to 3 is an exploded perspective view schematically showing the purification apparatus of the present invention, a schematic cross-sectional view of the main portion and an explanatory view showing the operation of the catalyst member.

Reference numeral 1 is a reactor of the present invention, the reactor 1 is separated from the lower side into the gas injection chamber 11, bubble chamber 12 and the reaction chamber 13, but the conventional fastening plan that can be assembled to be connected to each other The branch is integrally formed, and the shape thereof is preferably formed in a circular shape, but is not limited thereto, and may be manufactured in an oval or polygonal tubular shape.

The distribution member 5 of the porous material is disposed between the gas injection chamber 11 and the bubble chamber 12, and oxygen or pure air used as an oxidant is stored in the bottom of the gas injection chamber 11. The other end of the air cylinder 41 and the one end is connected to the gas injection pipe 61 is connected to provide a space that can be smoothly distributed and dispersed when oxygen or pure air injected through the distribution member (5) do.

The distribution member 5 is composed of a porous material that is a sintered glass filter plate having a pore diameter of about 70 μm to 100 μm to finely disperse oxygen or pure air introduced into the gas injection chamber 11. It is inserted into a groove formed between the injection chamber 11 and the bubble chamber 12, or is installed to be fixed at the same time as fastening the flange portion using a conventional asbestos gasket and bolt.

Bubble chamber 12 is disposed in the upper portion of the gas injection chamber 11 and is provided with a see-through window 121 that can visually identify the bubble phenomenon inside the side, the waste water storage tank 42 and one side The other end of the waste water injection pipe 62 is connected to one end, so that the gas and waste water supplied from the distribution member 5 and the wastewater storage tank 42 are mixed and provided with sufficient space to be bubbled. It is composed.

The reaction chamber 13 has a honeycomb catalyst member 3 disposed above the bubble chamber 12 and decomposes the bubbled wastewater into water and carbon dioxide, and disassembles the decomposed water and carbon dioxide into an upper discharge pipe 63. Is configured to discharge).

The honeycomb-shaped catalyst member 3 is manufactured in the same cross-sectional shape as the tubular shape of the reactor 1, and a ceramic material is used as a material and is formed integrally or in a double or triple stacked time for oxidation reaction. Its length can be increased to provide enough, and its surface has catalysts for promoting oxidation reactions suitable for the characteristics of wastewater, Pt, Ru, Rh, V₂O ₅ , Cr₂O₃, Fe₂O₃, CoO, CuO, NiO, MoO₃ Transition metal or metal oxide, such as, and the surface area coated with the metal oxide is to increase the oxidation reaction area to 2.5 ~ 4.0㎡ / g, which is larger than the general monolith surface area of 0.1 ~ 1.0㎡ / g Then, the inside of the reaction chamber 13 is firmly fixed by a support such as a separate silicone rubber or the like.

The heating member 43 provided on the outer circumference of the reaction chamber 13 provides 100 ° C to 150 ° C (1 atm to 10 atm) of low temperature heat, and the generated heat is a honeycomb catalyst disposed in the reaction chamber 13. It is delivered to the member 13 to increase the efficiency of the oxidation treatment process. On the other hand, the medium for providing heat may be used as the heating member 43 by circulating hot water, steam or the like, or by installing a heater using a heating line of iron chromium or nickel chromium.

Meanwhile, the gas injection pipe 61 and the waste water injection pipe 62 are provided to obtain a more efficient oxidation treatment process even with low temperature heat provided by the heating member 43 and to reduce excessive heating of the reaction chamber 13. Pure air and wastewater supplied to each gas injection pipe 61 and wastewater injection pipe 62 are disposed to pass through the preheating devices 64 and 65 of the respective constant temperature water tanks. As it is preheated to a temperature higher than room temperature when flowing into the furnace, pure air and wastewater are further activated in the bubble chamber 12 to obtain an optimal bubble state.

The separator (2) communicating with the discharge pipe (63) installed above the reaction chamber (13) is a liquid discharge pipe for discharging the separated water to separate the water and carbon dioxide oxidized and separated from the reaction chamber (13) by gravity. 21 is installed to communicate in the lower portion and the gas outlet pipe 22 for discharging the gas of carbon dioxide is installed in the upper portion, respectively. In addition, the back pressure valve 44 between the gas outlet pipe 22 which communicates one end of the condenser 45 with the upper part of the separator 2 in order to control the discharge flow of the gas separated by gravity in the separator 2. Is installed, the condenser 45 is a condenser 45 to condense a small amount of moisture contained in the gas discharged from the gas outlet pipe 22 and collect the condensed liquid to the liquid outlet pipe 21 Will be installed.

In addition, activated carbon filters 46 and 47 filled with granular activated carbon are disposed in the exhaust pipe 23 communicating with the condenser 45 and the liquid outlet pipe 47 communicating with the lower part of the separator 2, respectively. Substances and odor components are finally purified.

In addition, one end is connected to the bubble chamber 12 of the reactor 1 and the other end is installed to oxidize hydrogen peroxide tank 48 to supply hydrogen peroxide between the waste water injection pipe 62 connected to the waste water storage tank 42 The reaction efficiency will be improved.

Each reactor (1), separator (2), wastewater storage tank 42, hydrogen peroxide tank (48), pure air cylinder (41) has a pump for supply, flow for purification, such as a flow meter, a pressure gauge, a thermometer Automatic control devices are attached and they are used for general purpose but are resistant to chemical corrosion and suitable for high temperature and high pressure. In addition, the reactor, separator and connectors, which are main parts, are also preferably made of stainless steel, which is resistant to chemical corrosion, and is configured to be sealed with a gasket on each connection part to withstand high temperature and high pressure. do.

1 and 3, the air and waste water are supplied to the gas injection pipe 61 and the liquid injection pipe 62 from the pure air cylinder 41 and the waste water storage tank 42, as shown in FIGS. Air and wastewater supplied to the gas injection pipe 61 and the liquid injection pipe 62 are first preheated while passing through the preheaters 64 and 65, and the first preheated air is supplied to the gas injection chamber 11. After the distribution is passed through the distribution member (5) and at the same time the wastewater introduced into the bubble chamber 12 is mixed with the dispensed air to make a bubble form.

Hydrogen peroxide tank (48) with 35% of industrial hydrogen peroxide in order to increase the oxidation efficiency along with air as the main oxidizing agent and to obtain a practical treatment effect under conditions of 100 ° C to 150 ° C, 1atm to 10atm room temperature, and atmospheric pressure. Are supplied to the bubble chamber 12 together.

Bubble-bubble wastewater in the bubble chamber 12 moves to the honeycomb catalyst member 3 of the reaction chamber 13 to generate a slug flow. That is, as the sludge flows in the passage of the catalyst member 3, the diameter of the wastewater is compressed to be equal to or smaller than the passage diameter so as to enter the passage as shown in FIG. It happens. Wastewater passing through the passage of the catalyst member 3 while forming the slug flow state is reacted by heating the catalyst layer of the transition metal or metal oxide and the heating member 43 and oxidizing agent of air and hydrogen peroxide, and the catalyst member 3 Wastewater that has passed completely through) can be oxidized and separated into water and carbon dioxide.

In the above reaction process, the heating member 43 coated with a catalyst layer of a transition metal or a metal oxide on a honeycomb-shaped material made of a ceramic material,

①. Because of the ceramic material, the waste water treatment temperature is not limited.

②. Its excellent corrosion resistance makes it possible to treat various wastewater such as acid and alkaline liquid.

③. High mechanical strength and excellent durability.

④. Since the catalyst is coated on the ceramic, there is little catalyst loss, so it can be used for a long time.

⑤. Large reaction area, high efficiency of wastewater treatment.

⑥. It can be miniaturized and its installation and operation is simple.

⑦. Depending on the target wastewater, a suitable catalyst can be easily exchanged and used to treat various wastewaters.

⑧. The flow rate of the wastewater is at least supplied with the oxidant, so that the dispersion of the liquid phase is good and a uniform flow can be obtained.

⑨. There is no risk of fluidization of the catalyst beds and passages, which can increase the flow of waste water and provide advantages of low pressure drop.

As described above, the water and carbon dioxide obtained by the oxidation reaction while completely passing through the passage of the catalyst member 3 are moved to the upper portion of the reaction chamber 13 and then moved to the separator 2 through the discharge pipe 63 and the separator 2 Water and gaseous carbon dioxide separated by gravity are separated by gravity and the gas is discharged to the upper gas outlet pipe 22 in the internal pressure control state of the back pressure valve 44, and the liquid is discharged from the lower liquid outlet 21. To be discharged.

The gas discharged to the gas outlet pipe 22 passes through the condenser 45, and a small amount of liquid mixed in the gas is condensed and recovered into the recovery pipe 24, and the gas passes completely through the activated carbon filter 46. Purified and discharged to the atmosphere.

The liquid discharged to the recovery pipe 24 and the liquid outflow pipe 21 again passes through the activated carbon filter 47 to undergo a complete purification process.

As described above, the present invention makes it easy to add hydrogen peroxide to the air as an oxidant and to further increase the oxidation efficiency, thereby making them easily bubble-type bubbles, and these are oxidized at low temperature through a catalyst member coated with a transition metal or metal oxide on a honeycomb-type ceramic material. In addition, the reaction and separation process can be more effectively processed at low pressure, so that the wastewater can be treated perfectly, and the effect of reducing the excessive cost for providing heat for the oxidation reaction is reduced. According to the treatment target of the catalyst member can be easily replaced because it is very practical to increase the treatment efficiency at an economic cost.

Claims (7)

A gas injection chamber 11 having one end connected to the other end of the gas injection pipe 61 connected to the air cylinder 41, and disposed at an upper portion of the gas injection chamber 11 and facing sideways 121. And the other end of the wastewater inlet pipe 62 having one end connected to the wastewater storage tank 42 and having a bubble chamber 12 that bubbles and simultaneously bubbles the supplied gas and the wastewater, and an upper portion of the bubble chamber 12. A reactor separated and formed into a reaction chamber 13 for decomposing the wastewater bubbled and bubbled into water and carbon dioxide to be discharged to the upper discharge pipe 63; A distribution member 5 of porous material disposed between the gas injection chamber 11 and the bubble chamber 12 to distribute or disperse gas; A honeycomb catalyst member (3) inserted and fixed in the reaction chamber (13) and decomposing organic matter into water and carbon dioxide while causing the bubbled wastewater supplied from the bubble chamber (12) to undergo an oxidation reaction; A heating member 43 installed to be wrapped around the reaction chamber 13 to provide heat to promote the oxidation reaction to the honeycomb catalyst member 3; Communicating with the discharge pipe 63 installed in the upper portion of the reaction chamber 13, the separated water and carbon dioxide re-separated by gravity, the liquid discharge pipe 21 for discharging the separated water is a gas of carbon dioxide in the lower portion The gas outlet pipe 22 for discharging the separator is installed in communication with the upper portion; A condenser 45 connected to one end of the gas outlet pipe 22 of the separator 2 and in communication with an exhaust pipe 23 at the other end and condensing the gas discharged from the gas outlet pipe 22; A small amount of water, which is communicated to the lower side of the exhaust pipe 23 and contained in the gas discharged from the gas outlet pipe 22, passes through the condenser 45 to condense the liquid into the liquid outlet pipe 21. Organic wastewater purification apparatus comprising a recovery pipe 24 for collecting. The method of claim 1, Honeycomb catalyst member (3) disposed in the reaction chamber 13 is formed of a ceramic material, the organic wastewater purification apparatus, characterized in that the transition metal or metal oxide coated on the surface of the catalyst member (3). The method of claim 1, The porous member distribution member (5) is an organic wastewater purification apparatus, characterized in that the sintered glass filter having a pore diameter of 70㎛ ~ 100㎛. The method of claim 1, Organic wastewater purification apparatus, characterized in that the back pressure valve 44 is installed between the gas outlet pipe (22) for communicating the upper portion of the separator (2) and one end of the condenser (45). The method of claim 1, Activated carbon filter (46, 47) characterized in that the activated carbon filter (46, 47) disposed in the exhaust pipe (23) communicated to the condenser (45) and the liquid outlet pipe (21) communicated to the lower part of the separator. The method of claim 1, And a preheating device (64, 65) for primary preheating of the gas and the waste water supplied to the gas injection pipe (61) and the waste water injection pipe (62). The method according to any one of claims 1 to 6, The hydrogen peroxide tank 48 is installed so that one end is connected to the bubble chamber 12 of the reactor 1 and the other end is supplied between the waste water injection pipes 62 connected to the waste water storage tank 42. Organic wastewater purifier.