KR20060105969A - Apparatus for destroying organic wastes by electric incineration and mediated oxidation - Google Patents

Abstract

The present invention relates to a partial oxidation by organic incineration of an organic waste liquid and a complete oxidation apparatus and a complete oxidation method by electrochemical mediated oxidation, wherein the complete oxidation apparatus of an organic waste liquid according to the present invention is an electric incinerator for partially oxidizing an organic waste liquid. ; A cooler for cooling the partially oxidized organic waste liquid discharged from the electric incinerator; A mediated oxidation reactor for completely oxidizing the partially oxidized organic waste liquid cooled in the cooler by an electrochemical mediated oxidation reaction with mediated ions; A mediated ion feeder for supplying mediated oxidation ions to the mediated oxidation reactor; A scrubber for removing harmful gases by gas-liquid contact from the completely oxidized oxide discharged from the intermediate oxidation reactor; Characterized in that consists of.

The complete oxidation of the organic waste liquid according to the present invention is an eco-friendly treatment apparatus for the complete oxidation of the hardly degradable organic waste liquid and at the same time, the size of the mediated oxidation reaction apparatus can be reduced by combining the partial oxidation method by the electric incinerator with the electrochemical mediated oxidation. It is an economical treatment device because it can reduce the energy of mediated oxidation.

Organic waste, electric incineration, partial oxidation, mediated oxidation, electrochemical, mediated ions, scrubber, electrolytic cell, cerium

Description

Apparatus for Destroying Organic Wastes by Electric Incineration and Mediated Oxidation}

1 is a schematic diagram of a complete oxidation process according to the present invention.

2 is a block diagram of a complete oxidation apparatus according to the present invention.

Figure 3 is a schematic diagram of a complete oxidation process including a complex mediated oxidation device combined with an ozone oxidation process for implementing mediated oxidation according to the present invention.

          -Explanation of symbols for the main parts of the drawings-

10: electric incinerator 11: electric incinerator

12 organic waste liquid 13 high temperature oxygen

14 outlet 15 cooler

16: supply pump 17: injection nozzle

20: mediated oxidation reactor 21: liquid phase oxidation reactor

22: mixer 23: inlet pipe

24 jacket 25 liquid oxidation reactor scrubber

26: ventilation flow 27: concentration measuring instrument

30: complex oxidation reactor 31: diffuser

40: electrolytic cell 41: anode chamber

42: cathode chamber 43: diaphragm

44: rectifier 53: diffuser

50: reduction regenerator 60: scrubber

70: ozone generator

The present invention relates to a partial oxidation by electric incineration of organic waste liquid and a complete oxidation apparatus and electrooxidation method by electrochemical mediated oxidation.

Recently, organic waste liquids are generated in various chemical processes, and organic waste liquids are incinerated and removed or oxidized and removed by an electrochemical method. However, in the case of organic waste solution, if not completely oxidized during the treatment process, not only various complaints are generated due to the generation of dioxin, etc., but also various social problems are caused by bioconcentration to surrounding organisms.

In particular, in the case of Polychlorinated Biphenyl (PCB), which has been used in insulating oils, adhesives, and paints in transformers and capacitors since the 1930s, production was stopped in countries around the world after being considered as an environmental pollutant. In the case of incineration of the PCB, a large amount of dioxins are inevitably generated.In the case of general incineration using LPG fuel, a large amount of carbon dioxide, a greenhouse gas, is inevitably generated. Even if the process is improved, the process is far from environmentally friendly.

U.S. Patent No. 5,420,088 discloses a method of using a cerium ion in an electrochemical cell as a method of recovering a catalytic material from a waste solid catalyst material as a method of treating toxic organic substances such as PCBs. International Publication No. 97/38943 discloses the application of a high concentration of cerium ions to an anolyte mixed with an ultrasonic mixer and the use of an intermediary ion to oxidize organic materials in the anolyte using an electrochemical cell. Although a process for treating organic waste liquid through a chemical mediated oxidation reaction is known, the process has a disadvantage in that a sufficient oxidation reaction of the organic waste liquid is not sufficient due to insufficient gas-liquid oxidation reaction and the like. Recently, International Patent Publication No. 99/28239 converts organic waste into carbon dioxide and water through the mediated oxidation reaction of organic waste using the oxidizing power of cerium tetravalent cation by adding cerium tetravalent cation to the emulsion state of water and acid. Although the process of making this process is disclosed, this process is disadvantageous in that there are many problems in the maintenance and operation of the device as well as the initial investment cost due to too many device configurations.

On the other hand, the present inventor has filed a patent application 2004-23367 "complex mediated oxidation treatment apparatus of organic waste liquid by electrochemical mediated oxidation and ozone oxidation" to solve the above problems.

However, in order to process the organic waste liquid appropriately in the mediated oxidation treatment process, the amount of mediated ions, rectifier and reduction regenerator for oxidizing the mediated ions must be increased, and the organic waste liquid generated by the mediated oxidation is generated. As salts accumulate and become suspended in the mediated oxidation system, or the membrane of the electrolytic cell is clogged, the efficiency of the mediated oxidation reaction decreases, and there is a problem that requires frequent maintenance of the mediated oxidation system. .

The present invention is to solve the above problems, the object of the present invention is to provide a treatment apparatus for the complete oxidation of the hardly decomposable organic waste liquid, and another object of the present invention is to electrochemically mediated partial oxidation method by an electric incinerator By combining with, it is possible to reduce the size of the mediated oxidation reaction device and to reduce the energy of the mediated oxidation, thereby providing an economical treatment device. Also, the partial oxidation process in the electric incinerator also does not use auxiliary fuel, thereby reducing greenhouse gas. It is to provide an environment-friendly organic waste liquid treatment device that minimizes the generation of phosphorous carbon dioxide.

The present invention relates to a partial oxidation by organic incineration of an organic waste liquid and a complete oxidation apparatus and a complete oxidation method by electrochemical mediated oxidation, wherein the complete oxidation apparatus of an organic waste liquid according to the present invention is an electric incinerator for partially oxidizing an organic waste liquid. 10; A cooler 15 for cooling the partially oxidized organic waste liquid discharged from the electric incinerator 10; A mediated oxidation reactor 20 for completely oxidizing the partially oxidized organic waste liquid cooled in the cooler 15 by an electrochemical mediated oxidation reaction with mediated ions; A medium ion feeder for supplying medium oxidation ions to the medium oxidation reactor 20; A scrubber 60 for removing harmful gas by gas-liquid contact from the completely oxidized oxide discharged from the intermediate oxidation reactor 20; Characterized in that consists of.

In addition, the present invention comprises the steps of: a) partially oxidizing the organic waste in the electric incinerator (10); b) cooling the partial oxidation organic waste liquid discharged from the electric incinerator in a cooler (15); c) oxidizing the cooled partially oxidized organic waste liquid by electrochemical mediated oxidation reaction with mediated ions in the mediated oxidation reactor 20; d) removing harmful gases from the completely oxidized oxide discharged from the intermediate oxidation reactor by gas-liquid contact in the scrubber (60); Characterized in that the complete oxidation of the organic waste liquid consisting of.

Hereinafter, the configuration and the operation of the embodiment of the present invention will be described in detail with reference to the accompanying drawings.

1 is a schematic diagram of a complete oxidation process according to the present invention, FIG. 2 is a block diagram of a complete oxidation apparatus according to the present invention, and FIG. 3 is a complex mediated oxidation combined with an ozone oxidation process for implementing mediated oxidation according to the present invention. A schematic diagram of a complete oxidation process including a device.

The complete oxidizer of the organic waste liquid according to the present invention is first provided with an electric incinerator 11 for partially oxidizing the organic waste liquid 12. The electric incinerator 11 partially oxidizes the organic waste liquid 12 by simultaneously introducing the organic waste liquid 12 at an appropriate speed under high temperature oxygen 13 or air conditions from the outside. In the present invention, the partial oxidation means that the organic waste liquid 12 is not completely oxidized to carbon dioxide, water and other inorganic substances, but is decomposed as an organic substance having a molecular weight of an appropriate size, but the degree of partial oxidation is an electric incinerator (11). It may vary depending on the capacity of the) or the input rate of the organic waste liquid 12, and may also include some of the completely decomposed material.

The lower end of the electric incinerator 11 is provided with a discharge port 14 for discharging the inorganic material generated during the incineration process, the heating element is SiC heating element, MoSi ₂ heating element, etc., the heating element is in contact with the organic waste liquid with the catalyst It is possible to increase the efficiency of the incineration oxidation reaction, the operating temperature of the incinerator is preferably 900 ℃ to 1200 ℃. The electric incinerator 11 employed in the present invention may be a conventional electric incinerator, and a person skilled in the art may change and apply a conventional electric incinerator as necessary.

The partially oxidized organic waste liquid from the electric incinerator 11 is discharged in a hot gas state to the top of the electric incinerator, and the discharged partially oxidized organic waste liquid is cooled to an appropriate temperature before being introduced into the intermediate oxidation reactor 20. Go through (15). In order to increase the cooling efficiency, a spray nozzle 17 is provided in a line between the electric incinerator 11 and the cooler 15 to circulate the partially oxidized organic waste liquid discharged as a hot gas from the cooler by using a circulation pump 16. It is also the scope of the present invention to cool by utilizing the circulated partial oxidation organic waste liquid.

A mediated oxidation reactor which completely oxidizes the partially oxidized organic waste liquid cooled from the cooler 15 by the electrochemical mediated oxidation reaction by the mediated ions to oxidize the partially oxidized organic waste liquid cooled by the mediator ion. (20) and a medium ion feeder for supplying medium oxidation ions to the medium oxidation reactor (20) are provided to completely oxidize the partially oxidized organic waste liquid discharged from the cooler (15) by the medium oxidation reaction (20). .

The mediated oxidation reactor 20 is located at the upper end of the liquid oxidation reactor 21 and the liquid oxidation reactor 21 which mediates the introduced organic waste liquid by the mediated ion, and the mediated ion flowing out of the mediated ion supply is introduced into the liquid phase. The scrubber 25 for mediating the gas generated from the oxidation reaction tank is provided, and the mediated oxidation reaction occurs quickly at a high temperature, so the medium oxidation reaction tank 20 is provided with a jacket 24 for temperature control. The mediated ion inlet tube 23 is provided from the lower end of the scrubber 25 to the lower portion of the liquid oxidation reactor 21 so that the mediated oxidation reaction occurs while the introduced mediated ions are directly mixed.

The median ion supply 40 receives anode from the anode chamber 41 and anode chamber in which the mediated ions introduced and reduced by the mediation oxidation reactor 20 are oxidized by the current from the rectifier 44 to reduce the catholyte solution. Reduction regenerator for oxidizing the cathode chamber 42, the electrolytic cell 40 provided with a diaphragm 43 between the anode chamber 41 and the cathode chamber 42, and the reduced cathode liquid flowing out of the cathode chamber ( 50), a complex oxidation reactor for simultaneously performing the electrochemical mediated oxidation reaction by the mediated ion and the oxidation reaction using ozone generated from the ozone generator 70 in the unreacted organic waste liquid of the mediated oxidation reactor 20 It is preferable that 30 is further provided between the intermediate oxidation reactor 20 and the electrolytic cell 40.

As the ion used as the intermediate ion, a transition metal or a transition metal compound is suitable, and at least one selected from Ce ⁺⁴ , Ag ⁺² , Co ⁺³ , and Mn ⁺³ is preferable. In Ce ^{+ 4} , Ag ^{+ 2} is more preferable, and Ce (NO ₃ ) ₄ is most preferred as a compound of Ce ⁴⁺ ions. The mediated ions are dissolved in nitric acid or sulfuric acid aqueous solution to oxidize the organic waste solution by mediated oxidation reaction, and then reduced. The mediated ions are oxidized by electrochemical method in the anode chamber 41 of the electrolytic cell 40 and circulated again. The concentration of the mediated ion is 0.5M to 1.6M, preferably 0.8M to 1.5M.

In the cathode chamber 42 of the electrolytic cell 40, the catholyte is reduced simultaneously with the oxidation of the intermediate ion in the anode chamber 41, and the catholyte solution is preferably HNO ₃ or H ₂ SO ₄ .

At this time, the temperature of the mediated oxidation reaction is performed at room temperature to 100 ° C, preferably 70 ° C to 100 ° C, and the operating temperature of the catholyte is preferably room temperature to 70 ° C.

The mediated oxidation reactor 20 and the mediated oxidation ion feeder may be provided with reference to a conventional mediated ion reactor, and are described in detail in patent application 2004-23367 filed by the present inventors, and thus description thereof is omitted. .

On the other hand, the organic waste liquid contains a large amount of halogen elements, in particular chlorine, in addition to carbon, hydrogen and oxygen elements, and therefore, even if the organic waste liquid is completely oxidized by the mediated oxidation reaction, chlorine or the like is inevitably included. The complete oxidizer of the organic waste liquid according to the present invention includes a scrubber 60 at the rear end of the medium oxidation reactor 20 in order to scrub toxic gases such as chlorine from the gas discharged from the medium oxidation reactor with NaOH aqueous solution. The scrubber 60 used in the present invention may be used as long as it is a scrubber used in a chemical process. The scrubber 60 may be provided with a plurality of scrubbers 60 as necessary to minimize the gas discharged into the atmosphere by scrubbing different gases sequentially.

In addition, the present invention includes a method for the complete oxidation of the organic waste liquid through the following steps.

a) partially oxidizing the organic waste liquid in the electric incinerator (11).

b) cooling the partial oxidation organic waste liquid discharged from the electric incinerator (11) in a cooler (15).

c) completely oxidizing the cooled partial oxidation organic waste liquid by an electrochemical mediated oxidation reaction with mediated ions in a mediated oxidation reactor (20).

d) removing harmful gases from the completely oxidized oxide discharged from the intermediate oxidation reactor by gas-liquid contact in the scrubber (60).

As described above, in the method of fully oxidizing organic waste liquid according to the present invention, the organic waste liquid is partially oxidized in the first electric incinerator 10 and the second oxidation is completely treated by mediated oxidation in the intermediate oxidation reactor 20. Characterized in going through the steps.

In the step of partially oxidizing the organic waste liquid in the electric incinerator 10, the organic waste liquid is partially oxidized in the electric incinerator while the high temperature air or oxygen is added together while the organic waste liquid is pumped into the electric incinerator 11. The operating temperature of the incinerator 11 is preferably 900 ° C to 1200 ° C. The degree of partial oxidation of the organic waste liquid may vary depending on the operating conditions such as the capacity of the electric incinerator 11 and the input speed of the organic waste liquid, and in particular, the medium oxidation reactor at the rear end of the electric incinerator 11 according to the degree of partial oxidation of the organic waste liquid. This affects the capacity, input speed and the like of (20).

The partial oxidation step in the electric incinerator is preferably partially oxidized the organic waste liquid by hot air or oxygen and an electric heating element without auxiliary fuel such as LPG in order to reduce the amount of carbon dioxide generated.

By partial oxidation, the organic waste liquid is decomposed as an organic substance having an appropriate size molecular weight.

The partially oxidized organic waste liquid discharged from the electric incinerator 10 is discharged to the upper end of the electric furnace in a high temperature gas state, and the discharged partial oxidized organic waste liquid is provided at the end of the electric incinerator 11 and the electric incinerator 11. In the injection nozzle 17 provided in the line between the coolers 15, the first cooling is circulated by the partially oxidized organic waste liquid circulating fluid injected from the cooler, and the first cooled partially oxidized organic waste liquid is cooled by the cooler 15. Secondary cooling at is cooled to a temperature of 70 ℃ to 100 ℃ suitable for the medium oxidation reaction is introduced into the medium oxidation reactor 20 lower.

The partially oxidized organic waste solution introduced into the liquid oxidation reactor 21 provided below the medium oxidation reactor 20 is mixed with the medium ions supplied from the medium ion supply in the liquid phase, and the oxidation reaction proceeds. At this time, the liquid oxidation reactor 21 By using the ultrasonic mixer provided at the bottom of the ultrasonic mixing can increase the reaction rate of the organic waste liquid and the mediated ion.

The low-molecular-weight gas that is not completely oxidized during the intermediate conversion reaction in the intermediate oxidation reactor 21 flows into the lower end of the scrubber 25 located at the upper end of the liquid oxidation reactor 21 and flows in from the top of the scrubber 25. Contact of the mediator with gas-liquid induces complete oxidation of the waste fluid.

At the same time, the mediated ions are reduced and the mediated ions are reduced and the mediated ions are introduced into the mediated ion feeder and oxidized again by the rectifier 44 in the anode chamber 41, from the anode chamber 41. Receiving electrons through the diaphragm 43 to reduce the catholyte of the cathode chamber 42, the reduced catholyte is discharged from the cathode chamber 42 is oxidized in the reduction regenerator and again the cathode chamber ( 42).

The completely oxidized oxide discharged by the mediated oxidation reaction from the mediated oxidation reactor includes toxic gases such as chlorine, and the toxic gases are NaOH aqueous solution or the like by gas scrubber 60 provided at the rear of the mediated oxidation reactor. Contact and removal of toxic gases are removed from the atmosphere.

The above step of the mediated oxidation reaction is not intended to limit the present invention but only to clearly illustrate the present invention, and the conventional mediated oxidation reaction and its application, if applicable, are applied to the present invention. Anything that undergoes a partial oxidation process in the electric incinerator 10 is included within the scope of the present invention.

The complete oxidation of the organic waste liquid and the method of completely oxidizing the organic waste liquid according to the present invention combine the partial oxidation method by the electric incinerator with the electrochemical mediated oxidation, and it is possible to completely oxidize the hardly decomposable organic waste liquid at an economic cost. The partial oxidation process in an electric incinerator also has the advantage of minimizing the generation of carbon dioxide, a greenhouse gas, by not using auxiliary fuel.

Claims (8)

An electric incinerator for partially oxidizing the organic waste liquid; A cooler for cooling the partially oxidized organic waste liquid discharged from the electric incinerator; A mediated oxidation reactor for completely oxidizing the partially oxidized organic waste liquid cooled in the cooler by an electrochemical mediated oxidation reaction with mediated ions; A mediated ion feeder for supplying mediated oxidation ions to the mediated oxidation reactor; A scrubber for removing harmful gases by gas-liquid contact from the completely oxidized oxide discharged from the intermediate oxidation reactor; Complete oxidation apparatus of organic waste liquid which consists of. The method of claim 1, The electric incinerator is a complete oxidation of the organic waste liquid, characterized in that the organic waste liquid is partially oxidized by hot air or oxygen and electric heater without auxiliary fuel. The method of claim 2, And the cooler is a spray cooler having a spray nozzle for cooling the partially oxidized organic waste liquid discharged from the electric incinerator. The method of claim 3, wherein The medium ion supply device is an anode chamber in which the reduced medium ion flowing from the medium oxidation reactor is oxidized by the current from the rectifier, a cathode chamber receiving electrons from the anode chamber and reducing the cathode liquid, and between the anode chamber and the cathode chamber. An electrolysis cell provided with a diaphragm; A reduction regenerator for oxidizing the reduced catholyte flowing out of the cathode chamber; Complete oxidation device of organic waste liquid, characterized in that consisting of. The method of claim 4, wherein A complex oxidation reactor for simultaneously performing an electrochemical mediated oxidation reaction using an intermediate ion and an oxidation reaction using ozone is further provided between the mediated oxidation reactor and the electrolytic cell. Complete oxidation apparatus of organic waste liquid made with. The method according to claim 4 or 5, The mediated ion is a complex mediated oxidation treatment apparatus for organic waste liquid by electrochemical mediated oxidation and ozone oxidation, characterized in that the cerium ion or silver ion. a) partially oxidizing the organic waste liquid in an electric incinerator; b) cooling the partially oxidized organic waste liquid discharged from the electric incinerator in a cooler; c) completely oxidizing the cooled partial oxidation organic waste liquid by electrochemical mediated oxidation reaction with mediated ions in a mediated oxidation reactor; d) removing noxious gases by gas-liquid contact in a scrubber from the completely oxidized oxide discharged from the mediated oxidation reactor; Complete oxidation method of organic waste liquid consisting of. The method of claim 7, wherein The partial oxidation step of the electric incinerator of step a) is a complete oxidation method of the organic waste liquid, characterized in that the organic waste liquid is partially oxidized by hot air or oxygen and electric heater without auxiliary fuel.

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