The present invention relates to a treatment technique for decomposing components in various waste liquids, such as a hydrogen peroxide-containing waste liquid, by using fibrous activated carbon, and more specifically to a technique for obtaining excellent treatment efficiency by using fibrous activated carbon formed into a sheet.
Examples of treatment methods for various waste liquids such as a hydrogen peroxide-containing waste liquid discharged from a semiconductor or liquid crystal manufacturing process conventionally include: a method involving enzyme degradation; a method involving chemical neutralization; and a method involving catalyst decomposition.
The method involving enzyme degradation generally requires a predetermined reaction time and thus requires a large reaction tank. Further, the reaction tank must be provided with a stirring device, and thus the reactor itself may considerably increase in size depending on water volume.
The method involving chemical neutralization has problems of requiring the use of acid or alkali chemicals for neutralization, and the formation of neutralized byproducts. In waste liquid treatment, the discharge of those chemicals and byproducts out of the treatment system must be minimized. As a result, additional treatment facilities and the like are required.
The method involving catalyst decomposition has no problems associated with chemicals, byproducts, and the like. Further, the reaction is relatively fast, and thus the method is appropriate for a continuous waste liquid treatment process. However, in a case where a catalyst is in the form of particles, the small specific surface areas of the catalyst inhibit improvement in treatment efficiency, and thus the reactor itself tends to increase in size. In a case where a catalyst is in the form of particles and a gas generates through a decomposition reaction of waste liquid components, a reactor must have a passage structure for directing the flow of the waste liquid upward in order to discharge the gas out of the system. This case has problems in that the catalyst physically abrades, and that the abraded catalyst is liable to be scattered upward as fine powder.
Meanwhile, fibrous activated carbon has been recently developed. The fibrous activated carbon is molded into a sheet and then rolled spirally for use as a cartridge-type catalyst module (JP 07-144189 A)
The case of using a catalyst layer prepared by forming activated carbon into a sheet and spirally rolling the sheet form of the activated carbon can suppress the generation of fine power, but has problems of a large passage resistance to the waste liquid and difficulties in high-speed treatment. In a catalyst layer containing entangled fibrous activated carbon, the waste liquid oftentimes is hardly brought into uniform contact with the catalyst layer for a reaction, and the catalyst layer is liable to degrade at the part of the waste liquid inlet. Further, fine powder in the waste liquid is liable to clog the waste liquid inlet. In a case where a reaction proceeds at a part of the catalyst layer and a gas is generated through a reaction in the catalyst layer, the gas is not discharged smoothly. As a result, efficient waste liquid treatment cannot be assured.
Therefore, the present invention provides: a catalyst module employing fibrous activated carbon allowing for efficient waste liquid treatment; and a waste liquid treatment apparatus provided with the catalyst module.
The inventors of the present invention have conducted studies on a configuration of a catalyst module able to realize efficient waste liquid treatment. The inventors of the present invention have found that a catalyst module having a configuration in which a plurality of waste liquid inlet passages are arranged in a form of a bundle, or in which partition walls of waste liquid inlet passages are formed of layers of fibrous activated carbon, enables the formation of a uniform catalytic reaction field in the catalyst module and allows for efficient waste liquid treatment. Thus, the inventors have completed the present invention constructed as described below.
(1) A catalyst module having a waste liquid inlet passage for the inflow of a waste liquid, whose partition walls are formed of fibrous activated carbon, in which: the fibrous activated carbon is impregnated with or contains a catalyst; and the waste liquid in the waste liquid inlet passage passes through the partition walls and is discharged out of the waste liquid inlet passage.
(2) A catalyst module according to the above item (1), in which a plurality of the waste liquid inlet passages are arranged in the form of a bundle.
(3) A catalyst module according to the above item (2), in which the plurality of waste liquid inlet passages are each formed between a first partition wall formed to have a wavy section and a second partition wall arranged to follow one side of the first partition wall.
(4) A catalyst module according to the above item (3), in which the first partition wall and the second partition wall are arranged concentrically or spirally.
(5) A catalyst module according to any one of the above items (1) to (4), in which the fibrous activated carbon is impregnated with or contains silver as a catalyst.
(6) A catalyst module according to any one of the above items (2) to (4), including a surface layer surrounding an outer periphery of the plurality of waste liquid inlet passages arranged in the form of a bundle, in which the surface layer is formed of a material inhibiting the passage of a liquid.
(7) A catalyst module according to the above item (6), in which the surface layer is formed of a material inhibiting the passage of a liquid but allowing the passage of a gas alone.
(8) A catalyst module according to the above item (1), in which the partition wall is formed of a fibrous activated carbon layer prepared by laminating a plurality of layers of fibrous activated carbon in a form of a sheet.
(9) A catalyst module according to the above item (8), in which the partition wall has a projecting part projecting into the waste liquid inlet passage.
(10) A catalyst module according to the above item (8), in which the fibrous activated carbon in a form of a sheet is formed into a bag having an open lower end.
(11) A catalyst module according to the above item (8), in which a mesh member is arranged between the layers of fibrous activated carbon in the form of a sheet.
(12) A catalyst module according to the above item (8), in which: an inlet port of the waste liquid is provided at a lower end of the waste liquid inlet passage; and an end of the waste liquid inlet passage opposite to the inlet port is closed so as to inhibit the passage of a liquid.
(13) A catalyst module according to any one of the above items (8) to (12), in which the fibrous activated carbon is impregnated with or contains silver as a catalyst.
(14) A waste liquid treatment apparatus including a waste liquid treatment tank capable of holding one or a plurality of the catalyst modules according to any one of the above items (1) to (4), in which: the waste liquid storage tank temporarily stores a treated liquid discharged from the catalyst module; and the stored treated liquid is discharged out of the waste liquid treatment tank at a predetermined liquid level.
(15) A waste liquid treatment apparatus including a waste liquid treatment tank capable of holding one or a plurality of the catalyst modules according to the above item (5), in which: the waste liquid storage tank temporarily stores a treated liquid discharged from the catalyst module; and the stored treated liquid is discharged out of the waste liquid treatment tank at a predetermined liquid level.
(16) A waste liquid treatment apparatus including a waste liquid treatment tank capable of holding one or a plurality of the catalyst modules according to any one of the above items (8) to (12), in which: the waste liquid storage tank temporarily stores a treated liquid discharged from the catalyst module; and the stored treated liquid is discharged out of the waste liquid treatment tank at a predetermined liquid level.
(17) A waste liquid treatment apparatus including a waste liquid treatment tank capable of holding one or a plurality of catalyst modules according to the above item (13), in which: the waste liquid storage tank temporarily stores a treated liquid discharged from the catalyst module; and the stored treated liquid is discharged out of the waste liquid treatment tank at a predetermined liquid level.
(18) A waste liquid treatment apparatus according to the above item (15), in which a plurality of the catalyst modules are held in the waste liquid treatment tank in parallel with the inflow direction of the waste liquid.
Hereinafter, the best mode for carrying out the present invention will be described in detail by referring to the figures.
(Catalyst Module)
Further, the surface layer 44 maybe formed of a material having selective permeability, inhibiting the passage of a liquid but allowing the passage of a gas. The surface layer 44, formed of a material having selective permeability, allows a gas generated through a decomposition reaction or the like in the catalyst module 40 to separate from the waste liquid, and also allows a rapid discharge of the gas out of the system.
The surface layer 44 may be formed of a known material having a selective permeability or a selective barrier property. For example, the surface layer 44, inhibiting the passage of a liquid and a gas, maybe formed through a general resin coating. The surface layer 44, inhibiting the passage of a liquid but allowing the passage of a gas, may be formed through a coating or covering with a commercially available material having a selective permeability.
The waste liquid inlet passage 52 for inflow of the waste liquid may be formed at a height lower than the upper end of the catalyst module 50, but the waste liquid inlet passage 52 is preferably formed at the height of the catalyst module 50. A cylindrical member allowing the passage of a liquid may be provided as a core member inside of the waste liquid inlet passage 52. The core member may also serve as a structure-bearing member for the catalyst module 50. The core member may be formed of a cylindrical member having a wall portion in the form of mesh, or a cylindrical member having a porous wall portion of resin, ceramics, or metal, for example.
As shown in the catalyst module 50 of
The catalyst module 50, which is formed into a cylindrical shape, may have a projecting part projecting from an inner wall portion of the partition wall 54 into the waste liquid inlet passage 52. In a case where such a projecting part is formed, the passage of a waste liquid out of the catalyst module 50 is accelerated through the projecting part.
FIGS. 9 to 11 are each a perspective view showing an example of a catalyst module provided with a projecting part in a partition wall.
As shown in
As shown in
As shown in
Note that, the projecting parts 63, 67, and 71, are also formed so as to allow the passage of a waste liquid, similar to the other members. That is, the projecting parts 63, 67, and 71, are formed of fibrous activated carbon.
FIGS. 12 to 14 are each an explanatory drawing of a method of producing the catalyst module 60, 64, or 68, shown in each of FIGS. 9 to 11.
As shown in
As shown in
In this embodiment, examples of fibrous activated carbon for forming a partition wall of a catalyst module include: fibrous activated carbon in a form of a sheet prepared by mixing fibrous activated carbon with another binder fiber, such as a polyethylene fiber or a polypropylene fiber, and forming the mixture into a sheet through a paper making method; and fibrous activated carbon in a form of a sheet prepared by mixing fibrous activated carbon containing a catalyst for waste liquid treatment, such as silver, through the incorporation or the like with a polyester composite fiber of a core-in-sheath structure, and forming the mixture into a sheet through a dry process.
For formation of cylindrical fibrous activated carbon, fibrous activated carbon is dispersed in water by using several % of an organic polymer as a binder, such as polyethyleneimine, polyacrylic acid, polyacrylamide, a polyethylene fiber, or a polypropylene fiber, to thereby prepare a slurry. Then, the slurry is filtered under reduced pressure by using a cylindrical filter having a nonwoven fabric set to thereby form cylindrical fibrous activated carbon.
Pitch-based fibrous activated carbon, acrylic fibrous activated carbon, phenol-based fibrous activated carbon, cellulose-based fibrous activated carbon, or the like may be used as fibrous activated carbon for forming a catalyst module. However, a pitch-based fibrous activated carbon having an excellent oxidation resistance is preferable.
Examples of a catalyst added to or contained in a fibrous activated carbon include metals such as iron, cobalt, nickel, manganese, and silver. Of those, silver is particularly preferably used. Further examples of the catalyst may include compounds such as oxides or hydroxides of the metals. The amount of the metal used as a catalyst is preferably 0.01 to 5 wt % with respect to the amount of the fibrous activated carbon. If the metal content is less than 0.01 wt %, decomposition by the fibrous activated carbon itself is dominant over decomposition by the metal, and the fibrous activated carbon tends to be greatly consumed. If the metal content exceeds 5 wt %, the fibrous activated carbon hardly contains the metal as fine particles and the decomposition efficiency of hydrogen peroxide decreases on the contrary. Further, a metal content exceeding 5 wt % is expensive, especially for cobalt, nickel, silver, or the like.
Metals used as a catalyst may be contained in the fibrous activated carbon through any method. Silver may be contained in fibrous activated carbon, for example, through a method involving: immersion of fibrous activated carbon in an aqueous solution of silver nitrate; removal of the fibrous activated carbon from the solution; dehydration thereof; and heating thereof for the decomposition of silver nitrate. Further, silver may be contained in fibrous activated carbon through a method involving a silver mirror reaction or incorporation. Manganese, as a catalyst, may be contained in fibrous activated carbon through a method involving: blowing of ozone into an aqueous solution of manganese chloride for oxidation; and adsorption of produced manganese oxides and manganese ions on the fibrous activated carbon. Further, manganese may be contained as a catalyst in fibrous activated carbon through a method involving the mixing of fine particles of electrolytic manganese dioxide with a sheet of fibrous activated carbon.
Use of the catalyst module as described above can realize a waste liquid treatment appratus allowing for the formation of a uniform catalytic reaction field and an efficient waste liquid treatment.
(Waste Liquid Treatment Apparatus)
Hereinafter, specific structural examples of a waste liquid treatment apparatus employing the catalyst module will be described below by referring to figures.
The waste liquid treatment tank 104 is constructed for temporarily storing treated liquid discharged from the catalyst module 102, and for discharging the stored treated liquid from the discharge port 108 at a predetermined liquid level. In the waste liquid treatment apparatus 100, in the case where a surface layer 110 is provided on an outer periphery of the catalyst module 102, the treated waste liquid is discharged into the waste liquid treatment tank 104 from an upper surface of the catalyst module 102 alone. In contrast, in a case where no surface layer 110 is provided on an outer periphery of the catalyst module 102, the treated waste liquid is discharged into the waste liquid treatment tank 104 from the outer periphery of the catalyst module 102.
In the case where the catalyst module 102 is provided with the surface layer 110, a catalytic reaction in the catalyst module 102 maybe accelerated. In contrast, in the case where the catalyst module 102 is provided with no surface layer 110, an outer surface of the catalytic module 102 is exposed to the waste liquid stored in the waste liquid treatment tank 104. Thus, the catalytic reaction proceeds between the waste liquid in the waste liquid treatment tank 104 and the outer surface of the catalyst module 102.
The waste liquid treatment apparatus 100 preferably has a size capable of including almost the entire height of the catalyst module 102. The liquid level for discharging the stored waste liquid (treated liquid) preferably is substantially at the same height as the height of the catalyst module 102 in the waste liquid treatment tank 104. For discharge of the stored waste liquid at a predetermined liquid level, a circular tub 112 capable of temporarily receiving a waste liquid discharged from an upper end of the waste liquid treatment tank 104 is preferably provided, and the discharge port 108 is preferably provided at a bottom of the tub 112.
The waste liquid treatment apparatus 100 described above may be used for a treatment process of a waste liquid containing hydrogen peroxide, for example. To be specific, the waste liquid treatment apparatus 100 may be used for a treatment process of the waste liquid from the washing of substrates in a semiconductor substrate manufacturing plant, or a treatment process of the waste liquid in a liquid crystal manufacturing plant.
The waste liquid treatment apparatus 100 may be provided with a temperature control means capable of controlling the temperature in the waste liquid treatment tank 104 at an appropriate temperature for a catalytic reaction. For example, heating means, cooling means, or the like, of a jacket-type may be provided on an outer periphery of the waste liquid treatment tank 104 for controlling the temperature of the waste liquid. The temperature of the waste liquid is preferably controlled to 15° C. or higher and 60° C. or lower. A temperature of the waste liquid of 15° C. or lower reduces the decomposition rate of hydrogen peroxide. A temperature of the waste liquid exceeding 60° C. requires various measures for heat resistance. The temperature of the waste liquid is more preferably controlled to 30° C. or higher and 50° C. or lower.
As shown in
The catalyst module 102 and the waste liquid treatment apparatus 100 as described above may be used for the treatment of the waste liquid discharged in a semiconductor substrate or liquid crystal manufacturing process, or for the treatment of the waste liquid discharged in a food manufacturing process or a food fabrication process, for example. Examples of the components in a waste liquid to be decomposed through a catalytic reaction include: hydrogen peroxide; a sulfuric acid/hydrogen peroxide solution (a mixed liquid of sulfuric acid and hydrogen peroxide solution); an ammonia/hydrogen peroxide solution (a mixed liquid of aqueous ammonia and hydrogen peroxide solution); and ozone. In a case where a waste liquid containing hydrogen peroxide is treated, silver is particularly preferably used as a catalyst supported on a catalyst module.
According to the present invention, fibrous activated carbon having a large specific surface area is used. A catalyst module and a treatment apparatus are each constructed to provide a state of efficient contact, thereby attaining high treatment efficiency. Further, the treatment capacity can be easily increased corresponding to increases in the supply rate of the waste liquid. As a result, the treatment capacity can be easily increased at high treatment efficiency. For example, a space velocity (SV) of 50 or more can be easily attained.
During the start up of an operation, no special preliminary processes are required as long as the pH and temperature can be appropriately controlled, and the waste liquid can be supplied at once to start the treatment process.
For example, according to the treatment method of the present invention, in a case where a waste liquid containing about 5,000 ppm of hydrogen peroxide is treated, a decomposition efficiency of 99% or more can be attained.
Number | Date | Country | Kind |
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2003-025216 | Jan 2003 | JP | national |
2003-025215 | Jan 2003 | JP | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/JP04/00874 | 1/29/2004 | WO | 8/5/2005 |