KR102548062B1 - apparatus for treating wastewater produced from manufacture process of oxydianiline and treating mothed using the same - Google Patents

Abstract

The present invention relates to a pretreatment device for removing total nitrogen from wastewater from an oxydianiline manufacturing process and a pretreatment method using the same, and more particularly, to a pretreatment method using TDF (tire derived fuel) combustion ash, which is waste from a thermal power plant, to obtain oxydianiline It relates to a pretreatment device and method capable of effectively reducing total nitrogen in wastewater generated during manufacturing.
The pretreatment apparatus for removing total nitrogen from oxidianiline manufacturing process wastewater using TDF combustion ash of the present invention includes a treatment tank capable of inflow and outflow of water to be treated, and an ash filter installed inside the treatment tank.

Description

Pretreatment device for total nitrogen removal from oxydianiline manufacturing process wastewater using TDF combustion ash and pretreatment method using the same {apparatus for treating wastewater produced from manufacture process of oxydianiline and treating mothed using the same}

The present invention relates to a pretreatment device for removing total nitrogen from wastewater from an oxydianiline manufacturing process and a pretreatment method using the same, and more particularly, to a pretreatment method using TDF (tire derived fuel) combustion ash, which is waste from a thermal power plant, to obtain oxydianiline It relates to a pretreatment device and method capable of effectively reducing total nitrogen in wastewater generated during manufacturing.

In the case of a large-scale PC boiler of a general coal-fired power plant _, the main component of combustion ash generated because of the sulfur component of coal used as fuel is equipped with a separate desulfurization facility and operated.

However, in the case of small and medium-sized combined heat and power plants, coal, waste tires, and limestone are mixed and combusted in a fluidized bed boiler that performs in-furnace desulfurization. TDF (tire derived fuel) combustion ash generated at this time has a relatively high CaO content compared to coal combustion ash because it undergoes an in-furnace desulfurization process. In addition, the TDF combustion material also has a characteristic that a large amount of carbon and oil, which are incomplete combustion products of tires, are present.

TDF combustion ash is classified as industrial waste, and it is partially used as a filling material for asphalt or asphalt, but most of it is discarded.

Meanwhile, the following oxydianiline (4,4'-oxydianiline) is a monomer that is a raw material of polyimide such as a ketone, and is usually obtained through a condensation reaction of paranitrochlorobenzene and paranitrophenol in the presence of a base catalyst.

Looking at the general manufacturing process of oxydianiline (ODA) with reference to Figure 1, paranitrochlorobenzene (PNCB) and paranitrochlorobenzene (p-Nitrochlorobenzene; PNCB) under a DMSO (dimethyl sulfoxide) solvent using a base catalyst (K ₂ CO ₃ ) After the condensation reaction of phenol (p-Nitrophenol; PNP), the intermediate DNDPE (Dinitrodiphenyl Ether) produced by the condensation is hydrogenated and then recrystallized to obtain the finally synthesized oxydianiline.

A large amount of wastewater is generated in the process of recovering the solvent (DMSO) by filtering after washing the DNDPE produced through the condensation reaction during the manufacturing process of oxydianiline. Wastewater generated in such an oxydianiline manufacturing process has a high total nitrogen content, making it unsuitable for inflow into a conventional water treatment facility. Therefore, a pretreatment device for lowering the total nitrogen content is required to meet the inflow standard of the water treatment facility.

1. Republic of Korea Patent Publication No. 10-2014-0145514: Filler composition for asphalt pavement using TDF incineration ash 2. Republic of Korea Patent No. 10-1487180: Room temperature circulation ascon using oleic acid, TDF incineration ash and waste carbon black 3. Republic of Korea Patent No. 10-2092614: Manufacturing method of 4,4'-oxydianiline using 1,4-diiodobenzene

The present invention was created to improve the above problems, and effectively reduces total nitrogen in wastewater generated during the production of oxydianiline by using TDF combustion material, which is a waste of thermal power plants that has little application other than ascon or asphalt filler. The purpose is to provide a preprocessing device and method that can

In order to achieve the above object, the pretreatment device for total nitrogen removal of oxydianiline manufacturing process wastewater using TDF combustion ash of the present invention includes a treatment tank capable of inflow and outflow of the treatment target water; An ash filter installed inside the treatment tank, wherein the ash filter is formed of TDF (tire derived fuel) combustion material, and the water to be treated is generated when oxydianiline (4,4'-oxydianiline) is produced is wastewater.

The TDF combustion ash is generated in a thermal power plant that burns a mixture of coal, limestone, and waste tire chips.

First and second fiber filters are disposed on both sides of the ash filter with the ash filter interposed therebetween and form a filling space in which the TDF combustion material is filled.

A third fiber filter installed to be spaced apart from the second fiber filter, and a ball filter formed between the second fiber filter and the third fiber filter and made of a plurality of quartz balls.

Total nitrogen in the water to be treated is reduced by passing the water to be treated through an ash filter formed of TDF (tire derived fuel) combustion ash, and the water to be treated is generated during the manufacture of oxydianiline (4,4'-oxydianiline) is wastewater.

As described above, the present invention can effectively reduce not only total nitrogen, but also total phosphorus and organic matter in wastewater generated during the production of oxydianiline by utilizing TDF (tire derived fuel) combustion ash, which is waste from a thermal power plant.

In addition, the present invention can provide a new field of application of the TDF combustion material by enabling the use of the TDF combustion material, which has been extremely limited in use other than ascon or asphalt filler, in the water treatment field.

In addition, since the present invention uses waste as a material, it has the advantage of facilitating the supply and demand of materials, reducing manufacturing costs, and protecting the environment through recycling of waste resources.

1 is a schematic diagram showing a general manufacturing process of oxydianiline;
2 is a cross-sectional view schematically showing a pretreatment device according to an example of the present invention;
3 is a cross-sectional view schematically showing a pretreatment device according to another example of the present invention;
Figure 4 is a photograph showing the state before and after the pre-treatment of the oxydianiline manufacturing process wastewater.

Hereinafter, a pretreatment device for total nitrogen removal from oxydianiline manufacturing process wastewater using TDF combustion ash according to a preferred embodiment of the present invention and a pretreatment method using the same will be described in detail.

In the pretreatment method according to an embodiment of the present invention, total nitrogen in the water to be treated is reduced by passing the water to be treated through an ash filter.

The ash filter is formed from TDF (tire derived fuel) combustion ash. TDF combustion ash is produced in thermal power plants that burn a mixture of coal, limestone and waste tire chips. For example, ash generated when a mixture of coal, limestone, and waste tire chips is burned in a fluidized bed boiler equipped with an in-furnace desulfurization facility is TDF combustion ash.

The TDF combustion material is in the form of a fine powder and may have a specific surface area of 4000 to 6000 cm 2 /g. The main component of TDF combustion ash is calcium oxide (CaO). Unlike fly ash or bottom ash, TDF combustion ash is characterized by a high content of calcium oxide. The calcium oxide content in the TDF combustion ash is about 30 to 60% by weight. In addition to this, TDF combustion ash is SiO ₂ , Al ₂ O ₃ , SO ₃ , Fe ₂ CO ₃ , MgO, ZnO, etc. are included.

In addition, the TDF combustion material also has a characteristic that oil, which is an incomplete combustion product of a tire, is present. This oil plays a role in imparting suitable performance to the TDF combustion ash as a filter for water treatment. When the water to be treated passes through the fine pores between the particles of the TDF combustion material in the form of powder, clogging can easily occur, but the clogging of the pores is suppressed by the oil contained in the TDF combustion material.

The ash filter may be formed by molding the TDF combustion material into a certain shape or by filling a space of a certain size.

As a method for passing the water to be treated through the ash filter, the water to be treated may be introduced into the treatment tank after the ash filter is installed inside the treatment tank through which the water to be treated is continuously introduced and discharged. Water to be treated introduced into the treatment tank passes through an ash filter and is discharged to the outside of the treatment tank.

As the target water to be treated in the present invention, wastewater from the oxydianiline manufacturing process can be used. As shown in FIG. 1, a condensation reaction of p-Nitrochlorobenzene (PNCB) and p-Nitrophenol (PNP) was performed in a DMSO (Dimethyl sulfoxide) solvent using a base catalyst (K ₂ CO ₃ ). The intermediate DNDPE (Dinitrodiphenyl Ether) produced by post-condensation is hydrogenated and then recrystallized to obtain finally synthesized oxydianiline.

A large amount of wastewater is generated in the process of recovering the solvent (DMSO) by filtering after washing the DNDPE produced through the condensation reaction during the manufacturing process of oxydianiline. Wastewater generated in such an oxydianiline manufacturing process, ie, oxydianiline manufacturing process wastewater, has a high total nitrogen content, making it unsuitable to be introduced into a conventional water treatment facility.

The present invention reduces total nitrogen (T-N) in oxydianiline manufacturing process wastewater by pre-treating oxydianiline manufacturing process wastewater so as to meet the influent standard that can be introduced into a conventional water treatment facility. In addition to total nitrogen, total phosphorus (TP) and total organic carbon (TOC) can also be reduced.

The present invention has been described as treating wastewater from the oxydianiline manufacturing process as an example, but in addition to this, it can be utilized for treating various factory wastewater, domestic sewage, sewage, and the like.

Hereinafter, a preprocessing device according to an example of the present invention will be described.

Referring to FIG. 2 , the pretreatment device of the present invention includes a treatment tank 10 capable of inflow and outflow of water to be treated, and an ash filter 20 installed inside the treatment tank 10 .

The treatment tank 10 has a tubular structure with an empty interior. Of course, the treatment tank 10 may be formed in various shapes and sizes, such as a cylindrical shape and a square cylinder shape. The upper and lower portions of the treatment tank 10 may be open or closed. The water to be treated flows into one side of the treatment tank 10, and the water to be treated flows out to the other side of the treatment tank.

The water to be treated may be operated in a continuous flow method in which the water to be treated is continuously flowed into the treatment tank 10 while continuously flowing out. Unlike this, it may be operated in a batch type in which a certain amount of the target water to be treated flows into the treatment tank 10 and then flows out after a certain amount of time.

The ash filter 20 is installed inside the treatment tank 10. The ash filter 20 is formed of the TDF combustion material 25 as described above.

The ash filter 20 may be formed by molding TDF combustion material into a certain shape or by filling a space of a certain size. For example, an ash filter can be made by molding a powdered TDF combustion material into a plate shape. In addition, an ash filter may be formed by creating a filling space of a certain size inside the treatment tank and then filling the filling space with TDF combustion material.

In the illustrated example, the ash filter 20 is formed by creating a filling space of a certain size inside the treatment tank 10 and then filling the TDF combustion material 25 into the filling space. To this end, first and second fiber filters 31 and 33 are installed on both sides of the ash filter 20 inside the treatment tank 10 . The first and second fiber filters 31 and 33 are disposed on both sides of the ash filter 20 so as to sandwich the ash filter 20 therebetween. The space between the first fiber filter 31 and the second fiber filter 33 is a filling space in which the TDF combustion material 25 is filled.

The first fiber filter 31 is disposed above the ash filter 20, and the second fiber filter 33 is disposed below the ash filter 20. The ash filter 20 is formed by filling the TDF combustion ash 25 between the first fiber filter 31 and the second fiber filter 33.

The first and second fiber filters 31 and 33 are plate-shaped filters made of fibrous tissue. The first and second fiber filters 31 and 33 may be made of fibers of various materials. For example, the first and second fiber filters 31 and 33 may be made of quartz wool. Quartz fiber has excellent chemical resistance and durability.

The first and second fiber filters 31 and 33 serve to form a filling space for filling the TDF combustion material 25 and at the same time play a filtering role to filter out fine solids in the water to be treated.

When the water to be treated is introduced into the upper part of the treatment tank 10, the water to be treated sequentially passes through the first fiber filter 31, the ash filter 20, and the second fiber filter 33 to form the treatment tank 10. It leaks out through the lower part. When the water to be treated passes through the ash filter 20, nitrogen, phosphorus, organic matter, etc. in the water to be treated are adsorbed to the TDF combustion ash 25 and removed.

Meanwhile, in the present invention, as shown in FIG. 3 , a third fiber filter 35 and a ball filter 37 may be further installed inside the treatment tank 10 .

Referring to FIG. 3 , the third fiber filter 35 is installed below the second fiber filter 33 . The third fiber filter (35) is installed at a predetermined distance from the second fiber filter (33). A ball filter 37 is installed between the second fiber filter 33 and the third fiber filter 35.

The ball filter 37 is composed of a plurality of quartz balls 39. The quartz balls 39 fill the space between the second fiber filter 33 and the third fiber filter 35 to form a ball filter 37. As the quartz ball 39, ordinary quartz sand may be used. The ball filter made of quartz balls serves to prevent channeling of the fluid along with filtration.

The present invention can further improve the water treatment effect by further comprising a third fiber filter and a ball filter.

Hereinafter, the present invention will be described through an experimental example. However, the following experimental examples are intended to specifically explain the present invention, and the scope of the present invention is not limited to the following experimental examples.

(experimental example)

The TDF combustion ash generated from the Kumho Combined Thermal Power Plant was used, and the wastewater from the oxydianiline manufacturing process was used from Huchems Co., Ltd.

After placing two quartz fiber filters with a thickness of 10 mm at 50 mm intervals inside a treatment tank made of a transparent acrylic tube with a length of 300 mm and a diameter of 30 mm, a TDF combustion material was filled between the quartz fiber filters to form an ash filter with a thickness of 50 mm. Then, the oxidianiline manufacturing process wastewater was introduced into the upper part of the treatment tank and discharged into the lower part of the treatment tank for 15 minutes in a continuous circulation method. The total volume of wastewater was 1,000 ml and the flow rate was 100 ml/min.

The experiment was repeated three times. Suspended solids (SS), total nitrogen (T-N), total phosphorus (TP), and total organic carbon (TOC) of wastewater before and after treatment were measured and shown in Table 1 below. The unit of measurement is ppm.

Sample SS T-N T-P TOC NO.1 before processing 30 120 0.70 1,578 after processing 12 33 0.33 684 NO.2 before processing 32 128 0.72 1,632 after processing 15 36 0.38 712 NO.3 before processing 28 117 0.68 1,550 after processing 11 30 0.31 661

Referring to the results in Table 1, it was found that the suspended solids (SS), total nitrogen (T-N), total phosphorus (TP), and total organic carbon (TOC) of the wastewater were reduced after treatment. In particular, it was confirmed that total nitrogen was greatly reduced to about 71-74%.

Therefore, it was found that the present invention can remove suspended solids, total nitrogen, total phosphorus, total organic carbon, etc. in wastewater from the oxydianiline manufacturing process using TDF combustion ash. In particular, it was confirmed that the total nitrogen removal effect in the wastewater of the oxydianiline manufacturing process of the present invention was very good.

Figure 4 shows the appearance of wastewater before and after treatment. The wastewater before treatment had a pale yellow color, but the wastewater after treatment had a clear and transparent color. Through this, it was confirmed with the naked eye that the wastewater was effectively treated.

In the above, the present invention has been described with reference to one embodiment, but this is only exemplary, and those skilled in the art will understand that various modifications and equivalent embodiments are possible therefrom. Therefore, the true protection scope of the present invention should be defined only by the appended claims.

10: treatment tank 20: ash filter
25: TDF combustion ash 31: first fiber filter
33: 2nd fiber filter 35: 3rd fiber filter
37: ball filter 39: quartz ball

Claims (5)

delete delete delete A treatment tank having a tubular structure in which the water to be treated can flow in and out;
An ash filter installed inside the treatment tank;
The ash filter is formed of TDF (tire derived fuel) combustion material,
Disposed on both sides of the ash filter with the ash filter interposed therebetween, forming a filling space in which the TDF combustion material is filled, and installing plate-shaped first and second fiber filters made of fibrous tissue and spaced apart from the second fiber filter A third fiber filter and a ball filter formed between the second fiber filter and the third fiber filter and made of a plurality of quartz balls,
The water to be treated is wastewater generated during the manufacture of oxydianiline (4,4'-oxydianiline),
The wastewater is generated through the condensation reaction of p-Nitrochlorobenzene and p-Nitrophenol (PNP) in the presence of a dimethyl sulfoxide solvent using a base catalyst (K ₂ CO ₃ ). Wastewater generated when dinitrodiphenyl ether is washed with water and then filtered to recover the solvent;
The TDF combustion ash is generated in a thermal power plant that burns a mixture of coal, limestone and waste tire chips in a fluidized bed boiler that desulfurizes in the furnace, and has a calcium oxide (CaO) content of 30 to 60% by weight. A pretreatment device for total nitrogen removal from oxidianiline manufacturing process wastewater using materials. delete

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