KR102031920B1 - Manufacturing apparatus for pHospHoric acid granules recycling waste ammonium pHospHate and its manufacturing method - Google Patents

Abstract

The present invention relates to an apparatus and a method for preparing granules of first ammonium phosphate for recycling ammonium phosphate waste liquid discharged from a semiconductor etching process, which are eco-friendly. The apparatus of the present invention comprises: a plurality of waste liquid collectors; a storage tank; a pH adjusting unit; a buffer; a hot air granulator; a filter dust collector; an oxidation catalyst combustor; and an air cooling heat exchanger.

Description

Manufacturing apparatus for pHospHoric acid granules recycling waste ammonium pHospHate and its manufacturing method}

The present invention relates to a first ammonium phosphate granule manufacturing apparatus, in particular, after collecting the ammonium phosphate waste liquid to adjust the pH, the first ammonium phosphate granules crystallized in a solid state through hot air granules and bag filter,

The ammonia gas and acetic acid gas discharged in this process are decomposed by the high temperature and catalyst layer in the catalytic combustion furnace, and recycled the ammonium phosphate waste liquid which discharges the gas components to the discharger while reusing the waste heat through a heat exchanger or an economizer. It relates to a first ammonium phosphate granule production apparatus.

Liquid wastes are inevitably generated and discharged according to industrial activities such as manufacturing, processing and washing various products. Among them, acidic or basic liquid wastes (waste liquids) continue to be produced with the development of the domestic electronics industry. Is increasing.

Acidic or basic wastes generated in the electronics industry are generated in the process of washing various parts, semiconductor and LCD etching process, and contain a large amount of various harmful substances. So, if these acidic or basic wastes are discharged as it is, soil pollution, water quality In addition to the problem of environmental pollution such as pollution, odor generation, and accompanied by economic loss due to the waste of recoverable resources, the development of treatment and recycling technology for solving this is important.

In particular, the ammonium phosphate waste solution is used to make a gate as a control electrode on a wafer, which is a semiconductor manufacturing tube, using an acid mixed with various acids such as organic acid such as hydrofluoric acid, phosphoric acid, acetic acid, and nitric acid used in a semiconductor etching (etching) process. It is used as an etching solution for scrapping silicon oxide parts in the process.

The mixed acid solution mixed with phosphoric acid, nitric acid, and acetic acid is an important chemical in the semiconductor industry. Recently, the amount of etching solution is increasing as the production of semiconductor increases. Waste fluids are also produced in large quantities, but there is no known technique for recycling.

The technology of recycling the waste liquid reacted after cleaning the gas discharged from the etching (etching) process of the semiconductor in a wet cleaning facility can solve the environmental pollution problem caused by the waste liquid and has the advantage of recycling resources.

Ammonium monophosphate is used as a raw material for powdered extinguishing agents and organic phosphate fertilizers.

In the prior art, a method of preparing a first ammonium phosphate compound having a purity of 98% or more from an etching process waste solution (Korean Patent No. 10-0436173), and a method of treating a phosphoric acid-based mixed waste solution to obtain a powder of ammonium dihydrogen phosphate (Japanese Patent Laid-Open No. 2016- 16375) and the like are disclosed in the prior art, but the prior arts have a problem of low economic feasibility because they use a large amount of expensive pure ammonia.

In the proposed Patent Registration No. 1935820, a method of preparing ammonium dihydrogen phosphate of high purity is known, in which a pH is adjusted by adding a phosphate solution to an ammonium phosphate waste solution, followed by concentration under reduced pressure and cooling.

However, in the above prior art, there is a problem in that enormous equipment costs are required for the process of concentration under reduced pressure and cooling.

The present invention is to solve the above problems, and after collecting the ammonium phosphate waste liquid by a dedicated vehicle to adjust the pH, the first ammonium phosphate granules crystallized in a solid state through hot air granules and bag filter, and hot air The ammonia gas and acetic acid gas decomposed and discharged from the granulator are decomposed in the catalytic oxidation furnace, and the ammonium phosphate waste solution discharged from the semiconductor etching (etching) process, which is discharged to the discharger by recycling waste heat through a heat exchanger or an economizer, is used. It is an object to provide a first ammonium phosphate granule manufacturing apparatus for recycling.

In addition, the ammonium phosphate waste solution discharged from the semiconductor etching process through a simple step-by-step process of the pre-treatment step (S10), the aging step (S20), the first ammonium phosphate granules production step (S30), and the gas discharge step (S40). Another object is to provide a manufacturing method of recycling the first ammonium phosphate granules.

A plurality of waste liquid collectors for collecting ammonium phosphate waste liquids obtained in a plurality of semiconductor etching processes by a dedicated transport vehicle; A storage tank for storing the ammonium phosphate waste liquid collected through the plurality of waste liquid collectors; A pH adjusting unit for inputting an adjustment component made of a predetermined amount of an alkaline substance or an acidic substance to adjust the pH of the storage tank; A buffer for dividing and storing the mixed liquid in which the adjustment component is added to the ammonium phosphate waste liquid in the storage tank and waiting for a predetermined time; A hot air granulator for hot drying by hot air supplied from a heat exchanger while spraying the mixed liquid supplied from the buffer into ultra-fine particles through an atomizer nozzle; A bag filter for obtaining fine ammonium phosphate granules remaining in the gas discharged from the hot air granulator through a filter; A catalytic oxidation burner which directly burns and catalytically decomposes ammonia gas and acetic acid gas decomposed by hot hot air in the hot air granulator and transfers the gas from which the odor is removed to a heat exchanger; The technical features of the present invention include an air-cooled heat exchanger by intake of outside air which transfers the heat of the gas generated by the catalytic oxidation burner 80 to the hot air granules and recycles it, and transfers the cooled residual gas to the discharger.

In addition, the first method for producing ammonium phosphate granules for recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process according to the present invention collects the ammonium phosphate waste liquid through a waste liquid collector and stores it in a storage tank to adjust the pH of the ammonium phosphate waste liquid. A pretreatment step (S10) of adjusting the pH to 6 to 7 by dropping a control component containing a predetermined amount of an alkaline substance or an acidic substance through a pH adjusting unit; A maturation step (S20) of dividing and storing the mixed solution in which the adjustment component is added to the ammonium phosphate waste liquid and waiting for a predetermined time; The matured mixed liquor was dried at high temperature through a hot air granulator to extract the crystallized ammonium phosphate granules, and the ammonia gas and the acetic acid gas were reextracted the first ammonium phosphate granules which were not extracted from the hot air granulator through a filter in a filter bag. First ammonium phosphate granules producing step (S30) and the discharge; Ammonia gas and acetic acid gas discharged from the bag filter 70 are directly discharged and catalytically decomposed to a high temperature in a catalytic oxidizer to remove odor components and clean gas discharged to the outside through the discharger 100. It is a technical feature that step S40 proceeds sequentially.

The first ammonium phosphate granules manufacturing apparatus for recycling the ammonium phosphate waste liquid according to the present invention collects the ammonium phosphate waste liquid and adjusts its pH, and then simply extracts the first ammonium phosphate granules crystallized in a solid state through hot air granules and a bag filter. Therefore, the extraction rate of the first ammonium phosphate granules can be greatly improved through the two-step extraction process, and the residual gas component is directly burned and catalytically decomposed at a high temperature through a catalytic oxidizer to produce ammonia gas, which is an odor component, and Since acetic acid is removed and then discharged to the discharger, there is an eco-friendly effect and waste heat recycling through a heat exchanger.

1 is a block diagram of a first ammonium phosphate granule manufacturing apparatus for recycling ammonium phosphate waste liquid discharged from a semiconductor etching process according to the present invention;
2 is an embodiment of the present invention, the configuration of the waste liquid collector and the storage tank,
3 is a block diagram of a buffer according to an embodiment of the present invention;
4 is a configuration diagram schematically showing a hot air granulator and bag filter for extracting human granules, a catalytic oxidation burner and a heat exchanger for burning and catalytic decomposition of ammonia gas and acetic acid gas, as an embodiment of the present invention;
Figure 5 is a process step schematically showing a first ammonium phosphate granules manufacturing method for recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process according to the present invention.

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

The first ammonium phosphate granule manufacturing apparatus for recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process according to the present invention, as shown in Figure 1, the waste liquid collector for the process of collecting the ammonium phosphate waste liquid through a predetermined treatment process 10, a storage tank 20, a pH adjusting unit 30 and a buffer 40, and hot air granulator 50 to extract solid ammonium phosphate granules crystallized by hot air drying and a gas filter. A first ammonium phosphate granular collector (60) and a bag filter (70) are provided, and the heat exchanger (90) and the discharger (100) for recycling the catalytic oxidation furnace (80) and waste heat to discharge clean gas (clean gas). A plurality of installations, including a is connected.

First, in the waste liquid collector 10, the ammonium phosphate waste liquid obtained in the semiconductor etching process is collected by a dedicated transport vehicle, as shown by the process of 'I' of FIG. 2, and the plurality of waste liquid collectors 10 are collected. The ammonium phosphate waste liquid collected through is stored in the storage tank 20.

In order to adjust the pH of the storage tank 20, the pH adjusting unit 30 is introduced into the storage tank 20 of the adjustment component consisting of a predetermined amount of an alkaline substance or an acidic substance.

In one embodiment of the present invention, the pH adjuster 30 adjusts the pH of the mixed liquid with the ammonium phosphate waste liquid to 6-7 using caustic soda as the alkaline substance and sulfuric acid as the acidic substance.

In addition, the mixed liquid in which the adjustment component is added to the ammonium phosphate waste liquid in the storage tank 20 is transferred to a plurality of buffers 40, divided and stored as shown in the process of 'II' of FIG. It is aged.

This allows the mixed solution to cause sufficient chemical reaction, so that the solid crystallization more efficiently during hot air drying described later, and preferably aged for about 4 hours.

The mixed liquid supplied from the buffer 40 is supplied from the heat exchanger 90 while spraying the ultrafine particles through the atomizer nozzle in the hot air granulator 50 as shown in the process of 'III' of FIG. 4. It is dried by high temperature hot air of 300-350 ° C. to crystallize into granular powder, and the solid crystallized first ammonium phosphate granules are extracted by the first ammonium phosphate granular collector 60 provided below.

At this time, since the fine ammonium phosphate powder remains in the gas generated during the hot air drying (granulation) process, it is transmitted to the bag filter 70 again.

In the bag filter 70, the first ammonium phosphate granules, which are solid components, are extracted through a filter into the first ammonium phosphate granulator collector 60 provided below, and the catalyst is completely catalytically oxidized. Transfer to the combustor (80).

The catalytic oxidation burner (80) removes the odor component while catalytic oxidative decomposition of the ammonia gas and the acetic acid gas generated in the hot air granulator (50) at a high temperature of 450 ℃ or more, and the clean gas from which the odor component is removed is a heat exchanger. Is transferred to 90.
The ammonia (NH ₃ ) gas and acetic acid (CH ₃ COOH) gas refers to a gas which is discharged in the form of gas by hot air after the ammonia component and the acetic acid component contained in the waste liquid are injected into the superfine particle state. Since ammonia gas and acetic acid gas are the main causes of odor pollution around the equipment, the present invention is proposed to remove clean air from the catalytic oxidizer 80 to discharge clean air to the atmosphere.

The heat exchanger 90 cools the gas at high temperature by air cooling, and heats the ambient air at room temperature to about 300 to 350 ° C. with the waste heat of the gas to recycle the waste heat to the hot air granulator 50. In addition, the cooled clean gas is discharged to the outside through the ejector 100 having the stack.

The chimney is an accessory device for the purpose of diffusion and dilution of ventilation flue gas and exhaust gas by a combustion facility. In the present invention, a blower and a silencer are provided to effectively discharge clean gas without noise.

In another embodiment of the present invention, an economizer 91 may be separately added to the rear end of the heat exchanger 90.

The economizer 91 is a device for preheating the water supply using the heat of the flue gas that occupies the most part of the heat loss of the boiler, it can be provided to the facility using hot water.

On the other hand, the granule manufacturing method of the first ammonium phosphate granule manufacturing apparatus for recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process according to the present invention is carried out by a step-by-step process as shown in FIG.

First, the ammonium phosphate waste liquid is collected through the waste liquid collector 10 and stored in the storage tank 20, and a predetermined amount of alkaline or acidic substance is included through the pH adjusting unit 30 to adjust the pH of the ammonium phosphate waste liquid. The pretreatment step (S10) of adjusting the pH to 6-7 is carried out by dropping the adjusting component.

At this time, the pH adjuster 30 adjusts the pH of the ammonium phosphate waste liquid by using caustic soda. When the alkalinity is excessive, sulfuric acid is used again to finally adjust the pH of the mixed liquid with the ammonium phosphate waste liquid to 6-7. Will be adjusted.

Subsequently, a ripening step (S20) of dividing and storing the mixed solution in which the adjustment component is added to the ammonium phosphate waste liquid and waiting for a predetermined time is performed.

In addition, the matured mixed solution is dried at a high temperature through the hot air granulator 50 to extract the first crystallized ammonium phosphate granules, and then, the primary gas is transferred to the bag filter 70, and the first ammonium phosphate granules are again passed through the filter. While extracting the first ammonium phosphate granules generating step (S30) to discharge the secondary gas is in progress.

Finally, the ammonia gas and the acetic acid gas discharged from the bag filter 70 is heated to a high temperature in the catalytic combustion furnace 80 and oxidatively decomposed by a catalyst to remove odors, and the high-temperature gas from which the odors are removed is heat-exchanged. The gas discharge step (S40) of discharging clean gas to the outside through the discharger 100 while recycling waste heat through the gas 90 is performed.

At this time, a high temperature and a catalytic reaction of 450 ° C. or higher is performed in the catalytic oxidation combustor 80, and a high temperature gas is cooled to about 300 ° C. or lower in the heat exchanger 90, and then transferred to the discharger 100.

.

The heat exchanger (90) is configured by air cooling by intake of outside air to cool the gas and at the same time increase the temperature of air at 350 ° C or higher by heat exchange to recycle waste heat, and transfer it to the hot air granulator (50). It will be recycled to the heat temperature of the granulator 50.

10: waste liquid collector 20: storage tank
30: pH adjuster 40: buffer
50: hot air granulator 60: monoammonium phosphate granular collector
70: bag filter 80: catalytic oxidation burner
90 heat exchanger 91 economizer
100: ejector

Claims (8)

A plurality of waste liquid collectors 10 for collecting ammonium phosphate waste liquids obtained in a plurality of semiconductor etching processes by a dedicated transport vehicle;
A storage tank 20 for storing the ammonium phosphate waste liquid collected through the plurality of waste liquid collectors 10;
A pH adjusting unit 30 for inputting an adjustment component made of a predetermined amount of an alkaline substance or an acidic substance to adjust the pH of the storage tank 20;
A buffer (40) for storing a portion of the storage tank (20) by dividing and storing the mixed liquid in which the adjustment component is added to the wastewater of ammonium phosphate;
A hot air granulator (50) for drying at high temperature by hot air supplied from a heat exchanger (90) while spraying the mixed liquid supplied from the buffer (40) into an ultrafine particle through an atomizer nozzle;
A bag filter (70) for obtaining fine first ammonium phosphate granules remaining in the gas discharged from the hot air granulator (50) through a filter;
A catalytic oxidizer (80) for directly burning and catalytically decomposing ammonia gas and acetic acid gas decomposed by hot air granules in the hot air granulator (50) and transferring the gas from which odor is removed to a heat exchanger (90);
An air-cooled heat exchanger (90) by suctioning outside air to transfer heat of the gas generated by the catalytic oxidation burner (80) to the hot air granulator (50) for recycling, and to transfer the cooled residual gas to the discharger (100);
The first ammonium phosphate granules manufacturing apparatus for recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process comprising a.
The method of claim 1,
In the pH adjusting unit 30, caustic soda is used as an alkaline substance and sulfuric acid is used as an acidic substance.
A first ammonium phosphate granule manufacturing apparatus for recycling ammonium phosphate waste liquid discharged from a semiconductor etching process, characterized in that the mixed liquid pH with the ammonium phosphate waste liquid is adjusted to 6-7.
The method of claim 1,
Ammonium phosphate discharged from the semiconductor etching process, characterized in that the first ammonium phosphate granular collector 60 for collecting solid crystallized first ammonium phosphate granules is installed below the hot air granulator 50 and the bag filter 70. A first ammonium phosphate granule production apparatus for recycling waste liquid.
The method of claim 1,
The hot air granulator 50 is dried at a high temperature of 300 ~ 350 ℃ to extract the crystallized ammonium phosphate granules to produce ammonia gas and acetic acid gas,
The catalytic oxidation burner (80) is a first to recycle the ammonium phosphate waste liquid, characterized in that the ammonia gas and the acetic acid gas passing through the bag filter 70 to directly burn and catalytic decomposition again to a high temperature of 450 ℃ or more to remove the odor Ammonium phosphate granule production apparatus.
The method of claim 1,
The first stage of recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process, characterized in that the economizer (91) is added to the rear end of the heat exchanger (90) to generate hot water by waste heat. Ammonium phosphate granule production apparatus.
The ammonium phosphate waste liquid is collected through the waste liquid collector 10 and stored in the storage tank 20, and an adjustment including a predetermined amount of alkaline or acidic substance through the pH adjusting unit 30 to adjust the pH of the ammonium phosphate waste liquid. A pretreatment step (S10) of dropping the components to adjust the pH to 6-7;
A ripening step (S20) of dividing and storing the mixed liquid into which the adjustment component is added to the ammonium phosphate waste liquid and waiting for a predetermined time;
The matured mixed solution was dried at high temperature through the hot air granulator 50 to extract the crystallized ammonium phosphate granules, and the first ammonium phosphate that was not extracted from the hot air granulator 50 through the filter in the bag filter 70. Generating a first ammonium phosphate granule (S30) for discharging the ammonia gas and the acetic acid gas while re-extracting the granules;
Ammonia gas and acetic acid gas discharged from the bag filter 70 are directly burned and catalytically decomposed at a high temperature in the catalytic oxidation furnace 80 to release clean gas from which the odor component is removed to the outside through the discharger 100. A gas discharge step (S40);
Method for producing a first ammonium phosphate granules for recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process characterized in that proceeding sequentially.
The method of claim 6,
The ammonia gas and the acetic acid gas decomposed by the catalyst at a high temperature of 450 ° C. or higher and the catalyst in the catalytic oxidation furnace 80 are cooled to 300 ° C. or less through the heat exchanger 90, and are externally discharged to the discharger 100. A method for producing primary ammonium phosphate granules for recycling ammonium phosphate waste liquid discharged from an etching process.
The method of claim 7, wherein
The heat exchanger 90 is configured by air cooling by intake of outside air, and heats the air at room temperature to 300 ° C. or more by using waste heat generated from the hot gas of the catalytic combustion engine 80, thereby making it an energy source of the hot air granulator 50. Method for producing a first ammonium phosphate granules for recycling the ammonium phosphate waste liquid discharged from the semiconductor etching process, characterized in that the supply to.