KR101951139B1 - TRE TYPE WASTE NaS BATTERY DISASSEMBLING SYSTEM - Google Patents

Abstract

Provided is a system for recycling TRE-type waste sodium sulfur battery. The recycling system of TRE-type waste sodium sulfur battery comprises: a crusher which separates a waste sodium sulfur battery and pulls out an end cell, injects the same into the inside thereof, in which inert gases are filled, through a double door, and destroys the end cell; a thermal decomposition furnace which heats the end cell by means of an electric heater at 500°C or more to gasify polysulfide sodium sulfur contained in the end cell and sulfur pyrolyzed by sodium, pyrolyzes plugs made of plastic to gasify the same, and separates gas ingredients from crushed pieces of metals which are not gasified and sodium solutions; a sulfur recovery unit which condenses, heats and dehydrates the sulfur gasified from the thermal decomposition furnace, and gains sulfur in which water and reclaimed oil from plastics are separated and refined; a liquid sodium separating tank which separates a sodium solution having sulfur separated therefrom, crushed pieces of containers, and carbon from metals; a cooling tank which cools the metals from the sodium separating tank by means of oils therein, and floats the metals from the oils by means of a sealing liquid to discharge the metals; a sulfur refiner which separates a pyrolysis gas of plastics containing reclaimed oil from vaporization sulfur; a condenser which cools the vaporization sulfur from the sulfur refiner; an oil tank which accommodates the cooled vaporization sulfur from the condenser; and a ventilator which sends pyrolysis gas that does not become reclaimed oil to an exhaust gas processing device along with nitrogen, and detoxifies the same. The present invention safely recycles waste sodium sulfur batteries through a consistent system and uses existing facilities, thereby being economical.

Description

{TRE TYPE WASTE NaS BATTERY DISASSEMBLING SYSTEM}

The present invention relates to a pulmonary sodium sulphate cell, and more particularly to a TRE pulmonary sodium sulphate cell recycling system for recovering resources in a pulmonary sodium sulphate cell.

 When incineration is carried out by a waste disposal company, it is limited to using only a small part of the incinerator capacity to avoid operating problems due to sulfur and sodium components. There is a way to reuse containers in waste batteries, but there is little way to safely recycle the contents.

Tasks and countermeasures of NAS batteries According to Sayama Katai Yomima, prevention of Shinagawa Fire Department of Tokyo Fire Department, approximately 400 module batteries with a total of about 400 units of batteries were put into practical use. The unit cells consisted of a cylindrical container having a diameter of 90.5 mm and a height of 513 mm, And 1560 g of sulfur are separated and stored in a pelletized ceramic β-alumina electrolytic layer, totaling about 5 kg, which causes a chemical reaction at about 300 ° C. to generate a current when it becomes sodium sulfide. It is originally known to return to sodium sulfur.

Waste NAS cells contain sodium and sulfur, which can be charged, but most of them are shorted cells containing discharged di-emulsified sodium.

According to "16716 Chemical Product" published by Chemical Daily, Inc., the information on the constituent materials of the battery is as follows.

1. Sodium

(1) Melting point = 98 占 폚, flash point = 115 占 폚, ignition point = 280 to 290 占 폚, breaking point = 880 占 폚, and specific gravity = 0.97 kg / l.

(2) It reacts with water explosively.

(3) Contact with air containing moisture increases the temperature.

(4) The white smoke of stimulating sodium oxide comes out by combustion.

(5) It readily becomes sodium oxide by oxygen in the air: ignition

(6) does not affect petroleum and reacts with most elements, but B. N. Si. It is resistant to Fe.

(7) The price is between KRW 10,000 and KRW 10,500 per kilogram (as of October 2015)

2. Sulfur

(1) Melting point = 122 占 폚, flash point = 202 占 폚, flash point = 232 占 폚, boiling point = 444.7 占 폚, specific gravity = 2.07 g /

(2) Flammable gas generates harmful sulfur dioxide in case of fire.

(3) The transporting temperature of molten sulfur is usually from 140 to 160 캜.

(4) The lower limit of explosion limit is 2.0% and the lower limit of explosive limit of sulfur is 35g / Nm ³ .

(5) Insoluble in water - It is hardly soluble in ethanol.

(6) The price of powder sulfur is 900 won per 800yuan per Kg (as of October 2015)

3. Sodium polysulfide

(1) There is a risk of oxidative fever and ignition in the atmosphere

(2) Tilt = 252 캜 to 275 캜

(3) It is disturbing and fever when dissolved in water.

(4) Contact with acids may cause harmfulness and hydrogen sulfide.

(5) Corrosive on contact with skin

(6) The pyrolysis temperature is around 500 ° C

4. Melting point of metals

(1) Iron = 1200 ° C or more

(2) Stainless steel = 1400 ° C or more

(3) Aluminum = 660.2 DEG C

5. Carbon felt

(1) Heat resistance is increased under carbon nitrogen gas.

6. Plastic plug

Patent Registration No. 10-0942410 {Registered Date: February 08, 2010}

Waste disposal of waste NAS battery When incinerating waste incinerator, it is easy to get first to the front surface of boiler which contributes to the recovery of waste heat, and since the dust attached to the bag filter is also shaken and difficult to be shaken, The use of only a small portion of the incineration capability is required to take the product, which may increase the processing cost. Existing recycling methods include a method for reusing containers and associating contents or a method for recovering sodium polysulfide from waste batteries, and a method for disassembling batteries for recovering sodium and sulfur. However, economical efficiency such as disposal methods of disposal contents is low and sufficient Safety measures are not taken and safety may be lacking. In the prior art, there are many ways to open a single cell group and take out the contents. In case of a large scale, the apparatus is complicated, and if there is a failure, there is a concern that safety measures against the danger due to the exposed sodium can not be sufficiently secured.

It is an object of the present invention to provide a system for recycling a TRE-type waste sodium sulphate battery for recovering resources in a pulmonary sodium sulphate battery capable of solving the above-mentioned problems and safely recycling the disused sodium sulfur battery through a consistent system.

The TRE-type pulmonary sodium sulphate battery recycling system according to the present invention is a system for recycling a pulsed sodium sulphate battery, comprising: a pulverizer for taking out a pulmonary sodium sulfur battery separately from a released cell, The unit cell is heated to a temperature of 500 ° C or more by heating by means of an electrothermal heater to sulfurize the sulfurized polysulfide and sodium pyrosulfide contained in the unit cell, and the plastic plug is also pyrolyzed to gasify the gas component, A thermal decomposition furnace for separating crushed chips and sodium liquid; A sulfur recovery unit for condensing, heating and dewatering the gasified sulfur from the thermal decomposition furnace to obtain sulfur separated and purified from water and regeneration oil of plastic; The sodium solution remaining after the sulfur is separated, the crushed pieces of the vessel, and the liquid sodium separator for separating the carbon from the metal; A cooling tank for cooling the metal streams from the sodium separation tank with oil contained in the tank, A sulfur purifier for separating pyrolysis gas of plastics including regenerated oil from evaporated sulfur; A condenser for cooling the evaporated sulfur from the sulfur purifier; An oil tank for receiving said cooled evaporated sulfur from said condenser; And a decomposition gas which does not become a regenerated oil is sent to the exhaust gas treatment apparatus together with nitrogen to be detoxified.

Wherein the sulfur recovery unit comprises: a jet scrubber for receiving sulfur dioxide from the pyrolysis, which is mixed with a pyrolysis gas of a gasified plastic and nitrogen; A conveyor for reminding the sulfur contained in the condensed mixture in water to be heated again; And a water separating tank for converting the sulfur content into a sulfur powder by cooling and collecting action to float on the conveyor through the water surface and then dehydrate the water with the dryer.

The sodium separator is discharged in such a manner that the sodium solution is separated from other substances by the overflow tube so that the sodium liquid level is constant, the metal immersed in the sodium solution and the carbon are floated in the sodium solution by the screw formed on the bottom surface, It can be sent to the cooling bath.

The TRE-type pulmonary sodium sulphate battery recycling system includes partition walls between at least one of the pyrolysis furnace and the sodium separating tank and at least one of the sulfur recovery unit, the sulfur purifier, the condenser, and the oil tank, And may further include a containment vessel for preventing the mutual outflow.

The side wall of the partition wall is provided with a shelf in which a bag containing a coolant is placed at an upper end thereof, and a groove is formed at the bottom of the containment vessel to receive the sand when the bag is dropped.

The disused sodium sulfur battery can be safely recycled through a consistent system as shown in FIG. 1, which makes it possible to utilize the existing facilities according to the recycling company, which is economical. According to the present invention, when a single cell container is continuously reused in an automatic apparatus in which an inert gas is disposed in an enclosed chamber, the contents are subjected to fracture pyrolysis to separate sulfur and then sodium is separated by the difference in gravity. Simple and easy to recover sodium and sulfur. In addition, since the automatic device is enclosed in a containment vessel that is a protective barrier, it is a safe facility to prevent sulfur burning without leakage of sodium. In addition, the separation of the metals is economical because it is possible to use a conventional facility separation apparatus.

1 is a block diagram of a system for recycling a TRE-type pulmonary sodium sulphate battery according to an embodiment of the present invention.
Fig. 2 is an enlarged view of the thermal decomposition furnace shown in Fig. 1. Fig.
FIG. 3 is an enlarged view of the sodium separator shown in FIG. 1. FIG.
Fig. 4 is an enlarged view of the cooling bath shown in Fig. 1. Fig.
Fig. 5 is an enlarged view of the sulfur recovery device shown in Fig. 1. Fig.
6 is a view showing a containment vessel according to an embodiment of the present invention.

Hereinafter, a system for recycling a TRE-type pulmonary sodium sulfur battery according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

The TRE-type pulmonary sodium sulphate battery recycling system according to an embodiment of the present invention includes a pulverizer 110, a thermal decomposition furnace 120, a sulfur recovery unit 130, a liquid sodium separator 140, a cooling tank 150, A purifier 160, a condenser 170, an oil tank 180, an air blower 190, and a containment vessel 200.

The pulverizer 110 removes the spent sodium sulfur battery separately from the uncharged unit, and the pulverizer 110 is crushed by injecting it through the double door 1 and filled with an inert gas.

The thermal decomposition furnace 120 heats the unit cells to a temperature of 500 ° C or more by means of an electrothermal heater to gasify the sulfurized polysulfide contained in the unit cell and the sulfur pyrolyzed in sodium, pyrolyzes the plastic plug to gasify the gas, The components are separated from the crushed pieces such as non-gasified metals and the sodium liquid.

The sulfur recovery unit 130 condenses the gasified sulfur from the thermal decomposition furnace 120, and heats and dehydrates it to obtain sulfur separated from refinery oil and regenerated oil. The sulfur recovery unit 130 includes a jet scrubber 132, a conveyor 134, and a water separator 136.

The jet scrubber 132 receives the mixture of the pyrolysis gas of the gasified plastics and nitrogen from the nitrogen generator 15, and the sulfur content from the thermal decomposition furnace is condensed. The conveyor 134 recalls the sulfur contained in the condensed mixture in water and reheats it. The water separation tank 136 is made of sulfur powder by cooling and collecting action to float on the conveyor through the water surface, and then dehydrated by the dryer 138.

The sodium separator (140) separates the sodium solution from which the sulfur has been separated, the crushed pieces of the vessel and the carbon from the metals. The sodium separator (140) discharges the sodium solution by separating the sodium solution from other substances by a pump (not shown) or an overflow pipe (148) so that the sodium liquid level is constant, And is then sent to the cooling bath 150. The cooling bath 150 is connected to the cooling bath 150, In order to maintain the sodium liquid level, when liquid is drawn out by a pump (not shown), it is adjusted by a liquid level controller or an overflow pipe 148 is installed. In addition, since it is necessary to ensure fluidity in order to minimize the adherence amount to the metal pieces of the sodium solution, the tracing 144 for electric heating is provided below the conveyor 141.

The cooler 150 is cooled by the oil contained in the metal separator from the sodium separator 140, and is then discharged as a sealing liquid from the oil. The sulfur purifier 160 separates pyrolysis gas of plastics including regenerated oil from evaporated sulfur.

A condenser 170 cools the evaporated sulfur from the sulfur purifier 160. An oil tank 180 receives the cooled evaporated sulfur from the condenser. The decompressed gas, which does not become regenerated oil, is sent to the exhaust gas treatment apparatus (not shown) together with nitrogen to be detoxified.

The containment vessel 200 includes at least one of the pyrolysis furnace 130 and the sodium separator 140 and the at least one of the sulfur recovery unit 130, the sulfur purifier 160, the condenser 170, The barrier ribs 210 may be provided between at least one of the barrier ribs 180 to prevent the contents from flowing out to each other.

A shelf 220 on which a pouch 222 containing a coolant such as sand is placed is installed on the side of the partition wall 210 and a sand 220 of the pouch 222 is attached to a bottom 230 of the containment vessel 200. [ A groove 240 is formed to accommodate the drop.

The containment vessel 200 is disconnected from the sodium-related equipment and other devices and the bulkhead, and if the liquid flows out of the plant, a groove 240 is provided in the inside of the partition wall 210

And sand or the like such as a coolant is prepared on the upper part of the wall to sense the outflow of the liquid, so that it can be cooled down and prevented from spreading by being dropped on the groove 240, so that it can be safely operated. It is necessary to provide a device that considers the shelf 220 so that sand or the like can be placed at such a height that the influence of the splashing liquid upon dropping the sand does not adversely affect the apparatus.

According to the present invention, sodium, sulfur, metals and the like can be separated and recovered automatically by introducing a unit cell in the process by the system as shown in Fig. The outline is shown next.

1. Getting ready

(1) Put the sealing oil into the cooling bath (150).

(2) Inert gas is introduced into the containment vessel 200 of Fig.

(3) In a sodium separator (140), add the required amount of sodium and heat to the appropriate temperature.

(4) The battery in the charged state is discharged.

(5) Disassemble the package battery from the single battery.

(6) Insert the battery into the hopper (1) and close the closing door. The input door is opened and closed when additional input is made.

2. At the start, the unit cell is securely crushed in an inert gas and transported to the pyrolysis furnace 120 of FIG. 2 by the charging conveyor 3.

3. Since the pyrolysis furnace (120) is heated to 500 ° C or higher by the electrothermal heater, sodium polysulfide is thermally decomposed into sulfur and sodium. The sulfur component is mixed with the pyrolysis gas of the gasified plastics and nitrogen and sent to the jet scrubber 132. The sulfur component becomes the sulfur powder by the cooling and dust collecting action and is deposited on the water surface in the water separating tank 136, After dewatering with a dryer, the oil refiner 160 discharges the oil into the evaporated and separated product. Most of the pyrolysis gas of the plastic is separated from the evaporated sulfur in the sulfur purifier 11 and sent to the condenser 170 to be cooled and then sent to the oil tank 180. The decomposition gas which does not become the regenerated oil is sent to the exhaust gas treatment device (not shown) together with the nitrogen by the air blower 190 and is treated as harmless.

4. The sodium solution, the crushed pieces of the vessel, and the carbon remaining in the sulfur and the like are transferred by the screw 124 installed on the bottom of the pyrolysis furnace 120 and discharged to the sodium separator 140 of FIG.

5. The sodium separator 140 is composed of a vertical body 142 and a conveyor 141 connected to the vertical body and the lower end of the thermal decomposition furnace 120 to receive the sodium solution and metals and inclined upward at the outlet side, Since it is filled with sodium liquid so that the air layer of the conveyor 141 is not connected, there is a sealing function of a sulfur gas or the like generated in the pyrolysis furnace 120. The sodium solution is discharged by a pump or the overflow pipe 148 shown in FIG. 3 in such a manner that the sodium solution is constantly separated from other substances, and the metals, carbon and the like, which are caught in the sodium solution, are discharged to the screw 143 And then sent to the cooling bath 150. The sodium liquid on the screw side is evaporated by the entry of high-temperature metals in the cooler and serves to block the flow on the upstream side of the petroleum gas.

4 includes a vertical body 152 receiving a metal from the sodium separator 140 and a body 152 containing a conveyor 154 having an upwardly connected outlet connected to the lower end thereof, So that an air layer of the vertical body 152 and the conveyor 154 is not connected to each other. The hot metal in the sodium tank is cooled in petroleum, recycled from the oil in the conveyor 154, and sent to a separate metal separator for fractional recycling.

1: Double text
15: Nitrogen generator
110: crusher
120: pyrolysis furnace
130: Sulfur recovery unit
132: Jet scrubber
134: Conveyor
136:
138: Dryer
140: Sodium separator
141: Conveyor
142: Vertical body
143: Screw
148: Overflow pipe
150: Cooling tank
152: vertical body
154: Conveyor
160: sulfur purifier
170: condenser
180: Oil tank
190: Aerator
200: Containment container
210:
220: Shelf
222: Pocket
230: floor
240: Home

Claims (5)

A disintegrator for disposing a disused sodium-sulfur battery cell to take out a unit cell, putting it in an inert gas filled in a double door, and crushing it;
By heating the unit cell to a temperature of 500 ° C or more by means of an electric heater, the sulfur dissolved in the sodium sulfide and sodium pyrosulfide contained in the unit cell is gasified and the plastic plug is thermally decomposed to gasify the gas component, A pyrolysis furnace for separating the pyrolysis furnace from the crushed fragments and the sodium liquor;
A sulfur recovery unit for condensing, heating and dewatering the gasified sulfur from the thermal decomposition furnace to obtain sulfur separated and purified from water and regeneration oil of plastic;
The sodium solution remaining after the sulfur is separated, the crushed pieces of the vessel, and the liquid sodium separator for separating the carbon from the metal;
A cooling tank for cooling the metal streams from the sodium separation tank with oil contained in the tank,
A sulfur purifier for separating pyrolysis gas of plastics including regenerated oil from evaporated sulfur;
A condenser for cooling the evaporated sulfur from the sulfur purifier;
An oil tank for receiving said cooled evaporated sulfur from said condenser; And
Wherein the decomposition gas which is not regenerated oil is sent to an exhaust gas treatment device together with nitrogen to be detoxified. The apparatus of claim 1, wherein the sulfur recovery unit
Wherein the sulfur content from the thermal decomposition is supplied to a mixture of gasified plastic pyrolysis gas and nitrogen and is condensed;
A conveyor for reminding the sulfur contained in the condensed mixture in water to be heated again; And
And a water separating tank for converting the sulfur content into a sulfur powder by cooling and collecting action to float on the conveyor through the water surface, and then dehydrating the water on the conveyor, and a TRE-type waste sodium sulfur recycling system. 2. The method according to claim 1, wherein the sodium separator is formed by discharging the sodium solution by separating the sodium solution from the other material by an overflow tube so that the sodium liquid level is constant, , And then sent to the cooling bath. The apparatus according to claim 1, wherein a partition wall is provided between at least one of the pyrolysis furnace and the sodium separator and at least one of the sulfur recovery unit, the sulfur purifier, the condenser, and the oil tank, Wherein the TRE type waste sludge cell recycling system further comprises: [5] The method of claim 4, wherein a side wall of the partition wall is provided with a shelf in which a bag containing a coolant is placed at an upper end thereof, and a TRE type waste sodium Battery recycling system.

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