KR100591695B1 - Aluminum separator and method of multilayered composite materials containing aluminum layer - Google Patents

Abstract

The present invention relates to a method for separating only an aluminum component from a composite material such as a packaging multilayer film including an aluminum layer, and an apparatus suitable for the separation method.

The present invention is a method for continuously separating and separating the aluminum component in a composite material containing an aluminum layer, comprising the steps of: a) injecting a solid composite ground material containing an aluminum layer into the separator; b) adding a separation solution for separating the aluminum component of the pulverized product to the separation device, and selectively reacting only the aluminum component from the pulverized product into the separation solution to dissolve in an aqueous solution; c) separating the remaining solid material from the separation solution after the aluminum component is dissolved in the separation solution in the separation apparatus.

Packaging multilayer film, aluminum deposition film, composite material containing aluminum, aluminum separator, waste multilayer film

Description

Process and equipments for the separation of aluminum layer from multi-layer composites}

1 is a schematic diagram of an apparatus for carrying out the reproducing method of the present invention.

(Drawing reference is a short description)

1. Input part of separator

2. Inlet of composite material

3. Inlet Motor

4. Insert screw

5. Liquid interface at the input

6. Outlet of separator

7. Outlet motor

8. Outlet screw

9. Liquid interface at outlet

10. Composite outlet

11. Liquid reservoir for separation

12. Pump

13. Separation liquid inlet

14. Liquid inlet for separation

15. Separation liquid outlet

16. Liquid outlet for separation

17. Sieve, mesh

18. Sieve, mesh

19. Sieve, mesh

20. Sieve, mesh

21. Storage tank temperature measuring device

22. Input temperature measuring device

23. Outlet temperature measuring device

24. Angle between input and horizontal plane

25. Angle between outlet and horizontal plane

The present invention relates to a method and apparatus for separating an aluminum component from a packaging multilayer film including an aluminum layer, and recycling both the aluminum component and the film.

Currently, packaging multilayer films mainly containing polypropylene (PP), polyester (PET), polyethylene (PE), nylon, and aluminum layers for various purposes, such as moisture proofing and beautiful exterior, are mainly used as packaging materials for food or beverage. In use, the demand for such packaging multilayer films continues to increase.

When such a multilayer film is used for packaging a product, several steps of a bonding process and a printing process such as gravure printing are performed. Defects may occur during each bonding process or printing process, and these defects are mostly disposed of. In addition, the amount discarded after being used as a packaging for food or beverages is increasing. Aluminum components do not melt and disperse in most plastic molding processes, making the film difficult to recycle. The discarded packaging multi-layer film is partially recycled without special treatment, but only in the production of products with little added value due to poor mixing of various components and poor properties due to the undispersed aluminum layer. It is used locally. As a method of separating and recycling each of these waste packaging materials into its constituent components, there is a Korean Patent "Recycling Method for Packaging Multilayer Film Waste", Registration No. 10-0361735. In this patent, the aluminum layer was separated from the PET film using an aqueous alkali or acid solution. The apparatus used for separation is a mesh pass reactor and the like for batch processes. The present invention relates to a continuous aluminum component separation process and apparatus more efficiently than batchwise.

The inventors of the present application have completed the present invention as a result of conducting research and experiments to recycle the film waste containing the aluminum layer, which is a precious resource, without being embedded or incinerated.
It is an object of the present invention to provide a method and apparatus for continuously separating aluminum components using an aqueous alkaline or acid solution to recycle film waste containing an aluminum layer.

In order to achieve the object as described above, the present invention is a method for continuously separating and separating the aluminum component in the composite material containing an aluminum layer, a) separating a composite composite material of a solid state containing an aluminum layer Introducing into the device; b) adding a separation solution for separating the aluminum component of the pulverized product to the separation device, and selectively reacting only the aluminum component from the pulverized product into the separation solution to dissolve in an aqueous solution; c) separating the remaining solid material from the separation solution after the aluminum component is dissolved in the separation solution in the separation apparatus.

delete

delete

delete

delete

An object as described above is also a device for continuously separating and separating the aluminum component in the composite material containing aluminum, the grinding material inlet to which the composite grinding material containing the aluminum component is placed, the aluminum component of the grinding material A separation solution inlet having a predetermined temperature for separation is provided at the bottom thereof, while a discharge port of the separation solution is provided, and a cylindrical input portion disposed at a predetermined angle with a horizontal plane; A tubular discharge part connected to the input part at a predetermined angle from a lower part thereof, and having a pulverized material discharge port configured to discharge the pulverized material introduced into the pulverized material input hole of the input part; An inlet screw installed in the inlet to transfer the composite pulverized material injected into the inlet of the pulverized product at a predetermined speed; A discharge part screw installed in the discharge part to transfer the pulverized material transported by the input part screw to the pulverized material discharge port at a predetermined speed; And a pump for supplying the separation solution from the separation solution reservoir to the separation solution inlet.

Hereinafter, a continuous method of separating the aluminum component from the composite waste including the aluminum layer using the apparatus as schematically described in detail.

First, the length of one side of the composite waste including the aluminum layer is crushed or crushed to a size of 0.1 to 10 cm. The composite pulverized material is introduced at an appropriate speed into the inlet 2 of the inlet 1 of the separator. The composite pulverized material introduced into the input unit 1 moves downward by the input unit screw 4 and gravity which rotate by the input unit motor 3. The pulverized product moved downward reaches the separation solution interface 5 such as an alkali or acid aqueous solution and comes into contact with a suitable separation solution. As the composite pulverization comes into contact with the separation solution, the aluminum component of the composite pulverization reacts with the separation solution and begins to dissolve in the separation solution. While the aluminum component reacts with the separation solution to dissolve, the composite pulverized material continues to move by the operation of the inlet screw 4 to reach the bottom of the separator, and to the motor 7 of the outlet 6. It moves upward by the discharge part screw 8 which rotates. While the aluminum component continues to dissolve, the composite pulverized material moving upwards passes through the interface 9 of the separation solution, so that the composite pulverization no longer comes into contact with the separation solution. The composite pulverized material continues to move upward of the separation solution, the separation solution buried in the composite pulverized material falls downward by gravity, and the composite pulverized material is discharged out of the separation device through the outlet 10.

The separation solution is supplied to the apparatus by the pump 12 through the separation solution inlet 13 located at the bottom of the discharge section 6 from the reservoir 11 or the separation solution inlet 14 located at the bottom of the inlet 1. The separation solution discharge port 15 located in the middle of the discharge unit 6 or the separation solution discharge port 16 located in the middle of the input unit 1 is returned to the storage tank 11. Separation solution inlet (13,14) and the separation solution outlet (15,16) is provided with a sieve (mesh) (17, 18, 19, 20), the composite ground material having a side length of 0.1cm or more is a sieve (17) , 18, 19, 20, so that only the liquid can pass through the separation solution inlet (13, 14) and the separation solution outlet (15, 16). The interfaces 5, 9 of the separation liquid are located on the same plane as the separation liquid outlets 15, 16. While the composite pulverized material passes through the separating device, the separating liquid contacts with the separating liquid between the separating liquid interfaces (5, 9) in the separating device, during which the aluminum component of the composite pulverizing reacts with the separating liquid and dissolves in the separating solution. do.

As the separation liquid, an aqueous alkali solution of a suitable concentration may be used, for example, an aqueous NaOH solution, an aqueous KOH solution, an aqueous Ca (OH) ₂ solution, an aqueous LiOH solution, or an acid aqueous solution, for example, an aqueous HCl solution, an HI solution, an H ₂ SO ₄ solution, HNO ₃ aqueous solution, HF aqueous solution, HBr aqueous solution and the like can be used.

The separation liquid is preferably used at a temperature higher than the room temperature of the separation liquid in order to speed up dissolution and separation. When the separation liquid is used higher than room temperature, the inlet 1 and outlet 6 of the separator shown in FIG. 1 can be heated by heating or electric heating using fruit such as steam or silicon oil. have. Alternatively, the separation liquid is heated in the separation liquid storage tank 11 in the above-described manner, and the pipe from the separation liquid storage tank 11 to the separation device, the separation device, and the pipe from the separation device to the separation liquid storage tank can be used as heat insulation. have. The temperature of the separating liquid may be measured using the temperature measuring apparatuses 21, 22, and 23 in contact with the separating liquid of the separating liquid reservoir 11, the inlet 1, and the outlet 6.

It is preferable that the concentration of the aqueous alkali solution used is in the concentration range of 0.01% to saturated solution because the concentration of the aqueous alkali solution in excess of 0.1% indicates an appropriate dissolution rate. In addition, when the aqueous alkali solution concentration is in the concentration range of 5% to saturation concentration, the temperature of the alkali aqueous solution is preferably from room temperature to 30 ℃, when the aqueous alkali solution concentration is a relatively low concentration in the concentration range of 0.01% to 5%. As for alkali aqueous solution temperature, the range of the boiling point of 50 degreeC-aqueous solution is preferable.

The concentration of the acid aqueous solution used is in the concentration range from 1% to saturation concentration, 1.8% or more is preferred. The concentration of the acid aqueous solution may be increased to increase the dissolution rate of the aluminum component. The temperature of the acid aqueous solution may likewise increase the dissolution rate of the aluminum component at temperatures above room temperature.

The input screw 4 of FIG. 1 transfers the composite pulverized material downward at a uniform speed by a rotational movement, and while crushing the composite pulverized material and the separation solution while transferring the composite pulverized material, the composite pulverized material is pulverized. It helps the aluminum component of water to be easily dissolved by the separation solution. Inlet screw (4) is used to separate the composite material by using a screw, a stirring impeller, a caterpillar, a rolling roll, or two or more, depending on the properties of the composite grinding material Allow the solution to soak at a uniform rate. The shape, quantity, rotation speed, and the like of the composite pulverized material conveying apparatus of the input part 1 such as a screw are appropriately selected depending on the properties of the composite material, the reaction rate with the separation solution of the aluminum component, and the like.

The discharge screw 8 of FIG. 1 transfers the pulverized product at a uniform speed upward by the rotational movement, and the separation solution falls downward by gravity at the upper side of the interface 9 of the separation solution. In order not to fall, the distance between the inner surface of the grind outlet 10 and the screw rotary blade should be smaller than the size of the composite grind. In addition, the discharge screw 8 has a suitable shape so that the composite material can be easily dropped from the powder discharge port (10). The screw may be used instead of a catafil, a rotary roll, or the like depending on the properties of the composite grinding material. The shape, rotation speed, and the like of the composite pulverized material conveying device of the discharge part 6, such as a screw, are appropriately selected depending on the properties of the composite pulverized product, the reaction rate of the aluminum component with the separation solution, and the like. All surfaces of the discharge part 6 and the transfer device, such as the screw of the input part 1, and the separation solution must not react or dissolve with the separation solution used, and the surface must not be rough to allow the separation solution to flow well. . When the aqueous alkali solution was used as the separation solution, stainless steel was suitable as the device material of FIG. 1, and in the case of the acid aqueous solution, glass, a glass-coated metal, a plastic, or an alloy that does not react with the aqueous acid solution, etc. It is suitable as a material.

The aluminum component of the composite material is dissolved in an aqueous solution in a salt state of aluminum hydroxide by reacting with an aqueous alkali solution such as NaOH, and at this time, hydrogen gas is generated. The hydrogen gas discharged from the discharge port 10 and the crushed product inlet 2 of the separator can be properly collected and utilized.

The reaction rate of the aluminum component varies depending on the alkali or acid aqueous solution, that is, the temperature, concentration of the separation solution, and the mixing speed of the separation solution and the composite pulverized product. When this reaction rate is large, the dissolution time for dissolving aluminum is shortened. The reaction time of aluminum can be seen as the average time from when the composite pulverized product touches the separation solution interface 5 of the inlet 1 to leave the separation solution interface 9 of the outlet 6, It is determined by the rate of descending the composite pulverized material of the inlet 1 and the rate of pulverized material of the outlet 6. In the equilibrium operating condition, the pulverization descending speed of the input unit 1 and the pulverization rising speed of the discharge unit 6 become equal to each other. In the equilibrium operating condition, the residence time in the separating device of the composite pulverized material (FIG. 1) is discharged from the pulverized product discharge port 10 from the time when the composite pulverized material indicated by color or the like is introduced in the pulverized material inlet 2 You can find out by measuring the time until.

Inner diameters, lengths, and angles 24 and 25 of the inlet part 1 and the outlet part 6 of FIG. 1, the positions of the separation liquid inlets 13 and 14 and the outlets 15 and 16, respectively, The separation liquid transfer speed of the pump may vary depending on the properties of the target composite material and the composite material transfer device.

After the aluminum component is dissolved and separated, the composite material discharged from the separator is washed with excess water, dried and recycled. The aluminum component dissolved in the separation solution is precipitated and separated in the solid phase by neutralizing the separation solution to neutral (pH ~ 7). For example, when an aqueous alkali solution is used as the separation solution, aluminum hydroxide (Al (OH) ₃ ) is obtained.

The invention is further described below by way of the following non-limiting examples.

Example 1

The aluminum component was separated from the PET film on which the aluminum layer was deposited according to the separation process as described above. Separator as shown in Figure 1 was manufactured and used in the experiment. The separator used was about 45 ° with the inlet 1 and the horizontal plane of about 45 °, and about 25 ° between the outlet 6 and the horizontal plane. The lengths at the bottom of the inlet 1 and outlet 6 of the separator were 40 cm and 54 cm, respectively, and the inner diameters of the inlet 1 and outlet 6 were 10.5 cm. The agitator was stirred at 60 to 120 rpm instead of the screw 4 of the inlet 1, and the screw 8 of the outlet 6 was operated at 0.02 to 1.8 rpm. NaOH and KOH aqueous solutions were used as separation solutions, and the separation solution was supplied to the separation device through the separation liquid inlet 13 by the pump 12 in the storage tank 11, and the separation solution outlet ports 15 and 16. The plastic pipe was connected to return to the reservoir 11 again. A heater (not shown) was attached to the storage tank 11 of the separation solution to increase the temperature of the separation solution, and the experiment was performed when the separation solution temperature in the separation apparatus was measured to maintain a constant temperature. The material in contact with the separation solution in the separator used was stainless steel (SUS304), and the stainless steel did not react at all alkali solution concentrations and temperatures.

The packaging film waste consisting of only the PET layer and the aluminum layer was cut into squares having a side length of 3 cm with a cutter and put into the inlet 2 of FIG. 1. The film waste used was analyzed using a differential scanning thermal analyzer (DSC; Perkin Elmer DSC7) according to the manufacturer's standard protocol and consisted of only PET and aluminum layers. In the input unit 1, the stirrer was rotated at 60 to 120 rpm to allow the injected film and the separation solution to be evenly mixed. The injected film was moved downward by gravity, and was moved upwardly through the discharge port 6 by the discharge screw 8 through the bottom and discharged through the discharge port 10. The experiments were carried out at equilibrium conditions where the feed rate and discharge rate of the film were similar, and the average of the measured values was measured by measuring the time until discharged with 5 PET films of similar size but different in color. The average residence time of is calculated.

By adjusting the voltage used by the motor 7 of the discharge part 6, the rotational speed of the discharge part screw 8 could be adjusted. Consequently, the average residence time of the film in the equilibrium state can be adjusted in the range of 5 to 100 minutes. there was. Using various concentrations of NaOH and KOH aqueous solution, the aluminum layer was 100% dissolved and separated at 30, 50, and 70 ° C., and the average residence time was measured under experimental conditions in which pure PET film was discharged. Indicated.

Dissolution Separation Temperature (℃) NaOH aqueous solution concentration (%) KOH aqueous solution concentration (%) 1.0 2.5 5.0 10.0 1.0 2.5 5.0 10.0 30 28.5 27.3 26.8 23.4 40.5 33.4 29.7 26.2 50 15.0 6.7 5.0 5.0 21.7 11.8 5.5 5.0 70 10.5 5.0 5.0 5.0 12.0 5.2 5.0 5.0

It was visually confirmed that 100% of aluminum was separated. The higher the temperature of the separation solution in NaOH or KOH aqueous solution of the same concentration, all the aluminum layer was dissolved quickly. At the same separation solution temperature, the higher the concentration of the separation solution, the faster the aluminum layer dissolved all. At the same concentration and temperature, the NaOH solution was more efficient at dissolving aluminum than the KOH solution. The separation solution temperature of 50 ° C. or higher and the separation solution concentration of 2.5% or more were more efficient for dissolution separation than the separation solution temperature of less than 50 ° C. and the separation solution concentration of less than 2.5%, respectively.

Example 2

The packaging film waste used in this example was the same size as that used in Example 1, but 3 cm × 3 cm was a different kind, all other experimental conditions were the same as in Example 1. The film waste used was analyzed using a differential scanning thermal analyzer (DSC; Perkin Elmer DSC7) according to the manufacturer's standard protocol and consisted of only PET and aluminum layers. The higher the temperature of the separation solution in the same concentration of NaOH or KOH aqueous solution, all the aluminum layer dissolved in a faster time. At the same separation solution temperature, the higher the concentration of the separation solution, the faster the aluminum layer dissolved all. At the same concentration and temperature, the NaOH solution was more efficient at dissolving aluminum than the KOH solution. The separation solution temperature of 50 ° C. or higher and the separation solution concentration of 2.5% or more were more efficient for dissolution separation than the separation solution temperature of less than 50 ° C. and the separation solution concentration of less than 2.5%, respectively. When the concentration of the NaOH or KOH aqueous solution is 1.0% and the dissolution separation temperature is 30 ℃, part of the aluminum layer was stuck to the PET film without dissolving until the residence time is 100 minutes.

Dissolution Separation Temperature (℃) NaOH aqueous solution concentration (%) KOH aqueous solution concentration (%) 1.0 2.5 5.0 10.0 1.0 2.5 5.0 10.0 30 > 100 77.7 45.1 38.8 > 100 91.0 60.1 46.2 50 26.7 23.2 18.4 11.8 45.4 33.4 23.4 15.7 70 12.7 9.9 6.7 5.0 19.2 12.4 10.3 7.9

Example 3

The packaging film waste used in this example was the same size as that used in Example 1 or Example 2 but 3 cm x 3 cm, but was of a different type, all other experimental conditions were the same as in Example 1. The film waste used was analyzed using a differential scanning thermal analyzer (DSC; Perkin Elmer DSC7) according to the manufacturer's standard protocol, and consisted of three layers: PET layer, aluminum layer, and polypropylene (PP) layer. In the NaOH or KOH aqueous solution of 10.0% concentration, the higher the temperature of the separation solution, the faster the aluminum layer was completely dissolved. At the same concentration and temperature, the NaOH solution was more efficient at dissolving aluminum than the KOH solution. In the case of NaOH aqueous solution, the aluminum layer of the waste packaging film was not dissolved for 100 minutes at the concentration of 5% or less in the aqueous solution of KOH and in the case of dissolution separation temperature of 30 ° C in the concentration of 10% or less. And remained between the polypropylene film.

Dissolution Separation Temperature (℃) NaOH aqueous solution concentration (%) KOH aqueous solution concentration (%) 1.0 2.5 5.0 10.0 1.0 2.5 5.0 10.0 30 > 100 > 100 > 100 68.5 > 100 > 100 > 100 > 100 50 > 100 > 100 > 100 17.7 > 100 > 100 > 100 46.3 70 > 100 > 100 > 100 7.6 > 100 > 100 > 100 8.8

According to the regeneration method of the present invention, the aluminum layer is continuously separated and recovered from a composite waste material such as a multilayer film including an aluminum layer which is currently embedded or incinerated, thereby recycling both aluminum compounds and plastics from which aluminum is removed. have.

Claims (18)

A method for continuously separating and separating aluminum components from a composite material including an aluminum layer, (a) injecting a solid composite pulverized product including an aluminum layer into the separator; (b) adding a separation solution for separating the aluminum component of the pulverized product to the separator, and selectively reacting only the aluminum component with the separation solution from the pulverized product to dissolve it in the aqueous phase; (c) separating the remaining solid material from the separation solution after the aluminum component is dissolved in the separation solution in the separation device. The method of claim 1, wherein the separation solution is selected from aqueous alkali solutions including aqueous NaOH, aqueous KOH, aqueous Ca (OH) _2, aqueous LiOH. The method of claim 2, wherein the concentration of the aqueous alkali solution is in the range of 0.01% to saturation concentration. (delete) The method of claim 2, wherein the aqueous alkali solution is a NaOH aqueous solution. The method of claim 1, wherein the separation solution is selected from an aqueous acid solution including an aqueous HCl solution, an HBr solution, an HI solution, an HF solution, an H ₂ SO ₄ solution, and an H ₂ NO ₃ solution. The method of claim 6, wherein the concentration of the acid aqueous solution is in the range of 1.8% to saturation concentration. (delete) (delete) The method of claim 3, wherein the concentration of the aqueous alkali solution is in the range of 5% to saturation concentration, and the temperature of the aqueous alkali solution is in the range of room temperature to 30 ° C. The method according to claim 3, wherein the concentration of the aqueous alkali solution is 0.01 to 5%, and the temperature of the aqueous alkali solution is in the range of 50 ° C to the boiling point of the aqueous alkali solution. (delete) (delete) (delete) (delete) (delete) The method of claim 1, wherein the gaseous hydrogen generated by the reaction of the aluminum component and the separation solution is collected and recycled. A device for continuously separating and separating aluminum components from a composite material containing aluminum, In the upper part, a grind material inlet into which the composite grind including the aluminum component is introduced is provided, and a separation solution inlet at a predetermined temperature for separating the aluminum component of the grind is provided at the bottom, while an outlet for the separation solution is provided, Tubular input portion disposed at an angle of; A tubular discharge part connected to the input part at a predetermined angle from a lower part thereof, and having a pulverized material discharge port configured to discharge the pulverized material introduced into the pulverized material input hole of the input part; An inlet screw installed in the inlet to transfer the composite pulverized material injected into the inlet of the pulverized product at a predetermined speed; A discharge part screw installed in the discharge part to transfer the pulverized material transported by the input part screw to the pulverized material discharge port at a predetermined speed; And And a pump for supplying a separation solution from the separation solution reservoir to the separation solution inlet.

Images