JPH06220463A - Production of hydrocarbon oil from waste plastic or rubber material and equipment for use therein - Google Patents

Abstract

(57) [Abstract] [Purpose] Blocking the catalytic cracking gas passage due to crystallization of phthalic acid contained in the pyrolysis gas when catalytically cracking the pyrolysis gas of waste plastic material or waste rubber material to obtain hydrocarbon oil. The reduction in the recovery rate of hydrocarbon oil due to is prevented. [Structure] The recycled material (1), which is a waste plastic material or rubber material, is pyrolyzed together with 6-nylon (5), which yields ε-caprolactam which dissolves phthalic acid crystals by pyrolysis, and thereby obtains After the thermal cracking gas is catalytically cracked using aluminum chloride hexahydrate (21) to obtain a catalytic cracking gas, the catalytic cracking gas is cooled to recover a low boiling point hydrocarbon oil (50). To do.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for obtaining a hydrocarbon oil by utilizing a waste plastic material or rubber material, and an apparatus used for carrying out the method.

[0002]

2. Description of the Related Art In modern automobiles, body panels,
Various interior parts, tires, etc. are supposed to be formed of a plastic material or a rubber material which is a high molecular compound, and the use ratio of the plastic material or the rubber material is gradually increasing. So, for example, if one car ends its role and is simply scrapped,
A considerable amount of waste plastic or rubber material,
That is, waste plastic materials or waste rubber materials are generated, and in the current situation where a large number of automobiles are disposed of as waste vehicles every day, the amount of waste plastic materials or waste rubber materials generated thereby becomes enormous.

As described above, the waste plastic material or the waste rubber material, which is an enormous amount even if it is generated in connection with the automobile, can be effectively reused in various industries including the automobile industry. Is planned, and further,
Efforts are being made to further expand its reuse.
Under such circumstances, as a part of the recycling of waste plastic material or waste rubber material, for example, JP-A-63-17819
As shown in Japanese Patent No. 5, it has been proposed to produce a hydrocarbon oil from a waste plastic material, and the produced hydrocarbon oil is used as a fuel or the like.

In producing hydrocarbon oil from waste plastic materials, conventionally, waste plastic materials are pyrolyzed in a pyrolysis tank, and the pyrolysis gas produced thereby is further converted into a suitable catalyst such as zeolite. It is known to carry out catalytic cracking under the conditions of: and cool the catalytic cracking gas produced thereby to obtain a hydrocarbon oil having a relatively low boiling point, for example, having 22 or less carbon atoms. There is. Further, the method for obtaining a hydrocarbon oil through the steps of thermal cracking, catalytic cracking and cooling as described above is applied not only to waste plastic materials but also to waste rubber materials.

[0005]

Most of the waste plastic materials to be reused as described above are usually chlorine-based plastic materials such as polyvinyl chloride which generate a relatively large amount of hydrochloric acid by thermal decomposition. . When the thermal decomposition gas obtained by thermally decomposing such a chlorine-based plastic material is catalytically decomposed, for example, when zeolite is used as a catalyst, hydrochloric acid contained in the thermal decomposition gas invades the zeolite to form a catalyst. There is a problem of degrading the function.

Therefore, aluminum chloride hexahydrate (AlCl ₃ .6H ₂ O) containing hydrochloric acid as an active aid is used in place of zeolite for catalytic decomposition of pyrolysis gas obtained by thermally decomposing waste plastic material. And iron chloride hexahydrate (FeC
be performed using l ₃ · 6H ₂ O), etc. of the solid acid catalysts have been proposed.

As described above, even if a solid acid catalyst using hydrochloric acid as an active auxiliary agent is used to recover hydrocarbon oil from waste plastic material or waste rubber material, waste oil used for thermal decomposition is discarded. When the plastic material or waste rubber material contains a phthalate ester plasticizer used as a plasticizer for polyvinyl chloride, etc., the waste plastic material or waste rubber material is obtained by thermal decomposition. The pyrolysis gas contains phthalic acid which crystallizes below the melting point of about 190 ° C. When the thermal cracked gas containing phthalic acid is catalytically cracked, the catalytic cracked gas thus obtained contains phthalic acid, and the catalytic cracked gas is cooled to obtain hydrocarbon oil. In this case, phthalic acid is crystallized and deposited in the passage portion leading the catalytic cracking gas to the cooler, whereby the passage portion leading the catalytic cracking gas to the cooler is blocked by the deposited phthalic acid crystals and The cooling process may be hindered, and the hydrocarbon oil recovery rate may decrease.

Although phthalic acid crystals are difficult to dissolve in various substances which are usually used as a solvent, when the inventor of the present application uses a material having an amide group such as polyamide resin as a solvent. It has been confirmed that they can be dissolved relatively easily.

In view of the above point, the present invention catalytically decomposes a thermal decomposition gas obtained by thermally decomposing a waste plastic material or a waste rubber material using a solid acid catalyst, and obtains a catalytic decomposition gas obtained thereby. When obtaining a hydrocarbon oil by cooling, it is assumed that the waste plastic material or waste rubber material contains a phthalate ester plasticizer, and the catalytically cracked gas obtained by catalytically cracking the thermally cracked gas is phthalic acid. In the case of containing hydrocarbon oil, it is possible to carry out the cooling treatment of the catalytic cracking gas without any trouble and avoid the situation where the recovery rate of hydrocarbon oil decreases. It is an object to provide a method of obtaining and a device used for its implementation.

[0010]

In order to achieve the above-mentioned object, a method for obtaining a hydrocarbon oil from waste plastic or rubber material according to the present invention is a method in which waste plastic material or rubber material is thermally decomposed into phthalate. A catalytic decomposition product that is obtained by thermally decomposing in a thermal decomposition tank with a material having an amide group to obtain a dissolving agent that dissolves an acid crystal, and catalytically decomposing the thermal decomposition product obtained from the thermal decomposition tank using a solid acid catalyst. Then, the catalytic cracking product is subjected to a cooling treatment to obtain a hydrocarbon oil.

Further, the hydrocarbon oil producing apparatus according to the present invention is supplied with a waste plastic material or rubber material, and also has a material having an amide group capable of obtaining a dissolving agent for dissolving phthalic acid crystals by thermal decomposition. Is supplied,
The waste plastic material or rubber material and the material having an amide group are thermally decomposed to obtain a thermal decomposition product, and the thermal decomposition product obtained from the thermal decomposition portion uses a solid acid catalyst. The catalytic cracking part obtained by catalytic cracking in the catalytic cracking part to obtain a catalytic cracking product, the cooling part subjecting the catalytic cracking product obtained in the catalytic cracking part to a cooling oil to obtain hydrocarbon oil, and the carbonization obtained in the cooling part And a hydrocarbon oil recovery unit for recovering hydrogen oil.

[0012]

In the method and apparatus for producing hydrocarbon oil from the waste plastic or rubber material according to the present invention as described above, the waste plastic material or rubber material is thermally decomposed, and The resulting thermal cracking product is subjected to catalytic cracking under the use of a solid acid catalyst to obtain a catalytic cracking product, and the resulting catalytic cracking product is subjected to cooling treatment to obtain a hydrocarbon oil. In doing so, the amide group-containing material that yields a dissolving agent that dissolves phthalic acid crystals by thermal decomposition is pyrolyzed together with the waste plastic material or rubber material, and the waste plastic material or rubber material is thermally decomposed. The resulting thermal decomposition product will contain a solubilizer that dissolves phthalic acid crystals.
As a result, the catalytic decomposition product obtained by catalytically decomposing the thermal decomposition product under the use of a solid acid catalyst contains a solubilizer that dissolves phthalic acid crystals.

Therefore, the waste plastic material or rubber material to be subjected to thermal decomposition is considered to contain a phthalate ester plasticizer, and the thermal decomposition product is obtained by catalytic decomposition. The substance contains phthalic acid, and when such a catalytic cracking product is cooled to obtain hydrocarbon oil from it, phthalic acid is cooled and crystallized, and is deposited on the connection part between the catalytic cracking part and the cooling part, etc. The situation is consequently prevented by a solubilizer that dissolves the phthalic acid crystals contained in the catalytic decomposition products. As a result, it is possible to avoid a situation where the cooling of the catalytic cracking product is hindered and the recovery rate of the hydrocarbon oil decreases.

[0014]

EXAMPLE FIG. 1 schematically shows an example of a hydrocarbon oil producing apparatus according to the present invention, which is used for carrying out an example of a method for obtaining a hydrocarbon oil from waste plastic or rubber material according to the present invention.

In the example of the hydrocarbon oil production apparatus shown in FIG. 1, a waste plastic material or a waste material containing a polyvinyl chloride material containing a phthalate ester type plasticizer such as dioctyl phthalate is used. A hopper 2 in which a recycled material 1 which is a rubber material is stored and a polyamide resin having an amide group, such as 6-nylon 5
And a hopper 6 in which is stored. Then, in relation to the hoppers 2 and 6, the screw conveyor 11 that crushes the recycled material 1 supplied from the hopper 2 by the rotating screw 8 and transfers it to the thermal decomposition tank 10.
And the 6-nylon 5 supplied from the hopper 6 is crushed by the rotating screw 12 and the pyrolysis tank 1
And a screw conveyor 13 for moving to 0.

The thermal decomposition tank 10 includes a screw conveyor 11
Tank main body 10C provided with inlets 10A and 10B connected to the respective outlets of the screw conveyor 13 and the outlet of the screw conveyor 13, and the regeneration supplied to the inside of the tank main body 10C from each of the inlets 10A and 10B. The material 1 and the 6-nylon 5 are composed of a heating unit 15 that heats the nylon 5 to thermally decompose it. The heating unit 15 has a thermal decomposition temperature within the range of 400 ° C. to 500 ° C. in the tank body 10C, based on the detection output from the temperature sensor 17 arranged in the tank body 10C and detecting the temperature inside the tank body 10C. It is said that the temperature adjustment control is performed so as to be maintained at.

The upper part of the tank main body 10C in the thermal decomposition tank 10 is connected to the gas introduction port 20A of the catalytic decomposition tank 20 in which the thermal decomposition gas, which is a thermal decomposition product obtained in the tank main body 10C, is catalytically decomposed. Has been done. The catalytic cracking tank 20 contains a solid acid catalyst, aluminum chloride hexahydrate 21 containing hydrochloric acid as an activator, and the thermal cracking tank 1
The pyrolysis gas supplied from the tank body 10C at 0 through the gas inlet port 20A comes into contact with the aluminum chloride hexahydrate 21 and is catalytically decomposed. The catalytic decomposition tank 20 is
The catalytic decomposition temperature within the range of 200 ° C. to 250 ° C. is set by the heating unit (not shown) in which the temperature adjustment control is performed based on the detection output from the temperature sensor 22 that detects the internal temperature. It is heated so that it is maintained at.

Gas outlet 20 in catalytic cracking tank 20
One end of a conduit 24 is connected to B. Conduit 24
Has its other end connected to a separator 25 for separating a catalytic cracking gas, which is a catalytic cracking product obtained in the catalytic cracking tank 20, into a liquid component and a gaseous component.
5 is further connected to one end of each of the conduits 27 and 28. The other end of the conduit 27 is connected to the inlet of the cooler 30 where the catalytic cracking gas is separated in the separator 25 to cool the obtained gaseous component, and the other end of the conduit 28 is 20%. Sodium hydroxide (Na
A neutralizing solution 31 called OH) extends into a neutralizing tank 32 having a built-in solution. The outlet of the cooler 30 communicates with the neutralization tank 32 via a conduit 33. The neutralization tank 32 is equipped with a rotary stirrer 34 that stirs the neutralization liquid 31. The tip of the conduit 33 extending from the outlet of the cooler 30 reaches the neutralization liquid 31 in the neutralization tank 32. Further, the conduit 27 has a screw conveyor 1
A hydrochloric acid concentration sensor 36 that sends out a detection output is interposed to a dissolved material amount control unit 35 that adjusts the rotation speed of the screw 12 in No. 3.

An intermediate portion inside the neutralization tank 32 communicates with a hydrocarbon oil recovery tank 40 containing water 39 through a conduit 38, and an upper portion inside the neutralization tank 32 is It communicates with a blower 42 via a conduit 41. The blower 42 is connected to the accumulator 4 via the conduit 43.
4 and the accumulator 44 communicates with the heating unit 15 in the thermal decomposition tank 10 via the conduit 45.

In carrying out an example of a method for obtaining a hydrocarbon oil from a waste plastic or a rubber agent according to the present invention, using the example of the hydrocarbon oil producing apparatus according to the present invention thus constructed, first, The recycled material 1 stored in the hopper 2 is supplied into the thermal decomposition tank 10 by the screw conveyor 11 and is stored in the hopper 6-6.
Nylon 5 is supplied into the thermal decomposition tank 10 by the screw conveyor 13. Then, the tank main body 10C is heated by the heating unit 15 in the thermal decomposition tank 10, and the tank main body 10C is heated.
It is in a state where the recycled materials 1 and 6-nylon 5 are thermally decomposed. At this time, the temperature adjustment control based on the detection output from the temperature sensor 17 for the heating unit 15 is performed, and the thermal decomposition temperature in the tank main body 10C is 400 ° C to
The state is maintained at a predetermined value within the range of 500 ° C.
As a result, a thermal decomposition gas that is a thermal decomposition product is obtained inside the tank body 10C by the thermal decomposition of the recycled material 1 and 6-nylon 5. Such pyrolysis gas is recycled material 1
Hydrochloric acid generated from polyvinyl chloride forming a part of polyvinyl chloride, phthalic acid generated by thermal decomposition of dioctyl phthalate contained in polyvinyl chloride, and 6-nylon 5 are obtained by thermal decomposition. It contains ε-caprolactam, which is a dissolving agent for dissolving phthalic acid crystals.

The pyrolysis gas obtained inside the tank main body 10C is introduced into the catalytic cracking tank 20 through the gas inlet port 20A provided in the catalytic cracking tank 20, and the catalytic cracking tank 20 is discharged.
It comes into contact with aluminum chloride hexahydrate 21 as a solid acid catalyst contained in the catalytic cracking tank 20, and as a result, catalytic cracking of the thermal cracking gas from the thermal cracking tank 10 is performed in the catalytic cracking tank 20. At this time, the temperature adjustment control based on the detection output from the temperature sensor 22 for the heating unit provided in the catalytic cracking tank 20 is performed, and the catalytic cracking temperature in the catalytic cracking tank 20 is within the range of 200 ° C to 250 ° C. The state is maintained at a predetermined value. Thereby, inside the catalytic cracking tank 20,
A catalytic cracking gas, which is a catalytic cracking product by catalytic cracking of the thermal cracking gas from the thermal cracking tank 10, is obtained.

The catalytic cracking gas obtained inside the catalytic cracking tank 20 is supplied to a separator 25 through a conduit 24 and separated into a liquid component and a gaseous component. The liquid component obtained in the separator 25 is supplied into the neutralization tank 32 through the conduit 28, and the gaseous component contains hydrochloric acid, phthalic acid, ε-caprolactam and the like contained in the catalytic cracking gas. And the conduit 2 provided with the hydrochloric acid concentration sensor 36.
It is supplied to the cooler 30 through 7. In doing so, the conduit 2
The concentration of hydrochloric acid contained in the gaseous component passing through 7 is detected by the hydrochloric acid concentration sensor 36. Hydrochloric acid concentration sensor 3
Reference numeral 6 supplies a detection output indicating the concentration of hydrochloric acid in the gaseous component to the dissolved material amount control unit 35.

In the dissolved material amount control unit 35, the amount of polyvinyl chloride contained in the regenerated material 1 is calculated from the detection output from the hydrochloric acid concentration sensor 36, which indicates the concentration of hydrochloric acid in the gaseous component, and the calculated amount. From the amount of polyvinyl chloride obtained, the amount of dioctyl phthalate contained in the polyvinyl chloride is obtained, and the amount of phthalic acid produced by the thermal decomposition of dioctyl phthalate in the thermal decomposition tank 10 is estimated. It Then, the control drive signal formed based on the estimated amount of phthalic acid is the dissolved material amount control unit 3
5 is supplied to the drive unit of the screw conveyor 13.
In the screw conveyor 13, the rotation of the screw 12 is adjusted by the control drive signal supplied to the drive section thereof, and as a result, the hopper 6 causes the thermal decomposition tank 10 to move into the thermal decomposition tank 10.
When phthalic acid produced by dioctyl phthalate contained in polyvinyl chloride in recycled material 1 is crystallized, an amount of 6-caprolactam capable of dissolving the crystallized phthalic acid is obtained. Nylon 5 is supplied. As a result, the pyrolysis gas obtained in the pyrolysis tank 10 contains ε-caprolactam in an amount capable of preventing crystallization of the phthalic acid contained therein.

Therefore, the phthalic acid contained in the gaseous component supplied from the separator 25 to the cooler 30 through the conduit 27 is crystallized in the portion of the conduit 27 which is brought to a relatively low temperature due to the influence of the cooler 30. If such a situation occurs, the phthalic acid crystals are dissolved by ε-caprolactam contained in the gaseous component, so that the conduit 2
The situation that 7 is blocked by the deposited phthalic acid crystals is prevented, and the gaseous component is introduced into the cooler 30 in a good condition.

The gaseous component supplied from the separator 25 to the cooler 30 is cooled by the cooler 30. Thereby, in the cooler 30, the low boiling point hydrocarbon oil based on the gaseous component and the unreacted cracked gas component are obtained. And
The low boiling point hydrocarbon oil and the unreacted cracked gas component obtained in the cooler 30 are supplied into the neutralization liquid 31 contained in the neutralization tank 32 through the conduit 33. In the neutralization tank 32, the neutralization liquid 31 that sequentially overlaps from the bottom side upwards.
Layer, the layer of the low boiling point hydrocarbon oil 50 from the cooling unit 30, and the layer of the unreacted cracked gas component 51 from the cooler 30.

The low boiling point hydrocarbon oil 50 obtained by forming the intermediate layer in the neutralization tank 32 in this manner is introduced into the conduit 38.
To the hydrocarbon oil recovery tank 40 through
The low boiling point hydrocarbon oil 50 is brought into a state of being recovered.

The unreacted decomposed gas component 51 obtained by forming the uppermost layer in the neutralization tank 32 is supplied to the blower 42 through the conduit 41. The unreacted decomposed gas component 51 supplied to the blower 42 is sent by the blower 42 to the accumulator 44 through the conduit 43, and is further supplied from the accumulator 44 to the heating unit 15 in the thermal decomposition tank 10 through the conduit 45 to heat it. It is reused in the section 15.

In this way, the regenerated material 1 is generated,
Low boiling point hydrocarbon oil 5 recovered in the hydrocarbon oil recovery tank 40
0 is recovered because the conduit 27 connecting the separator 25 and the cooler 30 is not blocked by the phthalic acid crystal, and the gaseous component from the separator 25 is guided to the cooler 30 in a good condition. It is said that the rate has been improved. Further, the low boiling point hydrocarbon oil 50 recovered in such a hydrocarbon oil recovery tank 40 is led out from the hydrocarbon oil recovery tank 40 through a conduit 52 and used as, for example, a fuel.

Depending on the amount of ε-caprolactam, ε-caprolactam recrystallizes together with phthalic acid in the neutralization tank 32. However, the recrystallized ε-caprolactam can be dissolved by washing with hot water, and therefore phthalic acid By taking out the recrystallized product of ε-caprolactam from the neutralization tank 32 and washing with hot water, the phthalic acid crystal can be recovered as a useful substance.

[0030]

As is apparent from the above description, according to the method for obtaining a hydrocarbon oil from waste plastic or rubber material and the apparatus for producing a hydrocarbon oil according to the present invention, a dissolving agent that dissolves phthalic acid crystals by thermal decomposition. The resulting amide group-containing material is pyrolyzed with the waste plastic material or rubber material, and the waste plastic material or rubber material is pyrolyzed to dissolve the phthalic acid crystals in the resulting pyrolysis product. Since a solubilizer will be included, the catalytic decomposition product obtained by catalytically decomposing the thermal decomposition product under the use of a solid acid catalyst should contain a solubilizer that dissolves phthalic acid crystals. You can Therefore, it is assumed that the waste plastic material or rubber material used for thermal decomposition contains the phthalate ester plasticizer, and the catalytic decomposition product obtained by catalytically decomposing the thermal decomposition product is phthalate. Even when it contains an acid, phthalic acid is cooled and crystallized when such a catalytic cracking product is cooled to obtain a hydrocarbon oil from the catalytic cracking product. As a result, the dissolution agent that dissolves the phthalic acid crystals contained in the catalytic cracking product can be prevented as a result, which hinders the cooling of the catalytic cracking product and reduces the recovery rate of hydrocarbon oil. It is possible to avoid the situation.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing an example of a hydrocarbon oil production apparatus according to the present invention used for carrying out an example of a method for obtaining a hydrocarbon oil from waste plastic or rubber material according to the present invention.

[Explanation of symbols]

 1 Recycled material 2,6 Hopper 5 6-Nylon 10 Thermal decomposition tank 11,13 Screw conveyor 15 Heating part 20 Contact decomposition tank 21 Aluminum chloride / hexahydrate 25 Separator 30 Cooler 32 Neutralization tank 35 Control of dissolved material amount Part 36 Hydrochloric acid concentration sensor 40 Hydrocarbon oil recovery tank

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akemi Muraoka 3-1, Shinchi, Fuchu-cho, Aki-gun, Hiroshima Prefecture Mazda Motor Corporation

Claims (5)

[Claims] 1. A waste plastic material or a rubber material is thermally decomposed in a thermal decomposition tank together with a material having an amide group capable of obtaining a dissolving agent capable of dissolving phthalic acid crystals by thermal decomposition. After the catalytic decomposition of the resulting thermal decomposition product using a solid acid catalyst to obtain a catalytic decomposition product,
A method for obtaining a hydrocarbon oil from a waste plastic or rubber material, which comprises subjecting the catalytic cracking product to a cooling treatment to obtain a hydrocarbon oil. 2. A thermal decomposition product is separated into a liquid component and a gaseous component, and the concentration of hydrochloric acid contained in the gaseous component is detected,
The method for obtaining a hydrocarbon oil from waste plastic or rubber material according to claim 1, wherein the amount of the material having an amide group to be subjected to thermal decomposition is adjusted based on the detected concentration of hydrochloric acid. 3. A plastic material or a rubber material which has been scrapped is supplied, and a material having an amide group capable of obtaining a dissolving agent capable of dissolving phthalic acid crystals by thermal decomposition is supplied, and the plastic scraped as described above. Material or rubber material and the above amide group-containing material are thermally decomposed to obtain a thermal decomposition product, and the thermal decomposition product obtained from the thermal decomposition portion is catalytically decomposed under the use of a solid acid catalyst. And a catalytic cracking part where the catalytic cracking product is obtained, a cooling part where the catalytic cracking product obtained in the catalytic cracking part is subjected to a cooling treatment to obtain hydrocarbon oil, and a hydrocarbon obtained in the cooling part A hydrocarbon oil recovery unit configured to include a hydrocarbon oil recovery unit that recovers oil. 4. A separation part for separating a thermal decomposition product into a liquid component and a gaseous component, a detection means for detecting the concentration of hydrochloric acid contained in the gaseous component obtained from the separation part, and the detection. The hydrocarbon oil production according to claim 3, further comprising a control unit for adjusting the amount of the amide group-containing material supplied to the thermal decomposition unit based on the concentration of hydrochloric acid detected by the means. apparatus. 5. The hydrocarbon oil generator according to claim 3 or 4, wherein the material having an amide group is a polyamide resin.