JP3078953B2 - Method for producing cracking catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cracking catalyst for use in producing a low-boiling hydrocarbon oil by thermally decomposing an organic material such as a waste plastic material or a waste rubber material.

[0002]

2. Description of the Related Art In recent years, in order to prevent the global environment from being polluted by wastes such as plastic materials and rubber materials, and to solve energy problems, the wastes are thermally decomposed to be reused as fuel. It is considered to be used. For example, as disclosed in JP-A-63-178195, when a polyolefin-based plastic material is thermally decomposed to produce a low-boiling hydrocarbon oil, a zeolite catalyst is used to promote the above-mentioned thermal decomposition reaction and By causing an isomerization reaction, a low-boiling hydrocarbon oil having high fluidity at low temperatures is obtained.

[0003]

As described above, in a method for producing a low-boiling hydrocarbon oil from an organic material composed of a polyolefin-based plastic waste using a zeolite catalyst, the raw material contains polyvinyl chloride or polyvinyl chloride. When a chlorine-based plastic material such as vinylidene chloride is mixed, a chlorine compound such as hydrochloric acid is generated at the time of thermal decomposition. Then, there is a problem that the zeolite catalyst is eroded by the chlorine compound and its activity is reduced early.

The present invention has been made in order to solve the above-mentioned problems. Even when a chlorine-based plastic material is mixed in an organic material such as a waste plastic material, the above-mentioned problem is prevented without erosion. It is an object of the present invention to provide a method for producing a cracking catalyst capable of effectively thermally decomposing an organic material.

[0005]

The invention according to claim 1 is
A method for producing a cracking catalyst used when a low-boiling hydrocarbon oil is produced by thermally decomposing an organic material such as waste plastic material or waste rubber material, comprising a solid acid catalyst containing aluminum chloride hexahydrate. By calcining at a temperature of 300 to 700 ° C. to release the chlorine component and water molecules in the aluminum chloride hexahydrate, it is amorphous and has a surface acid property of Lewis acid, and has a Cl / (Cl + A
l) is 0.1 to 0.2, and 180 to 240 m ²
/ G of solid acid catalyst.

[0006]

According to the first aspect of the present invention, a solid acid catalyst containing aluminum chloride hexahydrate is used at a temperature of 300 to 700 °.
By heating at the temperature of C to release the chlorine component and water molecules in the aluminum chloride hexahydrate, a chemical structure mainly composed of aluminum oxide and having a hydroxyl group or chlorine added to part of aluminum Thus, a cracking catalyst comprising an amorphous solid acid catalyst having the following formula:

[0007]

Manufacturing method of EXAMPLE cracking catalyst according to the present invention, aluminum chloride hexahydrate (AlCl ₃ · 6H ₂ O)
Is heated and calcined in the air or in a nitrogen atmosphere to release the chlorine component and water molecules in the aluminum chloride hexahydrate to produce a cracking catalyst comprising a solid acid catalyst as shown in the following formula. It is something to do.

AlCl ₃ .6H ₂ O → 1/2 Al ₂ O ₃ +3
HCl + 9 / 2H ₂ O The above calcination temperature is in the range of 300 to 700 ° C. If the calcination temperature is lower than 300 ° C., the release of chlorine components will be insufficient as described later, and if it is higher than 700 ° C., the activity as a catalyst will be lost.

The cracking catalyst comprising the solid acid catalyst produced as described above is amorphous, has a surface acid property of a Lewis acid, and has a residual chlorine component of Cl / (Cl + Al).
Of 0.1 to 0.2, and 180 to 2
It has a surface area of 40 m ² / g, and is formed by adding a hydroxyl group or chlorine to a part of aluminum mainly of aluminum oxide.

FIG. 1 shows a specific example of an oiling apparatus for producing a low-boiling hydrocarbon oil using the cracking catalyst. This oiling apparatus includes an introduction means 1 for introducing an organic material into a system, a melting tank 2 for heating and melting the introduced organic material, and a molten state drawn out of the melting tank 2 by a screw conveyor 3. A pyrolysis tank 4 for thermally decomposing the organic material, a fractionation tower 5 for fractionating a vaporous product derived from the pyrolysis tank 4 into a heavy component and a light component, and derived from the fractionation tower 5 It has a cooling tank 6 for cooling the vapor component of the light component, and a gas-liquid separation tank 7 for separating a cracked oil and a cracked gas obtained by cooling the vapor component.

At the bottom of the pyrolysis tank 4, a residue take-out section 8 is provided. Moreover, on the upper part of the thermal decomposition layer 4,
A first catalyst tank 9 filled with the cracking catalyst for cracking and reforming the gas component derived from the thermal decomposition layer 4 is provided. The fractionation tower 5 is provided with a return passage 10 for returning fractionated heavy components to the melting tank 2. A second catalyst tank 11 filled with the cracking catalyst for cracking and reforming the light components derived from the fractionation tower 5 is provided downstream of the fractionation tower 5.

The organic material introduced into the melting tank 2 from the introduction means 1 may be the following general-purpose plastic, high-performance engineering plastic or rubber. Examples of the general-purpose plastic material include polyethylene, polypropylene, polystyrene, acrylonitrile butadiene styrene, polymethyl methacrylate, and polyvinyl alcohol. Examples of the high-performance engineering plastic include polyamide, polyacetal, polycarbonate, polyphenylene ether, polybutylene terephthalate, polysulfone, polyether sulfone, polyphenylene sulfide, polyarylate, polyimide, polyamide imide, and polyether ether ketone. Can be.

The type of rubber material used as the organic material is not particularly limited, and styrene butadiene rubber, high styrene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber, ethylene propylene diene rubber, acrylonitrile Butadiene rubber,
Synthetic rubber such as chloroprene rubber, butyl rubber or urethane rubber, and natural rubber can be used.

The organic material is usually formed into pellets by previously pulverizing plastic or rubber waste into a predetermined size, and is introduced into the melting tank 2 from the introduction means 1. It has become so.
The organic material led out of the melting tank 2 into the pyrolysis tank 4 is heated and vaporized in the pyrolysis tank 4,
It is introduced into the first catalyst tank 9 and cracked.

An example of an experiment conducted on the method for producing the cracking catalyst will be described below. First, as shown in FIG.
Put the salt 13 of water salt. Then, while injecting nitrogen gas from one end of the container 12, various temperatures (200 ° C., 250 ° C., 300 ° C., 500 ° C.)
C, 700 ° C, 1000 ° C) for 1 hour. Thus, the powder of aluminum trichloride hexahydrate 13
Was calcined to produce a cracking catalyst.

Then, as shown in FIG. 3, various manufactured cracking catalysts 15 are loaded in a quartz glass container 16 and 1 g of ABS resin pellets 18 are filled in a magnetic boat 17. Then, the above A
The pellet 18 of the BS resin is heated at a temperature of 450 ° C. to generate a pyrolysis gas, and the pyrolysis gas is
An oil 19 is produced by gas-phase catalytic cracking with the racking catalyst 15 placed under the condition of 00 ° C.
The product oil 19 was subjected to a gas chromatography analyzer to detect the presence of an organic chlorine compound such as 1-chloroethylbenzene, and the following test results were obtained.

That is, aluminum chloride hexahydrate is added to 30
When a cracking catalyst fired at a temperature of 0 ° C. or more was used, no organochlorine compound was detected, whereas when a cracking catalyst at a firing temperature of 200 ° C. was used, The presence of 0.7% of an organic chlorine compound was detected in the oil, and when the firing temperature was 250 ° C., the presence of 0.2% of the organic chlorine compound was detected.

From the above test results, the firing temperature was 300 ° C.
If it is less than 3, the chlorine component in the catalyst was not sufficiently released during the calcination, and it was confirmed that the chlorine component in the catalyst was released when the low-boiling hydrocarbon oil was generated.
In addition, without baking aluminum chloride hexahydrate,
This was used as it was as a cracking catalyst, and a test was conducted in the test apparatus shown in FIG.
% Of the organic chlorine compound was detected, and it was confirmed that a large amount of the chlorine component released from the aluminum chloride hexahydrate was mixed in the generated oil.

Further, in order to confirm the release state of the chlorine component corresponding to the change in the calcination time when producing the cracking catalyst, the calcination temperature was set to 250 ° C., 300 ° C. and 350 ° C. 15 hours
The aluminum chloride hexahydrate powder was calcined for minutes, 30 minutes, 1 hour and 2 hours, and the residual ratio of aluminum chloride hexahydrate was confirmed according to the change in weight.
The test results as shown in the following were obtained.

From the above test results, 300 ° C. and 35 ° C.
After calcining aluminum chloride hexahydrate at a temperature of 0 ° C. for 1 hour, the residual ratio of aluminum chloride hexahydrate did not change, confirming that the release of chlorine component and moisture was completed. When the firing temperature is 200 ° C., 1
Even after baking for more than an hour, the residual ratio of aluminum chloride hexahydrate tended to decrease, confirming that the release of chlorine components and moisture was not completed.

Also, as described above, 300 ° C. to 700 ° C.
By examining the physical and chemical properties of the produced cracking catalyst by calcining aluminum chloride hexahydrate for 1 hour or more at the temperature of C, the following data was obtained. That is, when an infrared absorption number spectrum was prepared by infrared spectrophotometry and the chemical structure of the cracking catalyst was examined, data as shown in FIGS. 5 and 6 were obtained.

From the data shown in FIG. 5, it was confirmed from the data shown in FIG. 5 that the cracking catalyst had a chemical structure in which aluminum oxide was a main component and a hydroxyl group or chlorine was added to a part thereof. Further, from the data shown in FIG. 6, the residual amount of the chlorine component in the cracking catalyst was Cl / (Cl +
It was confirmed that the weight ratio of Al) was in the range of 0.1 to 0.2.

Next, in order to confirm whether or not the cracking catalyst has a crystal structure, an X-ray diffraction spectrum diagram was prepared by an X-ray diffraction method, and data as shown in FIG. 7 was obtained. From this data, as shown in FIGS. 7 (A) and (B), the results obtained by firing aluminum chloride hexahydrate show the existence of a crystal structure as compared with the results obtained by not firing shown in FIG. 7 (C). It was confirmed that the peak was small. In particular, as shown in FIG.
In the case of baking at a temperature of ° C. for 2 hours, no sharp peak was present, and it was confirmed that the material was amorphous.

Also, aluminum chloride hexahydrate is added at 500 °
When pyridine was adsorbed on the cracking catalyst produced by calcining at the temperature of C for 2 hours, an X-ray diffraction spectrum was prepared by an X-ray diffraction method. As shown in FIG. (1450cm ~ ¹ )
, A peak was confirmed, and the nature of the surface acid was confirmed to be a Lewis acid.

When the specific surface area of the cracking catalyst was measured, data as shown in FIG. 8 was obtained, and it was confirmed that the specific surface area was in the range of 180 to 240 m ² / g.

Next, an experiment was conducted to confirm the components of the low-boiling hydrocarbon oil produced by the oiling apparatus using the cracking catalyst, and data as shown in FIG. 10 was obtained. Note that the above experiment was conducted using the experimental apparatus shown in FIG.
0.5 g of pellets of E) and 0.1 g of cracking catalyst
Are heated at a temperature of 450 ° C. in a nitrogen atmosphere to generate a pyrolysis gas, and then the pyrolysis gas is supplied to the racking catalyst 1 placed at 280 ° C.
5 by gas phase catalytic decomposition.

From the above data, it was found that the oil produced had many components with low molecular weight and excellent cracking performance was obtained because aluminum chloride hexahydrate was heated at 300-700 ° C.
(A) and (B) were confirmed when a cracking catalyst calcined at a temperature of was used. On the other hand, when a cracking catalyst obtained by calcining aluminum chloride hexahydrate at a temperature of 1000 ° C. is used (C),
It was confirmed that the cracking performance was remarkably inferior to that of Comparative Example (D) in which unoiled aluminum chloride hexahydrate was used as a cracking catalyst, because there were many components having a large oil molecular weight.

An experiment was conducted to compare the cracking performance between the case where the aluminum chloride hexahydrate was fired in a nitrogen atmosphere and the case where the aluminum chloride was fired in air. I couldn't.

Further, aluminum chloride hexahydrate is added at 500 °
The cracking catalyst produced by calcining at a temperature of C for 2 hours is filled in the first catalyst layer 9 and the second catalyst layer 11 of the oiling apparatus shown in FIG. 1, and polypropylene (PP),
When 2 kg of pellets composed of a waste plastic material of ABS and polyethylene (PE) mixed in a ratio of 7: 1: 2 were thermally decomposed into oil, 64% by weight (1600 ml) was obtained.
Was recovered, and most of the rest was recovered as light gas components.

Thus, aluminum chloride hexahydrate was added to 30
By firing at a temperature of 0 to 700 ° C. to release a chlorine component and water in the aluminum chloride hexahydrate, a cracking catalyst used for producing a low-boiling hydrocarbon oil is manufactured. Thus, it is possible to produce a cracking catalyst that can effectively crack organic materials without being affected by chlorine compounds generated when the low-boiling hydrocarbon oil is generated.

Therefore, even when a chlorine-based plastic material is used as a raw material for producing a low-boiling hydrocarbon oil by using the cracking catalyst, the activity of the cracking catalyst does not deteriorate early. The cracking catalyst can be used for a long period of time. In addition, since the chlorine component is not generated from the cracking catalyst when the low-boiling hydrocarbon oil is generated, the low-boiling hydrocarbon oil production apparatus is effectively prevented from being corroded by the chlorine component. can do.

[0032]

As described above, according to the present invention, aluminum chloride hexahydrate is calcined at a temperature of 300 to 700 ° C. to release the chlorine component and water in the aluminum chloride hexahydrate. A cracking catalyst comprising a solid acid catalyst which is amorphous and has a surface acid property of Lewis acid, a Cl / (Cl + Al) weight ratio of 0.1 to 0.2 and a surface area of 180 to 240 m ² / g. Since it is configured to be manufactured, it is possible to manufacture a cracking catalyst that is not affected by chlorine compounds generated when the low-boiling hydrocarbon oil is generated.

Therefore, when a low-boiling hydrocarbon oil is produced by thermally cracking a raw material made of a chlorine-based plastic material using the cracking catalyst, a situation occurs in which the activity of the cracking catalyst is reduced early. Without using the cracking catalyst for a long period of time. As a result, a high-boiling hydrocarbon oil that can be effectively used as a high-quality fuel oil and a naphtha raw material can be effectively produced.

In addition, since the chlorine component is not generated from the cracking catalyst when the low-boiling hydrocarbon oil is generated, the low-boiling hydrocarbon oil production apparatus is effectively prevented from being corroded by the chlorine component. There is an advantage that it can be suppressed effectively.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an example of a low-boiling hydrocarbon oil liquefaction apparatus using a cracking catalyst produced by a production method according to the present invention.

FIG. 2 is an explanatory view showing a test device for producing the cracking catalyst.

FIG. 3 is an explanatory view showing a test apparatus for producing a low-boiling hydrocarbon oil using the cracking catalyst.

FIG. 4 is a graph showing data of a test for calcining the cracking catalyst.

FIG. 5 is an infrared absorption spectrum of the cracking catalyst.

FIG. 6 is a chart showing the amount of chlorine components remaining in the cracking catalyst.

FIGS. 7A and 7B are X-ray diffraction spectrum diagrams showing the crystal structure of a cracking catalyst produced according to the present invention, and FIG. 7C is an X-ray diffraction spectrum diagram showing the crystal structure of a cracking catalyst according to a comparative example. is there.

FIG. 8 is an infrared absorption spectrum showing the surface acid properties of the cracking catalyst.

FIG. 9 is a table showing the specific surface area of the cracking catalyst.

FIG. 10 is a gas chromatograph showing the results of a test for producing a low-boiling hydrocarbon oil using the cracking catalyst.

[Description of Signs] 15 Cracking catalyst

────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Toshitaka Takahashi 3-1 Shinchi, Fuchu-cho, Aki-gun, Hiroshima Prefecture Inside Mazda Corporation (56) References JP-A-53-172322 (JP, A) JP-A-5 -287281 (JP, A) JP-A-6-220431 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 21/00-37/36 C10G 1/10

Claims (1)

(57) [Claims] 1. A method for producing a cracking catalyst used for producing a low-boiling hydrocarbon oil by thermally decomposing an organic material such as waste plastic material or waste rubber material,
300 solid acid catalysts containing aluminum chloride hexahydrate
By firing at a temperature of about 700 ° C. to release the chlorine component and water molecules in the aluminum chloride hexahydrate, the amorphous acid having a surface acid property of Lewis acid,
When the weight ratio of 1 / (Cl + Al) is 0.1 to 0.2, 18
Method of manufacturing a cracking catalyst, characterized in that so as to produce a solid acid catalyst having a surface area of 0~240m ² / g.