JP4912776B2 - Method and apparatus for producing pyrolysis oil from rubber waste - Google Patents

Description

  The present invention relates to a method and an apparatus for producing waste pyrolysis oil for effectively using rubber waste as a resource.

  Conventional methods for treating polymer waste such as rubber waste such as waste tires and plastics have been mainly simple incineration and landfilling, but in recent years the promotion of a recycling-oriented society has become a major social issue. Therefore, effective utilization as a resource of polymer waste is demanded. Therefore, as one of waste treatment methods aiming at effective utilization of polymer waste, for example, as described in Non-Patent Documents 1, 2, and 3, polymer waste is treated in a pyrolysis furnace at 400 to 700. After generating pyrolysis gas by heating to about ℃, cool the pyrolysis gas in the later stage to separate and recover the pyrolysis oil contained in the pyrolysis gas and use it as fuel oil, etc. There is proposed a waste pyrolysis oil conversion method in which the pyrolysis gas is used as fuel gas or chemical raw material gas.

  However, as a problem of the waste pyrolysis oil conversion method, for example, as described in Non-Patent Documents 4 and 5, etc., when polymer waste is pyrolyzed, oil having a molecular weight distributed over a wide range is generated. The recovered oil is a mixture of a low molecular weight gasoline component to a high molecular weight heavy oil component, which is difficult to use as a fuel oil as it is because of safety problems and industrial value problems.

  Among these, regarding the problem of safety, for example, in pyrolysis oil conversion for waste plastic, as described in Patent Document 1, the gaseous pyrolyzate generated by pyrolyzing waste plastic is cooled and Waste plastic pyrolysis oil with a flash point of 0 ° C or less containing 20-50% of the gasoline component obtained by condensation is stripped with an inert gas to drive off the gasoline component, and safety when transporting and storing waste plastic pyrolysis oil Devices that improve the performance have been proposed.

  However, as a problem of the method of Patent Document 1, the waste plastic pyrolysis oil recovered by the method of Patent Document 1 is still a mixed oil of kerosene component, light oil component and heavy oil component. Is greatly limited and is not a method for producing waste pyrolysis oil with high industrial value.

  Therefore, as a method for producing pyrolyzed oil having high industrial value from polymer waste, particularly as a method for producing pyrolyzed oil corresponding to heavy oil having a wide industrial application using rubber waste as a raw material, Patent Document 2 discloses, for example, As described, a distillation tower having a plurality of fractionation stages is provided after the pyrolysis furnace for rubber waste, and pyrolysis oil is fractionated into specific boiling fractions for pyrolysis equivalent to heavy oil. Methods for recovering oil are disclosed and known.

  However, the problem of the method of Patent Document 2 is that it is difficult to economically recycle rubber waste because the installation of a distillation tower requires a large amount of equipment.

Therefore, as a method for producing a waste pyrolysis oil of a specific boiling fraction, particularly a pyrolysis oil equivalent to heavy oil, from rubber waste by a simple method, for example, as described in FIG. In addition, a direct-cooling type pyrolysis oil generator is provided after the rubber waste pyrolysis furnace, and the pyrolysis gas is directly heat-exchanged with the cooling oil in the pyrolysis oil generator in a countercurrent manner. And a method for recovering pyrolysis oil that uses the condensed pyrolysis oil as cooling oil for pyrolysis gas has been proposed. In this case, it is considered that a pyrolysis oil controlled to a specific boiling point range can be obtained by controlling the temperature of the cooling oil, and it is possible to produce a pyrolysis oil equivalent to heavy oil by a simple method.
“The Journal of Japan Rubber Association” Vol. 59, No. 10, P565-P567 (1986), p. 565, FIG. "Recycling Technology Research Presentation Papers" 6th, P89-P92 (1998), p. 92, Fig. 4 “Cement Manufacturing Technology Symposium” No. 57, P90-P97 (2000), page 91, FIG. Mitsubishi Heavy Industries Technical Report Vol.35, No.6 (1988), p.416, Table 3 Hitachi Zosen Technical Report Vol.57 No.2 (July 1994), p.53, Fig.5 Japanese Patent Laid-Open No. 10-245569 JP-A-53-57180 JP-A-8-11024

  However, when the present inventors produce a pyrolysis oil equivalent to heavy oil by pyrolyzing rubber-based waste, in the pyrolysis oil recovery method as in Patent Document 3, the oil is not contained in the pyrolysis oil generator. It has been found that there is a problem in that the kinematic viscosity increases and the value of the recovered oil decreases. That is, in Table 1 below, the pyrolysis gas obtained by thermally decomposing rubber waste is cooled by the distillation tower system of Patent Document 2 and the direct heat exchange system using the generated oil as the cooling oil of Patent Document 3. Then, the kinematic viscosity of the pyrolysis oil when the pyrolysis oil equivalent to heavy oil is recovered (measurement temperature 50 ° C., measurement method JIS-K2283) is shown. The oil produced by the pyrolysis oil recovery method of Patent Document 3 is It has been found that it is difficult to produce a low kinematic viscosity oil of A heavy oil level, which has a higher viscosity than the oil of the distillation tower system and has a high value among heavy oils.

  Accordingly, an object of the present invention is to provide a method and an apparatus for reducing the kinematic viscosity of pyrolysis oil equivalent to heavy oil produced from rubber waste by a simple method that is difficult with the conventional method.

  Furthermore, an object of this invention is to provide the method and apparatus which can reduce the kinematic viscosity of the pyrolysis oil manufactured from a rubber-type waste to A heavy oil (JIS-K2205) level.

  As a result of intensive studies on a method for recovering pyrolysis oil corresponding to heavy oil with low kinematic viscosity from rubber-based waste pyrolysis gas using a simple method, the present inventors have conducted a direct heat exchange system as disclosed in Patent Document 3. The reason why the pyrolysis oil recovered by using this pyrolysis oil recovery device exhibits a high kinematic viscosity is that the pyrolysis oil temporarily stored in the pyrolysis oil generator as a pyrolysis gas cooling medium is as low as about 100 to 150 ° C. It was found that the molecular weight was increased by causing a polymerization reaction even under temperature conditions, and volatile components, especially volatile diene compounds, contained in the pyrolysis oil condensed by the pyrolysis oil generator were reduced. The present inventors have found that it is possible to suppress the polymerization reaction of pyrolysis oil, and invented this method of reducing the volatile diene compound in the pyrolysis oil and suppressing the increase in kinematic viscosity of the pyrolysis oil. .

  The present invention has been proposed in order to solve such problems, and the gist thereof is as shown in the following (1) to (6).

(1) A first aspect of the present invention is a method for producing pyrolysis oil from rubber waste, in which the rubber waste is pyrolyzed to generate pyrolysis gas, and the generated pyrolysis gas is brought into contact with a cooling medium. The oily component contained in the pyrolysis gas is condensed to produce a pyrolysis oil, and a part of the produced pyrolysis oil is used as the cooling medium, and the produced pyrolysis oil is heated, Treated by at least one of contact with an inert gas or reduced pressure to reduce volatile diene compounds in the pyrolysis oil and recover after suppressing an increase in kinematic viscosity of the pyrolysis oil It is characterized by doing.

(2) The second invention is that in the method for producing pyrolysis oil from rubber-based waste of (1), an average residence time from generation to recovery by condensation of the pyrolysis oil is set to 50 hours or less. Features.

(3) The third invention is the method for producing pyrolysis oil from rubber waste according to (1) or (2), wherein the produced pyrolysis oil is heated, contacted with an inert gas, or It is characterized by adjusting the kinematic viscosity of the recovered pyrolyzed oil to 2 × 10 ⁻⁵ m ² / sec or less by treating with at least one of the methods of decompression.

(4) A fourth invention relates to a pyrolysis oil producing apparatus for pyrolysis oil from rubber waste, a pyrolysis furnace for pyrolyzing rubber waste to generate pyrolysis gas, and the generated pyrolysis gas In contact with a cooling medium to condense the oily component contained in the pyrolysis gas to produce pyrolysis oil, a pyrolysis oil cooling device that cools the produced pyrolysis oil, and In order to volatilize and remove the volatile components in the generated pyrolysis oil, at least one of heating, blowing an inert gas, or reducing the pressure is performed, and the volatile diene compound in the pyrolysis oil is reduced to reduce the heat. and suppressing devolatilizer an increase in the kinematic viscosity of the cracked oil, circulates a portion of the pyrolysis oil generating device of the pyrolysis oil and the product to the pyrolysis oil generating device through said pyrolytic oil cooler a circulation pipe to the cooling medium, the raw Characterized in that the pyrolytic oil and a recovery pipe for recovering from the pyrolysis oil generator.

(5) A fifth invention relates to a pyrolysis oil producing apparatus for pyrolysis oil from rubber waste, a pyrolysis furnace for pyrolyzing rubber waste to generate pyrolysis gas, and the generated pyrolysis gas In contact with a cooling medium to condense the oily component contained in the pyrolysis gas to produce pyrolysis oil, a pyrolysis oil cooling device that cools the produced pyrolysis oil, and A circulation pipe that circulates a part of the generated pyrolyzed oil from the pyrolyzed oil generator to the pyrolyzed oil generator through the pyrolyzed oil cooler to form the cooling medium, and the pyrolyzed oil generator It has an oil storage tank that temporarily stores the generated pyrolysis oil and can adjust the storage amount, and the oil storage tank volatilizes and removes volatile components in the generated pyrolysis oil, Reducing the volatile diene compound in the pyrolysis oil to reduce the heat A recovery pipe for recovering the temporarily stored pyrolysis oil is provided with volatile component removal means for performing at least one of heating, blowing in an inert gas, and depressurization for suppressing an increase in kinematic viscosity of deoiling. It is characterized by providing.

(6) A sixth invention is (4) Symbol in the manufacturing apparatus of the pyrolysis oil from rubber waste loading, temporarily storing the pyrolysis oil to said pyrolysis oil generating device, the pyrolysis oil and the reservoir In addition, the pyrolysis oil generator also serves as the volatile component removing device by performing at least one of heating, blowing an inert gas, and reducing pressure .

  According to the present invention, it is possible to reduce the kinematic viscosity of pyrolysis oil equivalent to heavy oil produced from rubber waste using a simple method that has been difficult with the conventional method. Furthermore, the kinematic viscosity of the pyrolysis oil can be reduced to the A heavy oil level.

Hereinafter, preferred embodiments of the present invention will be specifically described with reference to the accompanying drawings.
[First Embodiment]
FIG. 1 is a block diagram showing an example of the equipment configuration for carrying out the method and apparatus for producing pyrolysis oil from rubber waste according to the first embodiment of the present invention.

  The rubber waste 1 is quantitatively supplied into the pyrolysis furnace 3 by using a waste feeder 2 such as a screw feeder, and the rubber waste is pyrolyzed in the pyrolysis furnace 3 from the combustible gas and oil. A pyrolysis gas 4 and a pyrolysis residue 5 are formed. The method of the pyrolysis furnace 3 is not particularly limited, and a general pyrolysis method such as an external heat rotary kiln type pyrolysis furnace or a fluidized bed type pyrolysis furnace is applicable.

  The pyrolysis gas 4 is introduced into a pyrolysis oil generator 6 provided at the subsequent stage of the pyrolysis furnace 3 and directly exchanges heat with the pyrolysis gas cooling medium 10 in a counter flow, so that the oily component contained in the pyrolysis gas is present. The pyrolysis oil 7 is generated by condensing the oil, and the generated pyrolysis oil 7 is temporarily stored in the pyrolysis oil generator 6. The pyrolysis gas 11 after pyrolysis oil condensation collects light oil components, gas purification, etc. in the subsequent steps and collects combustible gas.

  As a method of directly exchanging heat between the pyrolysis gas 4 and the pyrolysis gas cooling medium 10 in a countercurrent manner, it is generally used for vapor condensation or gas absorption such as a packed tower method, a wet wall method, a spray method, or a scrubber method. Is applicable. The pyrolysis oil 7 temporarily stored in the pyrolysis oil generator 6 is a volatile diene by at least one of heating, contact with an inert gas, or decompression in order to suppress an increase in kinematic viscosity due to polymerization. Remove the compound.

  The volatile diene compound in the present invention refers to a diene compound that volatilizes from pyrolysis oil by at least one of heating, contact with an inert gas, or reduced pressure.

  The pyrolysis oil after removal of the volatile diene compound removes dust components such as carbon contained in the pyrolysis oil by using a dust removing device 13 such as a centrifuge according to the dust concentration, as a product oil 14. While recovering, a part is used as the pyrolysis gas cooling medium 8 after cooling using a cooling device 9 such as an indirect heat exchanger.

  Since the rubber waste contains diene polymers such as isoprene polymer, butadiene polymer, butadiene-styrene polymer, etc. as a constituent component, when the rubber waste is pyrolyzed, a diene compound is obtained. When the pyrolysis gas is generated and the pyrolysis gas is condensed by the pyrolysis oil generator to produce pyrolysis oil, the diene compound is mixed in the pyrolysis oil. -Alder (Diels Alder) addition reaction and other low-temperature polymerization activity, the pyrolysis oil mixed with the diene compound undergoes a polymerization reaction in a low-temperature pyrolysis oil generator at about 100 to 150 ° C, resulting in a molecular weight It has been found that an increase in the amount of volatile diene compounds in the pyrolysis oil can be reduced, and it is possible to produce a low kinematic viscosity oil by suppressing the polymerization reaction. It is intended.

  Fig. 3 shows the behavior when the pyrolysis gas of rubber waste is condensed to produce pyrolysis oil using the pyrolysis oil generator based on the above-described method, and then the resulting pyrolysis oil is subjected to diene compound reduction treatment. Kinematic viscosity ratio with kinematic viscosity when not measured for diene compound reduction [that is, kinematic viscosity ratio = {(50 ° C. kinematic viscosity of pyrolysis oil with diene compound reduction treatment) / (heat without diene compound reduction treatment) The example shows a comparison of cracked oil at 50 ° C kinematic viscosity)}], but it is possible to reduce the kinematic viscosity to about half or less of the pyrolyzed oil subjected to the diene compound reduction treatment compared to the pyrolysis oil not subjected to the reduction treatment. It is. Note that the absolute value of the kinematic viscosity tends to increase with time, and is particularly remarkable when the volatile diene compound reduction treatment is not performed.

  Whether the volatile diene compound has been reduced can be determined by comparing the peak intensity of the diene compound with a gas chromatograph mass spectrometer (GC-MS) before or after the reduction treatment, or the diene value (iodine). It can be confirmed by comparing whether or not the amount of the diene compound after the reduction treatment is relatively decreased by comparing (also referred to as a value and defined in JIS-K0070).

  As a specific example of the means for reducing the diene compound in the pyrolysis oil described above, for example, as shown in FIG. 1, an inert gas 12 is blown into the pyrolysis oil once stored in the pyrolysis oil generator so that the diene compound. In addition to the method of lowering the gas phase partial pressure and removing the volatilization, a method of volatilizing and removing the diene compound by making the inside of the pyrolysis oil generator a reduced pressure atmosphere using a suction blower provided at the subsequent stage of the pyrolysis oil generator, A general method for separating and removing volatile substances such as a method of heating the pyrolysis oil generated in the pyrolysis oil generator using an indirect heat exchanger or the like can be applied.

  In this case, the operation conditions such as the flow rate of the inert gas, the set pressure in the apparatus at the time of decompression, the heating temperature, and the like may be appropriately set while observing the degree of suppression of the increase in the kinematic viscosity of the pyrolysis oil.

[Second Embodiment]
Furthermore, as shown in FIG. 2, the pyrolysis oil produced | generated by the pyrolysis oil production | generation apparatus 15 is supplied to the oil storage tank 18 provided with the inert gas blowing apparatus, and is made to contact with an inert gas in an oil storage tank. It is possible to further improve the diene removal performance. Note that the volatile diene compound may be removed by combining heating, depressurization, or contact with an inert gas, heating, or depressurization instead of contacting with the inert gas.

  FIG. 2 is a block diagram showing another apparatus configuration example for carrying out the pyrolysis oil kinematic viscosity adjusting method and apparatus of the rubber waste pyrolysis method according to the second embodiment of the present invention. A significant difference from the first embodiment described above is that an oil storage tank 18 including an inert gas blowing device is provided. Oil provided with an inert gas blowing device after the pyrolysis oil 16 obtained by condensing the pyrolysis gas 4 with the pyrolysis oil generator 15 removes dust such as carbon with the dust removal device 17 according to the dust concentration. Supply to the storage tank 18. At this time, a part of the pyrolysis oil 16 is cooled by the cooling device 9 and circulated through the pyrolysis oil generation device 15 through a circulation pipe. The pyrolysis oil is brought into contact with an inert gas in the oil storage tank 18 to transfer the diene compound in the pyrolysis oil to the gas phase side and removed together with the exhaust gas 20. The pyrolyzed oil after removal of the diene compound is recovered as product oil 21, but if the amount of dust brought into the pyrolyzed oil generator 15 accompanying the pyrolyzed gas is large, a part of the product oil is taken as necessary. It returns to the pyrolysis oil production | generation apparatus 15 via the pyrolysis oil return piping 22, and dust accumulation in a pyrolysis oil production | generation apparatus is prevented.

  The diene compound removal method according to the second embodiment performs volatilization and removal of the diene compound by blowing an inert gas in an atmosphere that does not coexist with the pyrolysis gas. There is no change in the decomposition gas composition, and the diene partial pressure on the gas phase side can be kept constant, so that more stable diene compound removal can be performed.

  In the second embodiment, as a method for removing the diene compound, in addition to the removal in the oil storage tank 18, the pyrolysis oil generator 15 is the same as the method described in the first embodiment. It may be removed by a method. In this case, more reliable removal is possible by removing the diene compound in both the oil storage tank 18 and the pyrolysis oil generator 15.

  In the first embodiment and the second embodiment described above, applicable inert gas species include general inert gases such as nitrogen, carbon dioxide, and water vapor. Combustible gases other than inert gases and gas species reactive with pyrolysis oil are not preferable from the viewpoint of safety (risk of fire and explosion) and product oil quality.

  The target volatile diene compound to be removed from the pyrolysis oil is preferably a diene compound having a boiling point of about 250 ° C. or lower, such as cyclooctadiene, dimethylcyclohexadiene, or dimethylcyclopentadiene. This is because when a diene compound having a boiling point exceeding 250 ° C. and a higher boiling point is included in the removal target, the proportion of the low molecular weight oil component in the pyrolysis oil that volatilizes with the diene compound increases, and the average of the pyrolysis oil This is because the molecular weight is increased, so that the effect of suppressing the increase in kinematic viscosity by removing the diene compound is saturated, and the kinematic viscosity may increase instead.

The amount of inert gas blown to remove the diene compound varies depending on the temperature and quality of the pyrolysis oil. For example, when the pyrolysis oil temperature is 130 to 140 ° C., the amount of pyrolysis oil recovered (m ³ -Oil) Then, if an inert gas is blown in an amount of about 50 to 100 Nm ³ / m ³ -Oil and brought into contact with the pyrolysis oil, a diene compound having a boiling point of about 250 ° C. or less can be removed.

  Further, in addition to removing the volatile diene compound by the above-mentioned means, the average of the pyrolysis oil from the condensation in the pyrolysis oil generators 6 and 15 to the recovery as the product oils 14 and 21 is further obtained. By setting the residence time to be 50 hours or less, the increase in kinematic viscosity of the pyrolysis oil can be further suppressed.

  As a result of investigating the reaction characteristics of the pyrolysis oil after contact with an inert gas to remove the diene compound, the inventors have conducted pyrolysis in the pyrolysis oil generator and the oil storage tank as shown in FIG. It has been found that an increase in kinematic viscosity due to polymerization of a high-boiling diene compound or the like remaining in the pyrolysis oil can be avoided by adjusting the average oil residence time to 50 hours or less.

  For example, when the amount of pyrolysis oil generated is reduced by switching to an operation that reduces the waste treatment speed in the pyrolysis furnace, the average residence time of pyrolysis oil in the pyrolysis oil production apparatus and oil storage tank is 50 hours or less The product oil can be maintained at a low kinematic viscosity by adjusting so as not to exceed.

As a method for adjusting the average residence time of pyrolysis oil, the following methods can be typically exemplified.
That is, for example, when the pyrolysis oil generation basic unit per waste unit processing amount is investigated in advance and the waste processing speed is changed, the pyrolysis oil volume in the pyrolysis oil generator or oil storage tank is changed. 1 is changed to the following formula {(set value of pyrolysis oil volume in the pyrolysis oil generator) / (waste treatment speed × pyrolysis oil generation basic unit)} ≦ In the configuration example of FIG. 2, the following formula {(set value of pyrolysis oil volume in pyrolysis oil generator and oil storage tank) / (waste treatment) Speed × pyrolysis oil generation unit)} ≦ 50 It is possible to include a method of adjusting the pyrolysis oil volume so as to satisfy 50 hours.

Further, for example, the pyrolysis oil volume in the pyrolysis oil generator or oil storage tank is maintained at a constant level using a liquid level meter or the like, and the pyrolysis oil from the pyrolysis oil generator or oil storage tank is also maintained. 1 is measured, and in the configuration example of FIG. 1, pyrolysis is performed so as to satisfy the following formula {(pyrolysis oil volume in pyrolysis oil generator) / (pyrolysis oil extraction speed)} ≦ 50 hours. The oil extraction speed is adjusted, and in the configuration example of FIG. 2, the following formula {(pyrolysis oil volume in pyrolysis oil generator and oil storage tank) / (pyrolysis oil extraction speed)} ≦ 50 hours is satisfied A method of adjusting the extraction speed of the pyrolysis oil can be mentioned.

  In addition to the above methods, various methods that can be considered as means for adjusting the residence time in a continuous tank reactor or the like can be applied.

Example 1
In the following, an example in which a waste tire, which is a rubber waste, is treated at a treatment scale of 200 t / day to produce pyrolysis oil equivalent to heavy oil, using the configuration example of the first embodiment shown in FIG. .

  An externally heated rotary kiln equipped with an LNG-fired hot air generator is used as the pyrolysis furnace, and the pyrolysis oil generator is directly heat-exchanged with the cooling medium in a countercurrent to condense the oily components as pyrolysis oil. As a method of removing diene compounds from pyrolysis oil, a pyrolysis oil temporarily stored in the pyrolysis oil generator is not used. A method in which nitrogen gas was blown as an active gas to volatilize and remove the diene compound was used, and a centrifuge was used as a dust removing device from pyrolysis oil.

Waste is charged into a pyrolysis furnace to produce pyrolysis gas and pyrolysis residue, and the pyrolysis gas is introduced into the pyrolysis oil generator and brought into contact with the pyrolysis gas cooling medium so that the pyrolysis oil is about 1 m. ³ / hr recovered, nitrogen gas is blown into the recovered pyrolyzed oil at 80 Nm ³ / hr to make contact with the pyrolyzed oil, and the pyrolyzed oil after contact with the nitrogen gas is treated with a centrifuge to focus on carbon dust. The dust content was separated and removed as sludge, and the pyrolysis oil after the dust separation and removal was recovered as product oil. The volume of pyrolysis oil in the pyrolysis oil generator was set to about 30 m ^3, and the average residence time of pyrolysis oil was about 30 hours.

The recovered product oil has a kinematic viscosity (measuring temperature 50 ° C.) 1.8 × 10 ^{−5 to} 2.5 × 10 ⁻⁵ m ² / sec (18 to 25 cSt), flash point 60 to 90 ° C., and rubber-based disposal It was possible to produce an oil equivalent to heavy oil having a low viscosity comparable to that of heavy oil A. When the molecular weight of the product oil was measured, it was a weight average molecular weight of 250 to 300.

  Gas chromatograph mass spectrometer (GC-MS) collects the product oil recovered without conducting a trial of removing the diene compound by volatilizing and removing nitrogen gas into the pyrolysis oil temporarily stored in the pyrolysis oil generator. As a result of component analysis in Fig. 1, peaks of plural kinds of diene compounds having about 5 to 10 carbon atoms such as cyclooctadiene and dimethylcyclopentadiene were detected, but in the product oil recovered by performing the operation of Example 1. The peak of the diene compound having about 5 to 10 carbon atoms disappeared or decreased to less than half, and it was confirmed that the diene compound was reduced by blowing nitrogen gas.

(Example 2)
In the following, using the configuration example of the second embodiment shown in FIG. 2, an example in which pyrolytic oil equivalent to heavy oil is produced by treating waste tires at a treatment scale of 200 t / day in the same manner as in Example 1 will be shown. .

  As in the first embodiment, an externally heated rotary kiln equipped with an LNG-fired hot air generator is used as the pyrolysis furnace, and as a pyrolysis oil generator, an oily component is obtained by directly exchanging the pyrolysis gas with a cooling medium in countercurrent As a method for removing diene compounds from pyrolysis oil, the condensed pyrolysis oil is removed by dust. After that, a method is used in which the diene compound is volatilized and removed by contacting the pyrolysis oil with an inert gas in an oil storage tank provided with a nitrogen gas blowing device. A centrifuge was used as the dust removing device.

Waste is charged into a pyrolysis furnace to produce pyrolysis gas and pyrolysis residue, and the pyrolysis gas is introduced into the pyrolysis oil generator and brought into contact with the pyrolysis gas cooling medium so that the pyrolysis oil is about 1 m. ³ / hr, and the generated pyrolysis oil is separated and removed as sludge by a centrifuge and then supplied to the oil storage tank. Nitrogen gas in the oil storage tank is blown in at 70 Nm ³ / hr to generate pyrolysis oil and The pyrolysis oil after contact with nitrogen gas was recovered as product oil. The pyrolysis oil volume in the pyrolysis oil generator and the oil storage tank was set to about 30 m ^3, and the average residence time of the pyrolysis oil was about 30 hours.

In this Example 2, since the stability of diene removal performance was improved compared to Example 1 by blowing an inert gas into an atmosphere without the presence of pyrolysis gas and performing volatilization removal of the diene compound, the recovered product oil Is kinematic viscosity (measurement temperature 50 ° C.) 1.7 × 10 ^{−5 to} 2.0 × 10 ⁻⁵ m ² / sec (17 to 20 cSt), flash point 70 to 80 ° C. It was possible to produce an oil equivalent to heavy oil with low viscosity.

(Comparative Example 1)
As Comparative Example 1, the inert gas was not blown into the pyrolysis oil temporarily stored in the pyrolysis oil generator and the diene compound was not removed by decompression. The other conditions were the same as in Example 1, and Waste tires with the same properties were treated at the same throughput of 200 t / day.

The product oil after removing dust with a centrifuge has a kinematic viscosity (measured temperature 50 ° C.) 5.0 × 10 ^{−5 to} 1.5 × 10 ⁻⁴ m ² / sec (50 to 150 cSt), flash point 60 to 90. It became oil with high viscosity and low industrial value compared with Example 1. Further, when the molecular weight of the recovered product oil was measured, the weight average molecular weight was 300 to 400, and it was found that the molecular weight was increased due to the progress of the polymerization of the pyrolysis oil as compared with Examples 1 and 2 above. It was.

(Example 3)
As Example 3, an example in which pyrolysis oil corresponding to heavy oil was produced using the same equipment as in Example 2 under the operating conditions in which the waste tire processing speed was reduced to 100 t / day and half that of Example 2 was shown.

The waste is charged into a pyrolysis furnace to produce pyrolysis gas and pyrolysis residue, and the pyrolysis gas is introduced into the pyrolysis oil generator and brought into contact with the pyrolysis gas cooling medium to reduce the pyrolysis oil to about 0. .5m ³ / hr is generated, and the generated pyrolysis oil is separated and removed by using a centrifugal separator as sludge, then supplied to the oil storage tank, and nitrogen gas in the oil storage tank is blown at 35 Nm ³ / hr for thermal decomposition. It was made to contact oil and the pyrolysis oil after nitrogen gas contact was collect | recovered as product oil.

Further, the set value of the liquid level of the oil storage tank is lowered as compared with the second embodiment, the pyrolysis oil volume in the pyrolysis oil generator and the oil storage tank is adjusted to 20 to 25 m ³ , and the oil storage tank and the heat The average residence time of the pyrolysis oil in the cracked oil production | generation apparatus was adjusted so that it might be 50 hours or less.

The recovered product oil had a kinematic viscosity (measurement temperature 50 ° C.) of 1.9 × 10 ^{−5 to} 2.0 × 10 ⁻⁵ m ² / sec (19 to 20 cSt) and a flash point of 70 to 80 ° C. Oil with almost the same properties as the above.

Example 4
As Example 4, the pyrolysis oil equivalent to heavy oil is generated under the condition that the processing speed of the waste tire is reduced to 100 t / day and half that of Example 2 as in Example 3, and the oil storage tank and the pyrolysis oil generation device An example of operation under the same conditions as in Example 3 is shown except that the volume of pyrolysis oil inside is 30 m ³ which is the same as that in Example 2.

The recovered product oil had a kinematic viscosity (measured temperature: 50 ° C.) 2.5 × 10 ^{−5 to} 3.5 × 10 ⁻⁵ m ² / sec (25 to 35 cSt) and a flash point of 70 to 80 ° C. Example 3 Oil with an increased kinematic viscosity was obtained.

FIG. 1 is a block diagram showing an example of equipment of the apparatus according to the first invention of the present invention. FIG. 2 is a block diagram showing another facility example of the apparatus according to the first invention of the present invention.

FIG. 3 shows the kinematic viscosity ratio (= diene compound) of the kinematic viscosity (measured temperature 50 ° C.) of the pyrolyzed oil subjected to reduction treatment of the diene compound and the pyrolysis oil not treated with diene compound reduction according to the first invention of the present invention. FIG. 4 is a correlation diagram of the kinematic viscosity of pyrolysis oil with reduction treatment / kinematic viscosity of pyrolysis oil without diene compound reduction treatment) and the average residence time of pyrolysis oil in the pyrolysis oil generator and oil storage tank.

FIG. 4 is a correlation diagram between the average residence time of the pyrolysis oil and the kinematic viscosity (measurement temperature 50 ° C.) of the pyrolysis oil in the pyrolysis oil generator and the oil storage tank according to the second invention of the present invention. is there.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Rubber waste, 2 ... Waste supply apparatus, 3 ... Pyrolysis furnace, 4 ... Pyrolysis gas, 5 ... Pyrolysis residue, 6 ... Pyrolysis oil production | generation apparatus, 7 ... Pyrolysis oil, 8 ... Pyrolysis Gas cooling medium, 9 ... Cooling device, 10 ... Pyrolysis cooling medium after cooling, 11 ... Pyrolysis gas after condensation of pyrolysis oil, 12 ... Inert gas, 13 ... Dust removal device, 14 ... Product oil, 15 ... Heat Decomposed oil generation device, 16 ... pyrolysis oil, 17 ... dust removal device, 18 ... oil storage tank, 19 ... inert gas, 20 ... exhaust gas, 21 ... product oil, 22 ... pyrolysis oil return pipe.

Claims (6)

  Pyrolysis gas is generated by pyrolyzing rubber waste, and the generated pyrolysis gas is brought into contact with a cooling medium to condense oil components contained in the pyrolysis gas to generate pyrolysis oil, A part of the generated pyrolytic oil is used as the cooling medium, and the generated pyrolytic oil is treated by at least one of heating, contact with an inert gas, or reduced pressure, and the pyrolysis is performed. A method for producing pyrolytic oil from rubber-based waste, characterized in that volatile diene compounds in the oil are reduced and the increase in kinematic viscosity of the pyrolytic oil is suppressed and then recovered.   The method for producing pyrolytic oil from rubber-based waste according to claim 1, wherein an average residence time from generation to recovery by condensation of the pyrolytic oil is 50 hours or less. The generated pyrolysis oil is treated by at least one of heating, contact with an inert gas, or reduced pressure, and the kinematic viscosity of the recovered pyrolysis oil is 2 × 10 ⁻⁵ m ² / sec or less. The method for producing pyrolysis oil from rubber-based waste according to claim 1 or 2, wherein A pyrolysis furnace for pyrolyzing rubber waste to generate pyrolysis gas, and contacting the generated pyrolysis gas with a cooling medium to condense the oily components contained in the pyrolysis gas and pyrolyzing oil A pyrolysis oil generator for generating the pyrolysis oil, a pyrolysis oil cooling device for cooling the generated pyrolysis oil, and heating and blowing an inert gas to volatilize and remove volatile components in the generated pyrolysis oil. From the volatile component removing device that reduces the volatile diene compound in the pyrolysis oil and suppresses the increase in the kinematic viscosity of the pyrolysis oil, and the pyrolysis oil generator A circulation pipe that circulates a part of the generated pyrolysis oil to the pyrolysis oil generator through the pyrolysis oil cooler as the cooling medium, and the generated pyrolysis oil from the pyrolysis oil generator. With recovery piping to recover Preparative pyrolysis oil of an apparatus for manufacturing a rubber waste, wherein. A pyrolysis furnace for pyrolyzing rubber waste to generate pyrolysis gas, and contacting the generated pyrolysis gas with a cooling medium to condense the oily components contained in the pyrolysis gas and pyrolyzing oil The pyrolysis oil generator that generates the pyrolysis oil, the pyrolysis oil cooler that cools the generated pyrolysis oil, and the pyrolysis oil generator that generates the pyrolysis oil from the pyrolysis oil generator through the pyrolysis oil cooler. A circulation pipe that circulates a part of the pyrolysis oil to serve as the cooling medium , and an oil storage tank that temporarily stores the pyrolysis oil generated by the pyrolysis oil generator and can adjust the storage amount. The oil storage tank has a volatile component in the generated pyrolysis oil removed by volatilization to reduce a volatile diene compound in the pyrolysis oil and increase the kinematic viscosity of the pyrolysis oil. Heating, inert gas blowing, or Provided with a least volatile component removing means for performing any of the pressure, pyrolysis oil of an apparatus for manufacturing a rubber waste, characterized in that it comprises a recovery pipe for recovering the pyrolysis oil which stores the temporarily. The pyrolysis oil is temporarily stored in the pyrolysis oil generation device, and the pyrolysis oil generation device is volatile by performing at least one of heating, blowing an inert gas, and decompressing the stored pyrolysis oil. pyrolysis oil of an apparatus for manufacturing a rubber waste according to claim 4 Symbol mounting, characterized in that also serves as a component removal device.

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