KR20180138188A - Recovery method of d-limonene by fast pyrolysis of waste tire and pyrolysis oil distillation and oil thereof - Google Patents

Abstract

Disclosed are a method for recovering di-limonene by rapid pyrolysis of waste tires and pyrolysis oil distillation and recovered oil using the same. The method for recovering di-limonene of the present invention comprises following steps of: (a) rapidly pyrolyzing the waste tire by injecting the same into a conical spray layer reactor; (b) condensing gas obtained by rapid pyrolysis in the reactor to pyrolyze the waste tire to extract oil; and (c) recovering di-limonene by subjecting the oil extracted in the step (b) to reduced-pressure fractional distillation. Accordingly, carbon black generated in the rapid pyrolysis process of the waste tire can be effectively discharged, thereby improving performance of rapid pyrolysis. Therefore, pyrolysis oil of the waste tire for producing di-limonene can be produced with high yield and improved quality.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for recovering di-limonene from waste tire quick-pyrolysis and pyrolysis oil distillation, and a method for recovering di-limonene from pyrolysis oil distillation,

The present invention relates to a method for recovering di-limonene, and more particularly, to a method for recovering di-limonene by rapid thermal decomposition of a waste tire to produce a waste tire thermal decomposition oil as a liquid product, Limonene recovery through waste tire quick pyrolysis and pyrolysis oil distillation, and recovered oils using the same.

Waste tires are wastes equivalent to polymer chemicals, and the amount of waste generated is increasing year by year due to the increase of automobile number due to the increase of industrial activities of mankind. In addition, domestic waste tire management is shifting from obsolete processing to obligation processing through Extended Producer Responsibility (EPR).

On the other hand, the domestic recycling of waste tires is largely bulky at the time of landfilling and it takes a long time for biodegradation, and thus it is difficult to secure a landfill site. Therefore, most of them rely on thermal recycling. However, It is not environmentally friendly, and there is a limit to the limited use of waste heat as a heat source.

Accordingly, these problems have created an opportunity to highlight the importance of developing a technology that can stably and economically regenerate waste tires.

The thermochemical conversion process, which is a technology using waste as an energy source, is generally divided into combustion, gasification and pyrolysis depending on the amount of oxygen. Among them, the pyrolysis process indirectly heats at 400 ~ 600 ℃ in anaerobic condition. Is a technology to obtain pyrolysis oil, which is mainly a liquid product, and it is an eco-friendly treatment technology which generates pollutants such as air pollution flue gas and dust unlike a combustion reaction.

The waste tires can be thermally decomposed to recover useful substances such as liquid (pyrolysis oil), solid (carbon black, iron core), gas phase (synthesis gas), etc. If the useful substance is subjected to an additional purification process It can be reused as a higher value added material, and in the case of syngas, it is used as a fuel that can produce steam and electricity.

The pyrolysis oil of the waste tire is composed of various organic compounds including an aromatic compound and a nitrogen / oxygen-containing compound, and is a high-value hydrocarbon such as benzene, toluene, xylene, limonene, . The d-limonene contained in the pyrolysis oil has the same characteristics as the d-limonene extracted from lemon or orange peel, which is a natural material, and the chemical formula (C ₁₀ H ₁₆ ) And it is considered that some of the imported d-limonene can be partially substituted.

Therefore, it is absolutely necessary to develop a rapid pyrolysis reactor dedicated to waste tires that can rapidly pyrolyze waste tires to recover di-limonene, which is a high-value-added substance. (Fractional distillation) is required to develop a device having the characteristic of fractional distillation.

Korean Registered Patent No. 1,744,558 (registered on June 1, 2017) Korean Registered Patent No. 1,230,332 (registered on March 31, 2013) Korean Registered Patent No. 943,671 (registered on Feb. 16, 2010)

 Lee, Kyungmin, Effect of Pyrolysis Condition on Recovery of Aromatic Compound in Waste Tire, Dept. of Sogang University (MS), 2009  Lee Jin-heon, Purification of Pyrolysis Oil from Waste Tire, Dept. of Chonnam National University, 2002  Park, Jin - Woo, Pyrolysis Characteristics and Kinetics of Waste Tires, Korean Journal of Environmental Engineering Vol. 1, No. 8, pp. 1595-1607, 1999  No Jae-Kyung, Recovery of useful components of waste tire through pyrolysis, Dept. of Hanyang University (MS), 1995

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a process for producing a waste tire by subjecting waste tires to rapid pyrolysis through development of rapid pyrolysis process technology of waste tires and recovery technology of di- Limonene recovery method using waste tire rapid thermal cracking and pyrolysis oil distillation capable of producing a commercial product from waste resources by providing a method of recovering di-limonene through reduced-pressure fractional distillation of the pyrolysis oil, And to provide recovered oil.

A method for recovering di-limonene by pyrolysis oil distillation using a di-limonene manufacturing system using waste tires according to an embodiment of the present invention includes the steps of (a) charging a waste tire into a conical spray layer reactor (B) condensing the gas obtained by the rapid pyrolysis in the reactor to pyrolyze waste tires to extract oil; and (c) separating the oil extracted in the step (b) - recovering the limonene.

wherein the step (a) further comprises feeding into the conical spray bed reactor by means of a sample dosing device, wherein the rapid pyrolysis is carried out in a temperature range of 400 to 700 ° C, and the condensation gas in the conical spray bed reactor To the outside.

Further, in the step (a), after completion of the rapid pyrolysis, the gas, the sand and the carbon black may be discharged to the outside of the conical spray layer reactor, and the sand and the carbon black may be separated from the gas through the cyclone.

The fractional distillation of step (c) is carried out at a temperature ranging from 96 to 175 캜, and is carried out at a pressure ranging from 60 to 760 mmHg.

Further, it is possible to further comprise a step of recirculating the condensed liquid product to the fractionation column for the reflux effect after condensing the vapor generated in the step (c) with a dim-rod reflux condenser provided on the fractionation column to be.

D-limonene manufacturing system using waste tires

A conical spray layer reactor for carrying out a rapid thermal decomposition reaction of waste tires introduced using a fluidized bed; a sample dosing device for supplying a waste tire provided in the upper part of the conical spray layer reactor; A carbon black discharge port connected to one side of the conical spray layer reactor for discharging carbon black, and a pyrolysis gas, carbon black and sand of a waste tire discharged from the conical spray layer reactor A condenser and an electrostatic precipitator for condensing and collecting the waste tire thermal decomposition oil in the pyrolysis gas from which the carbon black has been removed from the cyclone and an electrostatic precipitator for collecting the carbon black and the sand contained in the pyrolysis gas, Distillation material is extracted through vacuum fractionation distillation It is D-limonene may comprise a recovery unit.

In addition, the spray layer reactor has an inverted conical structure in which the cross-sectional area increases with height, and the carbon black outlet is installed inside the conical spray layer reactor, and the height thereof is adjusted while the opening portion is directed upward.

In addition, the discharge port through which the sample is injected in the sample quantitative dosing device is directed downward to discharge the sample to the upper end of the solid particle layer in the spray layer reactor.

Also, the gas supplied to the gas inlet of the conical spray layer reactor is characterized by controlling the gas flow rate by the flow meter and the regulator, and regulating the gas flow rate in the conical spray layer reactor.

On the other hand, the oil produced according to the di-limonene recovery method has a yield of 50 wt.% Or more, an oil calorific value of 42 MJ / kg (10,000 kcal / kg) or more and a water content of oil of 5 wt. .

Therefore, the method for recovering di-limonene by the rapid pyrolysis of waste tire and the pyrolysis oil distillation according to an embodiment of the present invention and the oil recovered using the method can effectively discharge carbon black generated in the waste tire rapid pyrolysis process, The pyrolysis performance can be improved and the pyrolysis waste tire for producing di-limonene can be produced with high yield and improved quality.

In addition, the pyrolysis oil, which is one of useful resources generated in the waste tire rapid thermal decomposition system according to the present invention, can be used as a fuel for boiler and power generation in addition to the purpose of recovering di-limonene, and carbon black can be used as a rubber reinforcing agent, It can be used as a raw material for an adsorbent and the like, and is thus excellent in terms of recycling waste resources.

On the other hand, when the pyrolysis oil produced according to the present invention is subjected to the reduced pressure fractionation step, distillation can be performed at a temperature lower than the original boiling point of the liquid when the pressure is lowered, thereby reducing the amount of heat energy required and increasing the heat transfer rate inside the distillation apparatus .

According to the present invention, the d-limonene manufacturing system using waste tires is more cost competitive than the orange extract di-limonene because of its high cost competitiveness. Accordingly, the total amount of the orange extract di-limonene used as the conventional industrial detergent It is economical because it can be used as a partial substitute for income.

1 is a block diagram schematically showing a di-limonene manufacturing system using a waste tire according to an embodiment of the present invention.
FIG. 2 is a block diagram of a waste tire rapid thermal decomposition system according to an embodiment of the present invention. Referring to FIG.
3 is a view showing a conceptual diagram of a fractionation device according to an embodiment of the present invention.
FIG. 4 is a configuration diagram showing a configuration of a de-limonene recovery apparatus according to an embodiment of the present invention in more detail.
FIG. 5 shows the yield of the product produced by rapid pyrolysis of a waste tire under the reaction temperature condition according to Experiment 1. FIG.
6 shows the moisture content, calorific value and viscosity of the pyrolysis oil produced by the rapid thermal decomposition of the waste tire under the reaction temperature condition according to Experiment 1.
FIG. 7 shows the yield of the product produced by rapid pyrolysis of a waste tire under an inlet velocity condition of nitrogen gas according to Experiment 1. FIG.
8 shows the moisture content, the calorific value and the viscosity of the pyrolysis oil produced by rapid pyrolysis of a waste tire under an inlet velocity condition of nitrogen gas according to Experiment 1.
9 is a graph showing the yield of a product produced by rapid pyrolysis of a waste tire under the condition of the input rate of the sample according to Experiment 1.
10 shows the moisture content, the calorific value and the viscosity of the pyrolysis oil produced by rapid pyrolysis of the waste tire under the input rate condition of the sample according to Experiment 1.
Fig. 11 shows GC / MS analysis of pyrolysis oil produced by rapid thermal decomposition of waste tire according to Experiment 1. Fig.
12 shows the efficiency of the di-limonene recovery apparatus according to the variation of distillation time according to Experiment 2.
13 is a GC / MS analysis of the pyrolysis oil of the waste tire according to the distillation time change according to Experiment 2.

Hereinafter, embodiments according to the present invention will be described in detail with reference to the accompanying drawings. However, the following examples are intended to assist the understanding of the present invention, and the present invention is not intended to be limited or limited by the embodiments.

Hereinafter, the present invention will be described in more detail with reference to the drawings.

FIG. 1 is a schematic view showing a system for producing di-limonene using a waste tire according to an embodiment of the present invention. FIG. 2 is a schematic view showing a structure of a waste tire rapid thermal decomposition system according to an embodiment of the present invention, Fig.

Referring to FIGS. 1 and 2, a rapid pyrolysis system for a waste tire according to an embodiment of the present invention is an apparatus for producing pyrolysis oil from a polymer compound or a mixture using a rapid pyrolysis technique.

The method for recovering di-limonene according to the present invention comprises the steps of: a) developing a di-limonene manufacturing system using a waste tire, using a rapid thermal decomposition technique, and b) introducing waste tires into a conical spray layer reactor And c) condensing the gas obtained by the rapid pyrolysis in the reactor to extract pyrolysis oil of waste tire; and d) recovering di-limonene by subjecting the extracted oil to reduced-pressure fractional distillation .

On the other hand, the reactor in which the reaction is performed in the rapid pyrolysis process is the core of the whole process, and the characteristics of the process and the pyrolysis product change depending on the kind of the reactor. Conditions required for rapid pyrolysis include rapid heating rates of 1,000 to 10,000 ° C / s, pyrolysis temperature of 500 ° C, and pyrolysis product retention time of 1 to 2 seconds. Research has been conducted. Generally, the reactors currently being developed and in use include a bubble fluidized bed, a circulating fluidized bed, a sprayed bed, a conical, and a spiral type reactor. The reactor according to an embodiment of the present invention uses a spray layer reactor.

As shown in FIG. 1, the spray layer reactor has an inverted conical structure in which the cross-sectional area increases with height. The conical spray layer rapid pyrolysis reactor is excellent in heat and mass transfer and can operate irregular and highly viscous materials as compared with commonly used bubbling fluidized bed reactors, thus saving energy required for particle grinding. In addition, the conical spray layer reactor is suitable for continuous operation because it has less pressure loss than the fluidized bed reactor because there is no dispersion plate in the conical spray layer, and because of the short retention time in the reactor in the lean phase spray layer region, Which has a higher advantage than the reactor.

The waste tire rapid pyrolysis system according to the present invention includes a conical spray layer reactor 10, a sample dosing device 20 coupled to the upper end of the reactor, a heater 30, a cyclone 40, a condenser 50, an electrostatic precipitator 60 ).

The conical spray layer reactor 10 is a device for injecting a high-temperature gas through a heater 30 and rapidly pyrolyzing a sample supplied from an internal and external heating source sample dosing device 20 using a high-temperature fluidized yarn. In addition, when the sample is rapidly thermally decomposed as described above, pyrolysis gas containing oil mist can be generated from the sample. The gas discharge port through which the pyrolysis gas is discharged may be formed on the side surface of the conical spray layer reactor 10.

The sample quantitative dosing device 20 is installed on the upper part of the conical spray layer reactor 10 and supplies the sample to the inside of the conical spray layer reactor 10. On the other hand, various types of materials such as a polymer compound material and a mixture can be used as the sample to be supplied.

The heater 30 is configured to heat the outside of the conical spray layer reactor 10, which is installed under the conical spray layer reactor 10 and externally. On the other hand, various types of heaters can be used if the heater 30 satisfies the above-described configuration conditions.

The high temperature gas is injected through the gas inlet of the lower portion of the reactor by the heater 30 capable of heating the fluidized yarn in the conical spray layer reactor 10, wherein the flow rate of the gas injected by the flow meter 80 and the regulator is Thereby regulating the gas flow rate in the conical spray bed reactor 10.

The cyclone 40 is a device for removing impurities in the pyrolysis gas discharged through the outlet of the conical spray layer reactor 10 by using the cyclone phenomenon. Generally, the foreign matter removed by the cyclone is carbon black which is generated upon rapid thermal decomposition of the waste tire. In addition, a plurality of cyclones 40 may be continuously arranged as needed, so that the pyrolysis gas discharged from the conical fluidized bed reactor 10 can be processed stepwise by a plurality of cyclones.

In the present invention, the carbon black separated by the layer is removed through the carbon black discharge port 70 connected to one side of the conical spray layer reactor 10, and then the untreated micro carbon black is discharged through the cyclone 40 Remove. On the other hand, in order to continuously operate the rapid thermal decomposition reactor, carbon black produced after rapid thermal decomposition of waste tire as a sample should be discharged. For this purpose, a carbon black discharge port 70 is provided inside the conical spray layer reactor 10, and the height thereof is adjusted while the opening portion is upward, thereby more effectively separating and discharging the carbon black.

As described above, in the present invention, it is possible to efficiently remove carbon black that adversely affects the production process of the pyrolysis oil and efficiently remove the carbon black that degrades the quality of the pyrolysis oil of the waste tire.

The condenser 50 is a device for condensing the pyrolysis gas from which the carbon black is removed in the carbon black outlet 70 and the cyclone 40 to extract pyrolysis oil. The condenser 50 may be a general heat exchanger structure, And the condensation oil is directly contacted with the pyrolysis gas to condense the pyrolysis oil.

The electrostatic precipitator 60 electrostatically collects the non-condensable pyrolysis gas discharged from the condenser 50 and collects pyrolysis oil in a droplet state contained in the non-condensing pyrolysis gas.

Reference numeral 90 denotes a blower, and reference numeral 110 denotes a vacuum pump.

1, a di-limonene manufacturing system according to an embodiment of the present invention includes a decompression fractionation unit 120, It is a device for recovering di-limonene from pyrolysis oil of waste tire extracted through rapid thermal decomposition using distillation technology.

In general, the method of extracting the essential oil component from the raw materials includes a dipping method, a solvent extraction method, a distillation method, and a supercritical extraction method. Among them, the distillation method is advantageous in that it can obtain a high yielding essential oil component in a short time on average in comparison with other extraction methods even in the case of a material containing a small amount of essential oil components, and is easy to use a liquid raw material such as petroleum. Accordingly, the present invention uses fractional distillation according to one embodiment.

3 is a view showing a conceptual view of a fractionation device according to an embodiment of the present invention.

Fractional distillation refers to a process in which a mixture of liquid organic compounds is heated to convert a portion of the mixture into a vapor phase, followed by cooling to convert the vapor back into a liquid phase by condensation, Each material uses the principle that there is a unique boiling point.

Decompression distillation is based on the principle that the boiling point temperature inherent to the liquid material at atmospheric pressure is gradually lowered as the pressure decreases. Since the distillation can be performed at a temperature lower than the inherent boiling point of the liquid when the pressure is reduced, It is possible to reduce the required amount and increase the heat transfer rate in the distillation apparatus.

The di-limonene recovery apparatus 100 according to the present invention is a device for heating the inside and the outside of a distillation flask via a heating mantle to decompressively distill the supplied pyrolysis oil. Further, when the raw material is fractionally distilled as described above, steam containing di-limonene may be produced from the raw material.

On the other hand, the di-limonene-containing vapor is phase-reversed to the liquid phase by packing in the fractionation column, where the regeneration and the separation of the mixture occur due to the energy of the other vapor phase coming up in the distillation flask The purity becomes high.

As described above, in the present invention, it is possible to increase the purity of the gas through repetitive phase transition upon recovery of the dithymonane, and to obtain the final target material by dividing the final target material according to the characteristics when a large amount of materials are mixed.

Meanwhile, a liebig cooler coupled to one side of the fractionation column condenses the di-limonene-containing vapor that has undergone repetitive phase transformation to recover as a distillate, and a dimroth reflux condenser coupled to the fractionation column has reflux some steam is condensed for the reflux effect and the liquid material is recovered to the lower fractionation column.

Another aspect of the present invention relates to a method for producing waste tire pyrolysis oil.

The method for recovering di-limonene from waste tire rapid pyrolysis and pyrolysis oil distillation according to the present invention comprises the steps of: (a) introducing a waste tire into a conical spray layer reactor to rapidly pyrolyze the pyrolysis product; and (b) And (c) recovering the di-limonene by subjecting the extracted oil to fractional distillation under reduced pressure.

First, in step (a), the waste tire is supplied to the conical spray layer reactor 10 through the sample quantitative injection device 20. When the sample is supplied into the conical spray layer reactor 10 as described above, the sample is rapidly pyrolyzed to generate a condensed gas, a non-condensed gas, and a carbon black.

The rapid pyrolysis in step a can be carried out in a temperature range of 400 to 700 ° C and more specifically in a temperature range of 400 to 550 ° C. If the temperature at the pyrolysis is lower than 400 ° C or higher than 700 ° C, the yield of pyrolysis oil of waste tire to be finally produced may be low, which is disadvantageous.

Meanwhile, the retention time of the condensed gas in the conical spray layer reactor 10 should be within 2 seconds. If the residence time exceeds 2 seconds, a secondary reaction of the condensed gas occurs, which may be disadvantageous.

After completion of the rapid pyrolysis, gas, sand and carbon black are discharged to the outside of the conical spray layer reactor 10, and the sand and the carbon black are separated from the gas through the cyclone. On the other hand, the pyrolysis gas separated from the sand and the carbon black is transferred to the condenser and condensed in the condenser to obtain pyrolysis oil (step b).

Another aspect of the present invention relates to a method for producing di-limonene from waste tire thermal cracking oil.

First, the waste tire pyrolysis oil extracted from the rapid pyrolysis system is introduced into the di-limonene recovery apparatus 100 and subjected to fractional distillation (step c).

On the other hand, the flask portion containing the raw material of the di-limonene recovery device 100 is heated to fractionally distill the pyrolysis oil of the waste tire, so that the fractional distillation can be performed at a temperature of 175 ° C, which is the boiling point of di-limonene.

The pressure in the di-limonene recovery apparatus 100 was reduced to 60 mmHg at atmospheric pressure (760 mmHg), and the fractionation was carried out at a temperature of 96 ° C., which is the boiling point of di-limonene according to the reduced pressure condition.

On the other hand, after finishing the fractional distillation, some of the substances in the pyrolysis oil of the waste tire are phase-changed into vapor phase and transferred to the cooler, which is condensed in the cooler to obtain a distillate.

According to the di-limonene production method described above, since a subject sample is subjected to a rapid pyrolysis process prior to fractional distillation, waste tires, which are solid substances, can be phase-changed into pyrolysis oil of waste tire, which is a liquid product, So that it has a faster vaporization rate.

When the waste tire is subjected to the rapid pyrolysis process according to the present invention, as shown in each of FIGS. 5 to 11, the yield of the pyrolysis oil of the waste tire obtained according to the reaction temperature, the nitrogen gas inlet velocity, , Moisture content, calorific value, and viscosity of the tire were investigated to determine the optimum condition of pyrolysis waste tire for the production of di - limonene.

On the other hand, when the decompression fractional distillation process is carried out using the pyrolysis oil waste tire according to the present invention, it can be confirmed that di-limonene is contained in the obtained distillate as shown in FIG.

As described above, the method of recovering di-limonene from the waste tire rapid thermal decomposition and pyrolysis oil distillation of the present invention and the oil recovered by using the method are believed to be more cost competitive than the orange extract di-limonene because of its high cost competitiveness Therefore, it is economical to replace some of the imported orange extract di-limonene which is used as the conventional industrial cleaning agent.

Example

Experiment 1: Rapid thermal decomposition of waste tire

For the rapid thermal decomposition of the present invention, Passenger Car Tire (PCT) scrap was used as a target sample.

First, to analyze the physico-chemical properties of PCT scrap samples, we have selected 1.00 mm and 2.00 mm size of 1 ~ 2 mm. The selected PCT scrap was 0.65 wt.% Moisture, 67.59 wt.% Volatile matter, 25.16 wt.% Fixed carbon, 6.61 wt.% Ash and 35.69 MJ / kg calorific value.

The rapid pyrolysis unit used a conical spray layer reactor and a certain amount of nitrogen was injected in order to prevent the backflow of the fluidized bed, which is a flow medium, to the gas and the sample dosing device produced by the pyrolysis reaction. In the lower part of the reactor, nitrogen was added to form an appropriate area for spraying the solid particle layer, and an oxygen-free atmosphere was maintained.

The experimental conditions were pyrolysis reaction temperatures of 400, 450, 500 and 550 ℃, nitrogen inlet rates of 1.10, 1.27 and 1.44 m / s, and sample feed rates of 8.33 and 16.67 , And 25.00 g / min, respectively.

The sample in the sample reservoir was transferred into the conical spray bed reactor using a sample dosing device and rapidly pyrolyzed under each experimental condition. After the rapid thermal decomposition, the syngas and the solid particles generated by the rapid heat transfer are passed through the cyclone, where the solid particles are collected by the cyclone and the syngas is transferred to the condenser. The syngas transferred to the condenser was condensed into pyrolysis oil through heat exchange, and the remaining noncondensable gas was transferred to the electrostatic precipitator and then transferred to the flue gas treating apparatus after collecting the oil mist.

는 투입 시료인 PCT 스크랩의 무게,

는 급속열분해 후 제조된 생성물질의 무게이다. 이후 합성 가스 수율은 전체 투입된 시료의 무게에서 나머지 생성물의 무게를 뺀 값을 이용하여 산정하였다(도 5 내지 10 참조).The yields of the pyrolysis oil and carbon black produced were determined by weighing the PCT scrap and the pyrolysis product, using the following equation. In Equation (1)

The weight of the PCT scrap,

Is the weight of the product produced after rapid pyrolysis. The synthesis gas yield was then calculated by subtracting the weight of the remaining product from the weight of the entire charged sample (see FIGS. 5 to 10).

Moisture content, volatile matter, fixed carbon content, and ash content of the waste tire pyrolysis oil were measured using TGA701 manufactured by LECO Co., Ltd. according to the industrial analysis method ASTM D 3172. The contents of carbon, hydrogen, nitrogen, and sulfur were measured by Perkin Elmer 2400 Series II CHNS / O analyzer according to ASTM D 3176, an elemental analysis method. The high calorific value was measured using an AC 600 calorimeter (LECO) according to ASTM D 4809 (see FIGS. 5 to 10).

는 투입 시료인 PCT 스크랩의 고위발열량,

는 폐타이어 열분해 오일의 고위발열량이다(도 5 내지 10 참조).On the other hand, the energy yield of pyrolysis oil waste tire was calculated using the following equation. In Equation 2,

Is the high calorific value of PCT scrap,

Is a high calorific value of the waste tire pyrolysis oil (see Figs. 5 to 10).

On the other hand, the GC / MS (gas chromatograph-mass spectrometer) analysis of pyrolysis oil was performed using an external standard method. First, the peak detected after preparing the calibration curve using (+) - Limonene area values were obtained, and samples of all samples were diluted 10,000 times in chloroform (see FIG. 11 and Table 1).

<GC / MS analysis result of pyrolysis oil of waste tire> Reaction temperature
(° C) N ₂  inlet velocity
(m / s) Feeding rate
(g / min)

Response
(area, y) Concentration
(wt. % , x) 400 1.36 16.67 14,269 1.0175 450 1.27 18,333 1.2349 500 1.19 22,021 1.4323 550 1.10 11,808 0.8858 450 1.10 27,844 1.7439 1.44 12,959 0.9474 1.27 8.33 3,369 0.4342 25.00 23,441 1.5083

Experiment 2: D-limonene recovery from pyrolysis oil waste tire

The pyrolysis oil of the waste tire obtained from Experiment 1 was used as a raw material and pyrolysis oil of the used tire was analyzed by GC / MS analysis under conditions of a pyrolysis reaction temperature of 450 ° C, a nitrogen inlet rate of 1.27 m / s and a sample feed rate of 16.67 g / min, were used as the optimum conditions.

On the other hand, the di-limonene recovery apparatus was operated under a reduced pressure of -700 mmHg at atmospheric pressure using a vacuum pump in order to utilize the reduced pressure fractionation. Experiments were conducted under conditions of 96 ° C, 60 mmHg and 1, 2, 4, and 8 hours, respectively, which affect the content of di-limonene. The distillation flask was charged with the target material by fractional distillation at the experimental condition temperature using a heating mantle. The steam generated from the raw material during the distillation time passes through the fractionation column packed with the packing and is subjected to the re-collection and separation process, wherein some of the steam is collected as distillate through the heat exchange of the cooler provided at one side.

는 원료로부터 증발된 기체의 양,

는 회수된 액상 생성물의 양이다(도 6 참조).The efficiency of the di-limonene recovery unit was calculated by measuring the weight before and after the fractional distillation of the waste tire pyrolysis oil as the raw material. In Equation 3,

Is the amount of gas evaporated from the feed,

Is the amount of recovered liquid product (see Figure 6).

On the other hand, the GC / MS analysis of the distillate was performed using the external standard method under the same conditions as the GC / MS analysis of the waste tire pyrolysis oil (see FIG. 13 and Table 2).

<GC / MS analysis result of distilled material> Distillation time
(h) Vapor pressure
(m / s) Boiling temperature
(° C)

Response
(area, y) Concentration
(wt. % , x) One 60 96 873 2.9907 2 3,774 3.5001 4 29,454 8.0096 8 0 0

The di-limonene content of the distillation material is preferably 8 wt.% Or more.

10: Conical spray layer reactor 20: Sample quantitative dosing device
30: heater 40: cyclone
50: condenser 60: electrostatic precipitator
70: Carbon black outlet 80: Flow meter
90: blower 100: di-limonene recovery device
110: Vacuum pump

Claims (14)

A method for recovering di-limonene by pyrolysis oil distillation using a di-limonene manufacturing system using waste tires,
(a) rapidly pyrolyzing a waste tire by injecting it into a conical spray layer reactor;
(b) condensing the gas obtained by rapid pyrolysis in the reactor to pyrolyze the waste tire to extract oil;
(c) recovering di-limonene by subjecting the oil extracted in the step (b) to reduced-pressure fractional distillation to recover di-limonene from waste tire rapid thermal cracking and pyrolysis oil distillation.
The method according to claim 1,
The step (a)
Feeding the solution into the conical spray bed reactor by a sample dosing device;
Wherein the rapid pyrolysis is carried out at a temperature in the range of 400 to 700 占 폚. The method for recovering di-limonene by rapid pyrolysis of waste tire and pyrolysis oil distillation.
The method according to claim 1,
The step (a)
And discharging the condensed gas in the conical spray layer reactor to the outside within 2 seconds. &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt;
The method according to claim 1,
The step (a)
Wherein the gas, the sand and the carbon black are discharged to the outside of the conical spray layer reactor after completion of the rapid pyrolysis, and the sand and the carbon black are separated from the gas through the cyclone. Method of recovering di-limonene.
The method according to claim 1,
Wherein the fractional distillation in step (c) is carried out at a temperature ranging from 96 to 175 ° C.
The method according to claim 1,
Wherein the fractional distillation in step (c) is carried out in a pressure range of 60 to 760 mmHg.
The method according to claim 1,
(d) condensing the vapor generated in the step (c) with a dim-rod reflux condenser provided on the fractionation column, and recycling the condensed liquid product to the fractionation column for the reflux effect A method for recovering di - limonene by rapid pyrolysis of waste tires and pyrolysis oil distillation.
The method according to claim 1,
The di-limonene manufacturing system using the waste tire
A conical spray layer reactor for accelerating the rapid pyrolysis reaction of the waste tires introduced by using the fluidized yarn;
A sample dosing device for supplying a waste tire provided in the upper part of the conical spray layer reactor;
A heater for heating the gas injected into and from the inside and the outside of the conical spray layer reactor;
A carbon black outlet coupled to one side of the conical spray layer reactor to discharge carbon black;
A pyrolysis gas of the waste tire discharged from the conical spray layer reactor, a carbon black, a cyclone which receives the sand and collects carbon black and sand contained in the pyrolysis gas;
A condenser and an electrostatic precipitator for condensing and collecting waste tire pyrolysis oil in pyrolysis gas from which carbon black is removed from the cyclone;
A method for recovering di-limonene by rapid thermal decomposition of waste tire and distillation of pyrolysis oil, comprising the steps of: receiving a sample from a waste tire rapid pyrolysis system and extracting distillate material through reduced pressure fractional distillation;
9. The method of claim 8,
The spray layer reactor
Wherein the carbon black outlet is provided inside the conical spray layer reactor and the height is controlled with the opening directed upward, and the carbon black discharge port is formed in the conical spray layer reactor through a decomposition of the waste tire and pyrolysis oil distillation, Recovery method.
9. The method of claim 8,
The discharge port through which the sample is injected into the sample quantitative charging device may include a rapid thermal decomposition of waste tire and a di-limonene recovery method through pyrolysis oil distillation, which are provided to be directed downward to discharge the sample to the upper end of the solid particle layer in the spray layer reactor .
9. The method of claim 8,
Wherein the gas supplied to the lower gas inlet of the conical spray layer reactor is controlled by a flow meter and a regulator to control a gas flow rate and to control a gas flow rate in the conical spray layer reactor. - Method of recovery of limonene.
An oil produced according to the process for recovering di-limonene according to any one of claims 1 to 11, wherein the yield of the pyrolysis oil is 50 wt.% Or more.
An oil produced according to the method for recovering di-limonene according to any one of claims 1 to 11, which has an oil calorific value of 42 MJ / kg (10,000 kcal / kg) or more.
11. An oil produced according to the process for recovering di-limonene according to any one of claims 1 to 11, wherein the oil has a moisture content of 5 wt.% Or less.

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