KR19980067398A - Process for producing high quality fuel oil by simultaneous pyrolysis of waste lubricant and waste plastic - Google Patents

Abstract

The present invention relates to a process capable of producing high quality fuel oil by pyrolysis of waste lubricant and waste plastic at the same time.

The waste plastic, which is a solid, was converted into a liquid phase using waste lubricants to solve the problems caused by treating solids in the existing process.

After decomposing the fuel in the liquid phase into the pyrolysis reactor, high-quality fuel oil having 21 or less carbon atoms was separated by using an equilibrium distillation drum, and the bottom product was circulated to pyrolyze again. All the ingredients except for the ingredient can be converted into high-quality condensed milk.

Recycling the bottom products thus increased the production of high quality fuel oil by more than 19%.

In addition, the coke component generated during pyrolysis is sedimented in the flash drum to be discharged to the lower part of the drum to develop a breakthrough process to ensure the stability of the process by maintaining the content of coke in the process below a certain amount.

Description

Process for producing high quality fuel oil by simultaneous pyrolysis of waste lubricant and waste plastic

The present invention can pyrolyze waste lubricating oil (hereinafter referred to as waste oil) alone and waste lubricating oil and waste plastic at the same time to produce a mixture of up to 21 carbon atoms (hereinafter referred to as high-grade fuel oil), thereby producing high-grade fuel oil and also producing coke components It is about a process that can be easily separated.

The amount of waste lubricating oil that is disposed of after use in internal combustion engines and transmission gearboxes is an enormous amount of 1 million drums per year as of 1994.

In addition, the amount of plastics amounted to 2.6 million tons in 1994, and considering the increase, the technology to replace the landfill method, which is the current major disposal method, is urgently needed.

Therefore, in the present invention, as a result of several experiments and studies on how to effectively treat them and obtain recycling of resources, the inventors have invented a continuous process capable of producing high-grade fuel oil having high calorific value using waste plastic and waste oil. .

The present invention will be described in detail below.

As shown in FIG. 1, the process is largely composed of a dissolution tank A, a pyrolysis reactor B, and an equilibrium distillation drum C. Coke receiver D of waste plastic.

First, the production process of high quality fuel oil using only waste oil is as follows.

At this time, the waste oil is preheated to a certain temperature in the melting tank, fed to the reactor, given a certain residence time, pyrolyzed and sprayed on an equilibrium distillation drum, and the steam component, which is light oil, is discharged to the upper part of the column.

At this time, the equilibrium distillation drum was carried out under reduced pressure to 2 ~ 100mmHg to keep the temperature of the drum as low as possible.

In addition, the temperature of the reactor was maintained at 400 ~ 500 ℃, the residence time was given to 20 ~ 50min enough to minimize the generation of C ₁ ~ C ₅ gas.

As pyrolysis proceeds, the ratio of hydrogen to carbon (H / C) in the oil is about 1.6, which is apparently in the category of ordinary fuel oil, but coke is inevitable because no separate hydrogen supply proceeds.

However, the coke produced is the biggest obstacle to continuous process operation and its removal is essential.

Therefore, as a result of this study, the liquid residence time was given in the flash drum so that the coke component could settle down to the lower part of the coke receiver.

The bottoms of the equilibrium distillation drum used a unique method of circulating through the reactor and re-establishing time for pyrolysis.

Therefore, the yield of high-grade fuel oil is 19 compared to the method of terminating primary pyrolysis by converting the entire amount to high-quality fuel oil except for the hydrocarbon component which discharges coke and gas components in the fuel oil supplied by the breakthrough method developed in the present invention. Could increase by more than%.

The method of simultaneous fuel emulsification of waste oil and waste plastic is as follows.

Waste oil and waste plastic were supplied to a dissolution tank maintained at 250 to 280 ° C. to convert waste plastic into liquid phase and then supplied to a pyrolysis reactor.

Using such a dissolution tank it was possible to facilitate the continuous operation of the solid waste plastic as a liquid phase.

At this time, by supplying the waste oil at the same time with the waste plastic, the waste oil acts as a solvent and heat transfer medium as a dispersion medium of the waste plastic, thereby achieving a synergistic effect of the ease of the continuous process and the reaction efficiency than when the plastic alone.

The process after transferring the waste plastic converted into liquid phase to the pyrolysis reactor is the same as when using only waste oil.

The temperature of the reactor, the residence time of the reactants, and the mixing ratio of waste oil and waste plastic in pyrolysis were set using the optimized results for each of the five general purpose resins in a small reactor, and the composition of waste plastic was set based on the generation ratio.

1 is a schematic view of a process constructed in the present invention

* Description of the symbols for the main parts of the drawings *

A: melting tank of waste plastic B: pyrolysis reactor

C: Flash type drum D: Coke receiver

2 shows the yield of gas, oil and coke after primary pyrolysis

* Description of the symbols for the main parts of the drawings *

A: Yield of each component when primary pyrolysis of only waste lubricant

B: Yield of each component during primary pyrolysis by mixing 33wt.% Of waste plastic with waste lubricant

C: Yield of each component during primary pyrolysis by mixing waste plastic 50wt.% With waste lubricant

D: Yield of each component during primary pyrolysis by mixing waste plastic 66wt.% With waste lubricant

3 shows the composition of waste lubricating oil and the product gas during co-pyrolysis

* Description of the symbols for the main parts of the drawings *

A: Composition of gas produced when pyrolyzing only waste lubricant

B: When 33wt.% Of waste plastic is mixed with waste lubricant

C: When 50wt.% Of waste plastic is mixed with waste lubricant

D: When 66wt.% Of waste plastic is mixed with waste lubricant

4 is a composition of the oil produced according to each condition

* Description of the symbols for the main parts of the drawings *

A: Carbon number distribution of waste lubricating oil

B: Distribution of carbon number of produced oil when pyrolyzing only waste lubricant

C: Distribution of carbon number of waste plastic 33wt.% Mixed pyrolysis oil in waste lubricating oil

D: Carbon number distribution of waste plastic 50wt.% Mixed pyrolysis oil in waste lubricating oil

E: Carbon number distribution of waste plastic 66wt.% Mixed pyrolysis oil in waste lubricating oil

5 is a change in the amount of high-grade fuel oil produced by the circulation of undecomposed top bottom products

* Description of the symbols for the main parts of the drawings *

A: Yield of high grade fuel oil during primary pyrolysis according to the amount of waste plastic added

Final yield of high quality fuel oil during circulation of the bottom product obtained in B: A

6 is a change in carbon number distribution according to vacuum distillation

* Description of the symbols for the main parts of the drawings *

A: Carbon number distribution of co-pyrolysis oil (66 wt.% Plastic)

The composition of the tower top product when the product obtained in B: A is vacuum distilled at 252 ° C and 2torr.

Example 1

This is an example of pyrolysis of waste lubricating oil alone, and the method is as follows.

Waste oil is supplied to the dissolution tank A maintained at 260 ° C., preheated, and continuously supplied to the pyrolysis reactor.

The temperature of the reactor was kept constant at 460 ℃ and the average residence time of the waste oil was given 30 minutes.

As shown in FIG. 2, the pyrolysis product was able to obtain 6.2 wt% of a gas component, 70.2 wt.% Of an oil component, and 23.57 wt.% Of coke.

At this time, the gas component is analyzed by gas chromatography (HP 5890, gamma alumina column, FID detector) as a result of the mixture of 1 to 3 carbon atoms as shown in A (Fig. 3), a small amount of C ₄ compound and a small amount of C ₅ ~ C _It was _six components.

Carbon number distribution of the oil component is a gas chromatograph which the initial feed material as a mixture of C ₆ ~ C _40, as shown in B of the results (Figure 4), simulated distillation using a (HP 5890, capillary column, FID detector) ( Compared with the average carbon number C ₃₅ of the waste oil of FIG. 4), it can be seen that most of them were decomposed and hardened.

As shown in (Table 1), the calorific value of the oil component and the element concentration of sulfur were 4100ppm, but the concentration after pyrolysis was reduced to 1000ppm, and the calorific value of the produced oil was at least 10.370cal / g.

After the reaction, the product oil was continuously sprayed on a flash drum to separate a light component.

The flash drum temperature and the pressure is significant results produced being kept in a 252 ℃, 2torr carbon atoms, C ₆ ~ C ₂₁ hydrocarbons is 95.5wt.% Gasoline, premium fuel consisting baekdeungyu, diesel, a mixture of a small amount of heavy oil significantly specifications ( BP 350 ° C. or less).

In addition, unlike the existing pyrolysis process, the lower part of the flash drum was re-supplied to the reactor to perform pyrolysis again, so that the total amount of oil produced from the supplied raw material can be obtained in the form of high quality fuel oil.

As a result (as shown in Figure 6) it was possible to increase the production of high-grade fuel oil more than 10%.

TABLE 1

Percentage and Calorific Value of Primary Pyrolysis Generating Oil and Waste Oil

Example 2

The amount of waste plastic is absolute based on the actual amount of waste oil and waste plastic produced.

Therefore, when producing high-quality fuel oil using waste oil and waste plastic, the amount of waste plastic as raw material is much richer than waste oil. Therefore, it is expected to have advantages in many ways if the operation of the process is possible by increasing the content of waste plastic. Several experiments and studies have been carried out on the production of high quality fuel oils according to the plastic and waste oil contents.

As an example, the results of thermal decomposition of waste plastics content of 33%, 50%, and 66% by mixing waste oil are as follows.

First, the amount of non-condensing gas, oil, and coke in the pyrolysis reactor according to the amount of waste plastic is shown in FIG. 2.

As the plastic was mixed, the yield of oil component increased by 8-15 wt%.

As shown in FIG. 3, the carbon number composition ratio of the generated gas showed the same tendency as pyrolysis of only waste lubricant oil.

However, the composition of produced oil showed a completely different result.

As seen in C-E of FIG. 4, the content of 7-10 carbon atoms was significantly increased due to the gasoline content.

In addition, the concentration of sulfur in the product fraction could be reduced to half the level of waste oil treatment (Table 1).

Therefore, by adding a certain amount of plastic components to the production of high-quality fuel oil by waste oil alone pyrolysis, a higher quality of oil can be obtained, and a smooth continuous process can be invented by allowing plastic to be operated as a liquid.

In addition, the final yield of oil, gas, and coke components when recycling the bottom product was astonishing, with the highest yield of high fuel oil when plastic was added, as shown in (Table 2).

As shown in FIG. 5, the yield of high-grade fuel oil was increased by up to 19.4% as compared to when the bottom product was not recycled.

The carbon number distribution of the final product co-pyrolyzed by mixing 66wt% of plastics is the same as B in (Fig. 6), and it corresponds to the diesel oil as compared to A in (Fig. 6), which is the property of the oil supplied to the flash drum from the reactor. It can be seen that the oil has been completely recovered.

The composition of the final product was analyzed by requesting the Petroleum Quality Inspection Center. As a result of pyrolysis oil, no heavy metals such as residual carbon 0.01%, ash 0.01 or less, sulfur 900ppm, calorific value 10,490cal / g, cadmium, lead, chromium and arsenic were not detected. It was confirmed that the product satisfies.

TABLE 2

Final yield of each ingredient

Claims (3)

Circulating waste oil and waste plastic at the same time in batch or continuous process and then circulating to the reactor or pre-reactor process for the purpose of re-pyrolysis of the produced oil, dissolving waste plastic in liquid tank and converting coke component A method for producing advanced fuel oil by simultaneous pyrolysis of waste lubricant and waste plastic, characterized in that the step of sedimentation separation in an equilibrium distillation drum. The method of claim 1, wherein the amount of waste plastic is added at a weight ratio of 0 to 70%. The high-quality fuel oil according to the simultaneous pyrolysis of waste lubricating oil and waste plastic is characterized in that when thermally decomposing waste oil and waste plastic or waste oil, a reactor temperature of 380 to 500 ° C. and a residence time of 10 to 50 minutes are given. Manufacturing method.