KR20010108725A - A thermal cracking process for manufacturing the cracking gas oil from the used oil - Google Patents

Abstract

The present invention relates to a high-temperature pyrolysis method for producing a colloidal material by pyrolyzing oxides and sludges such as heavy metals contained in waste oil, and evaporating and condensing the pyrolysis oil into low sulfur cracking gas oil. As a process according to the present invention, a cracking heavy oil obtained by removing the colloidal material contained in the waste oil alone or in the high boiling hydrocarbon oil generated at the bottom of the distillation process in a primary eliminator is mixed with the waste oil, Circulated through a vertical pyrolysis heater composed of a plurality of pipes, and the water contained in the waste oil is condensed and removed from the condenser through a sieve tray distillation column, and the off-gas of the column is used as a heat source of the pyrolysis heater, Low-boiling hydrocarbons vaporized are condensed in the cooler to produce reformed diesel fuel. It consists of.

The present invention simplifies the process by complementing the drawbacks of the conventional waste oil treatment technology, as well as the treatment of heavy metals and other harmful substances that are agonizing in the waste lubricant resource recycling industry by mixing waste lubricant and cracking heavy oil as raw materials. In addition, it is possible to solve the improvement of the quality and yield of reformed diesel fuel by pyrolysis of waste lubricating oil on the basis of economic feasibility. It is an opportunity to contribute to environmental conservation.

Description

A high temperature pyrolysis method for producing reformed diesel fuel from waste oils {A THERMAL CRACKING PROCESS FOR MANUFACTURING THE CRACKING GAS OIL FROM THE USED OIL}

The present invention is made of a colloidal material by pyrolyzing oxides and slurries, such as heavy metals contained in the waste oil, and the pyrolysis oil obtained by evaporating condensation is produced with low sulfur cracking gas oil. It relates to a high temperature pyrolysis method for.

There are various types of "waste oil", but gasoline and diesel engine oils used in internal combustion engines, two cycle engine oils, agricultural engine oils and automotive gear oils. This is mainly used petroleum hydrocarbon, which is a substance that can be exchanged after a certain distance, and cannot be used as a new oil.

The waste oil Looking at the environmental contaminants from (Used oil), a high concentration of heavy metals and toxic substances (C1 ^-, F ^-, PCB, PCT) were remains and which, when using a fuel flow path without any purification step, barium (Ba), clear ( Br), chromium (Cr), cadmium (Cd), lead (Pb), arsenic (As), etc. are generated as soot and harmful to the human body, as well as enormous damage to biological growth, as well as thrown away In addition to polluting streams, so-called oil-based and wear-resistant additives, which are toxic additives contained in waste lubricating oils, are toxic additives, which are difficult to be purified when they enter the drinking water, remain in the tap water. It is a fact that everyone is aware of.

Although there are many patents that have various technology development or pros and cons of refining these used oils as a conventional technology, it has not been continued as practical use, but excessive tar is generated as reformed fuel oil, disgusting smell, and constant There was a drawback that economic feasibility was lacking in consideration of unsuccessful change of kinematic viscosity, yield level including color level, etc.

The present invention has been made to solve the problems of the prior art, simplifies the process in compensating the drawbacks of the conventional waste oil treatment technology, as a raw material by mixing waste lubricating oil and cracking heavy oil (Cracking Heavy oil) In addition to the treatment of heavy metals and other harmful substances, which are struggling in the resource recycling industry, it is possible to thermally decompose waste lubricants to improve the quality and yield of by-produced reformed diesel fuels on an economical basis, as well as manpower, time and specific waste disposal costs. The aim is to provide a high temperature pyrolysis method for the production of reformed diesel fuel from spent lubricating oil, which can reduce fuel consumption and contribute to global environmental conservation.

The above object is a heater for pyrolyzing waste lubricating oil. It is made of stainless steel SUS 304 which is resistant to corrosion and heat. The flow rate is turbulent to prevent caking during pyrolysis. (3 inch Vertical Cracking Heater), which is designed with a tube size of 3 inches of vertical, separates and distills low-boiling hydrocarbons and high-boiling hydrocarbons in the oil from which the waste oil is pyrolyzed from the heaters, and adjusts the constant kinematic viscosity of the reformed gas. 18 stage sieve tray distillation column for improved (odor and color improvement), colloid filter to remove oxides and solids, including heavy metals contained in high boiling hydrocarbons from distillation column The primary colloidal material remover is used to remove the remaining cracked heavy oil. Non-condensable gas from intermediate tanks and distillation columns needed to improve the yield of reformed diesel fuel as well as to minimize colloidal substances and impurities remaining in cracked heavy oils. Off gas burning system that uses gas as a heat source for cracking heater in consideration of economical efficiency, and condensate to condense and remove moisture contained in waste oil. pots), heat exchangers needed to utilize thermal energy in terms of economic efficiency between processes, coolers required to condense low-boiling hydrocarbons vaporized from distillation towers and make them via reforming, and various pumps necessary for transporting liquids. Instrumentation system for automatic and continuous control of all processes ystem) and a high temperature pyrolysis method according to the present invention using a system consisting of a raw material storage tank and a product storage tank, which will be described in detail below.

1 is a schematic diagram of a system for practicing the method of the present invention

The process of the present invention consists of 1) preparation step, 2) continuous processing step, 3) cracking heavy oil mixing step, 4) end of work.

1. Preparation

First, as shown in the process of Figure 1 by operating a feed charge gear pump (Gp-1) of 5,000 liters of raw material oil of the storage tank (TK-101) mixed with various waste lubricating flows (Flash) (Flash) (Flash The oil is fed to the column side of the distillation column (T-201) in which 18 sieve trays are installed through the zone FZ-1. Subsequently, when the amount of waste oil stored in the distillation column (T-201) is confirmed to be the column bottom level (LIC-1), the waste oil of the distillation column (T-201) is operated by operating a heavy oil circulation process pump (PP-1). This SUS 304 is a 3 inch tube consisting of a Vertical Cracking Heater (H-201) and continues to the used oil (Side Zone) (FZ-2) to the side of the distillation column. Circulate

2. Continuous Processing Step

The procedure of the process and operation method for performing the continuous processing of the waste oil of the preparation step is as follows.

(1) Complete circulation is achieved by continuously rotating waste oil from the distillation column (T-201) to the vertical pyrolysis heater (H-201) and from the vertical pyrolysis heater (H-201) to the distillation column (T-201). When the heater (H-201) is provided separately, a service fuel supply source (KT) provided with oil is supplied with oil and the oil burner (burner output 100%) operated in the heater (H-201) is operated to burn the heater. Heat (H-201).

(2) When the time to be heated in the heater (H-201) gradually passes and the outlet temperature of the heater (H-201) is more than 90 ℃, the water contained in the waste oil is vaporized in the distillation column (T-201) Condensate in the condensate pot (CP-1) via the column top causes separation of the water contained in the waste oil. Therefore, when the outlet temperature of the heater (H-201) is 100 ℃ or more, the oil burner (H-202) output of the heater (H-201) is lowered to 25% by TIC-1 to operate.

The reason for this is to minimize some plugging of Flame Arrester due to the scattering of carbon when using Opgas as a gas burner heat source, the burner system (H-203) of heater (H-201) in normalization operation. Furthermore, the time to completely remove the water contained in the waste oil in the condensate pot (CP-1) depends on the amount of water contained in the waste oil, but it takes about 3 to 4 hours.

(3) As the heating temperature of the heater (H-201) continues, water is removed from the waste oil, and when the bottom temperature of the distillation column (T-201) reaches 150 ° C, the low boiling point hydrocarbon component evaporates in the distillation column (T-201). The bottom level (LIC-1) begins to lower. Therefore, in this case, the waste oil of the waste oil storage tank (TK-101) is operated by the oil feed pump GP-1, and the control valve FIC-2 adjusts the amount of raw material to be evaporated by the amount of heat exchanger E-1 and E-2. Charging to the distillation column (T-201) through).

(4) If the steam color of the vent stack of the heater (H-201) turns blue while the method of (3) above is continued, the heater recognizes that water has evaporated in the lung oil. Automatic control of gas burning system (PI-201) to lock the oil burner of H-201 and to use off gas generated in the distillation column (T-201) as fuel for the heater (H-201). The off gas is adjusted to 200 Nm ³ / hr and the pressure to 0.03 kg / cm 2 by automatic control (PI-201).

(5) On the other hand, while the method of (3) continues, the outlet temperature (FZ-2 of T-201) of heater (H-201) gradually increases, and as the temperature of heater (H-201) increases Automatic thermal flow meter (FC-1), which increases the amount of off gas due to active thermal cracking and 5% of off gas by mass balance. In the 18-stage sieve tray of the distillation column (T-201), deodorization proceeds along with gas stripping, while gas-liquid contact occurs by hydrocarbon boiling point.

(6) If the outlet temperature of the heater (H-201) reaches 499 ° C while the method of (5) is continued, the internal temperature of the distillation column (T-201) also increases.

Therefore, in the distillation column (T-201), high concentration of heavy metals and harmful substances, which are impurities in the waste oil, do not evaporate due to high temperature and are generated at the bottom of the colloidal material, so the bottom process pump (PP-1) is automatically controlled by the bottom water level (LIC-1). 2) by using the high temperature of 400 ℃ as inter-process energy by using the heat exchanger (E-1) through the heat exchanger (E-1) and heavy metal remover (F-1) to the colloidal substances contained in the waste oil to filter 1 Waste heavy oil is removed and residual heavy oil is sent to the intermediate product tank (TK-302) by automatic control device and high boiling point hydrocarbon oil generated by material balance is 20%. Colloidal material generated in the heavy heavy metal remover (F-1) is 3.50% of the cracking heavy oil.

On the other hand, when the top temperature of the distillation column (T-201) reaches 160 ° C, the liquid in the accumulator (A-1) between # 6 and # 7 of the distillation column (T-201) is overhead process pump. Pump (PP-4) was operated to reflux the liquid cooled to 90 ° C in the cooler (EC-1) to the top of the distillation column (T-201) to maintain the temperature of the tower at 80-150 ° C. Adjust with automatic control unit (FIC-3) if possible (the purpose of reflux is to remove carbon contained in pyrolysis steam and to improve the color of modified diesel products).

(7) As the method of (6) is continued, the level (LIC-2) of the accumulator of the distillation column (T-201) also increases, and the temperature of the accumulator also increases. When the temperature reaches 260-380 ℃, the temperature of the sheave tray directly below the accumulator of the distillation column (T-201) is maintained at 330-360 ℃ through the automatic controller (FIC-4).

(8) Meanwhile, as the method of (7) is continued, the reformed diesel oil is discharged by the automatic control of the liquid level LIC-2 of the distillation column T-201, and 80% is discharged by the material balance. 301).

(9) If the normal operation is reached after 12 hours while the operation methods of (5), (6), (7) and (8) continue, the level of the intermediate tank (TK-302) It will reach 30%.

Therefore, the colloidal material in the high boiling point hydrocarbon oil is actively generated in the column bottom of the distillation column (T-201) and the colloidal material in the cracking heavy oil can be sufficiently removed by the heavy metal remover (F-1) at the column bottom level (LIC-1). Adjust

3. Cracking Heavy Oil Mixing Stage

(1) The cracking heavy oil is obtained as intermediate product by removing the colloidal substances with heavy metal remover (F-1) from the high boiling point hydrocarbon oil generated in the bottom of the distillation column (T-201). In order to remove solids that were not removed first by the eliminator (F-1), separate instrumentation equipment should be installed so that the ratio of feed oil to cracking heavy oil is in the range of 80-84% to 20-16%. Use automatic adjustment. At this time, the maximum pressure of the oil pump (GP-1) should not exceed 3.5 ㎏ / ㎠ during normalization.

(2) It can be seen that the solution of accumulator between # 6 and # 7 of the continuous processing operation process increases by 10% when time elapses while the method of (1) continues. Therefore, when the normalization stage 12 hours, cracking heavy oil mixing stage 12 hours, a total of 24 hours after the liquid level (LIC-2) is automatically adjusted, the yield of reformed diesel oil from the waste oil reaches 90%.

(3) On the other hand, as the process of (2) is continued, the column is further drawn out to the bottom process pump (PP-2) as much as the mixing ratio shown in the above (1). By automatically adjusting to the low water level (LIC-1), the impurities removed in the heavy metal remover (F-2) secondary become 1.5% of the high boiling hydrocarbon oil 20%.

(4) The properties of the modified diesel fuel obtained from the waste lubricating oil through this process are as follows.

Test Items Test Methods Modified gas phase Specific gravity (15/4 ℃) KS M 2002 0.8180-0.8290 Calorific value (Cal / g) KS M 2057 10,400-10,900 reaction KS M 2012 neutrality Flash point (PM ℃) KS M 2010 55-60 Pour point (℃) KS M 2016 -25.0- -27.5 Kinematic viscosity (50 ℃) KS M 2014 4. 00-4. 30 Sulfur (%) KS M 2027 0. 09-0. 07 Color (ASTM) KS M 2106 1. 0-1. 5 Ash KS M 2044 0.01 or less Acid value (mg KOH / g) KS M 2004 0. 023-0. 03 Odor Sensory method detection threshold Cetane Index 1 KS M 2610 55- 60 Heavy metals (Cd, Pb, Cr, As) Inductively Coupled Plasma Emission Spectrophotometer Not detected Midstream (℃) IP (%) 95 (%) KS M 2031 80-150260-360

4. End of work

The preparation, sequential processing and cracking heavy oil mixing steps are completed and the normal operation takes 24-48 hours depending on the water content in the waste oil. If you want to shut down after 88-90%, 5-6% of colloidal substances and impurities are generated normally and continuous work is continued for 300 days, follow the procedure below.

(1) First, when the flame of the burning system of the heater H-201 is lowered, the outlet temperature of the distillation column tower side FZ-2 is gradually lowered. At the same time, the mixing ratio of the cracking heavy oil of the intermediate tank (TK-302) is stopped by automatic control and parallel, and the oil supply of the storage tank (TK-101) is also stopped.

(2) Coking is prevented in the pyrolysis heater by continuously operating only the circulating process pump PP-1 of the bottom process pump PP-2.

(3) As the method of (2) above is continued, if the pressure of the top of the column becomes atmospheric pressure and the temperature of the pyrolysis heater is 80 ° C under automatic control, the operation of the circulating process pump (PP-1) is stopped and the distillation column The operation is terminated by feeding the high boiling point hydrocarbon oil remaining in the distillation column (T-201) to the intermediate tank (TK-302) with the bottom pump (PP-2) of (T-201).

The present invention simplifies the process by complementing the drawbacks of the conventional waste oil treatment technology, as well as the treatment of heavy metals and other harmful substances in the waste lubrication resources recycling industry by mixing waste lubricant and cracking heavy oil as raw materials In addition, the improvement of the quality and yield of reformed diesel fuel by pyrolysis of waste lubricating oil can be solved on the basis of economic feasibility. It is an opportunity to contribute to environmental conservation.

Claims (3)

In the high-temperature pyrolysis method for producing reformed light oil from waste oil, a cracking heavy oil obtained by removing the colloidal material contained in the waste oil alone or in the high boiling hydrocarbon oil generated at the bottom of the distillation process in a primary eliminator is mixed with the waste oil. The oil is circulated through a vertical pyrolysis heater composed of a plurality of pipes, and the water contained in the waste oil is condensed and removed from the condenser through a sieve tray distillation column, and the off gas of the tower top is used as a heat source of the pyrolysis heater. And a low boiling point hydrocarbon vaporized from the distillation column is condensed in a cooler to produce reformed diesel fuel. The method of claim 1, Extraction of the accumulator gas from the distillation column to maintain the top temperature at 80-150 ℃ during reflux and to maintain the temperature of the bottom of the accumulator at 260-380 ℃ to produce a modified diesel from waste oil High temperature pyrolysis method. The method according to claim 1 or 2, A high temperature pyrolysis method for producing a reformed diesel fuel from waste oil, characterized in that the waste oil is circulated to a fresh zone on the side of the distillation column through a pyrolysis heater at the top of the distillation column.