KR20150088540A - Method for purifying fuel oil - Google Patents

Abstract

The present invention relates to a method for desulfurizing and denitrifying fuel oil at high speed and for collecting and reusing an ionic liquid. The method comprises: a fuel oil extraction processing step, an oxidation processing step, a centrifuge separation processing step, a fuel oil recovery processing step, an ionic liquid recovery processing step, and a utility facility processing step. More particularly, the oxidation processing step enables fuel oil to be quickly reacted in the extraction processing step of desulfurizing and denitrifying fuel oil by using ozone (O_3), instead of existing hydrogen peroxide (H_2O_2) as an oxidizing agent, without changing physical properties of an ionic liquid or aromatic hydrocarbon. In addition, fuel oil having low sulfur and low nitrogen and ionic liquid are collected respectively in the fuel oil recovery processing step and the ionic liquid recovery processing step by using a short-path distillator. The present invention is capable of carrying out deep desulfurization and deep denitrification in a work environment under low temperature and low pressure, preventing the occurrence of second contamination, providing a safe operation, saving energy, and reducing manufacturing costs.

Description

METHOD FOR PURIFYING FUEL OIL

The present invention relates to a fuel oil purification method, and more particularly, to a fuel oil accelerated desulfurization, denitrification, and ionic liquid recovery reusing method.

Although conventional hydrogen desulfurization technology is currently used, conventional hydrogen desulfurization technology still contains about 50 PPM of sulfur in the fuel oil produced after deep desulfurization and desulfurization depth of less than 10 PPM of sulfur content Demand in the market demanding low sulfur fuel oil is imminent. Thus, conventional hydrogen desulfurization techniques can not achieve the goal of depth desulfurization as long as the catalytic reaction rate is increased, the operating pressure is increased, and the reaction temperature is not increased.

Depending on the nature of the technology being used, the following five technologies are currently under development.

1. Solvent Extraction Desulfurization Technique: It is possible to pollute the environment because a certain solvent is used as an extracting agent and these solvents have volatility and toxicity.

2. Oxidative Desulfurization Technology: First, the fuel oil is oxidized using a strong oxide such as hydrogen peroxide (H ₂ O ₂ ), ozone (Ozone-O ₃ ), ultraviolet (Ultraviolet), peroxyacid peracid, ), DMSO (dimethylsufoxide), and DMF (N, N-dimethyformamide). However, since these polar solvents have high volatility and pyrophoricity, they are prone to fire and explosion.

3. Adsorption desulfurization technology: The main method is to adsorb sulfides in the fuel by adding an adsorbent in the desulfurization process and achieve the desulfurization purpose through the hydrodesulfurization reaction again. However, there is a problem that the adsorption ability to sulfides such as DBT (dibenzothiophene) in the sulfide is undesirable.

4. Microbial desulfurization technology: Desulfurization is promoted by using a desulfurizing enzyme that is produced by microbial metabolism as a catalyst to achieve a desulfurizing effect. However, there are defects such as slow reaction rate, low efficiency, high cost of desulfurization culture.

5. Desulfurization and denitrification of an ionic liquid as an extraction agent: This method is similar to the above-mentioned method of using a solvent as an extraction agent. This method mainly uses Room Temperature Ionic Liquid as an extraction agent and oxidizing agent such as hydrogen peroxide (H ₂ O ₂ ) and ethanoic acid (CH ₃ COOH) after the extraction process, And a catalyst such as formic acid (HCOOH) or trifluoroacetic acid (CF ₃ COOH) is added to increase the desulfurization reaction rate.

However, when the oxidizing agent is used at a high concentration such as hydrogen peroxide (H ₂ O ₂ ) used in the process of increasing the reaction rate by adding an oxidizing agent, when a water-soluble ionic liquid is encountered, a violent chemical reaction occurs, The hydrolysis reaction may be caused and the ionic liquid may be recovered and can not be reused. Therefore, it is necessary to use an oxidizing agent that does not cause a hydrolysis reaction without causing a violent reaction, and if this problem is not solved, the mass of the ionic liquid may be changed so that it can be partially recovered, This is because it is absent.

The present invention provides an improved method for the associated problem of performing extraction desulfurization with the ionic liquid in order to operate more safely, increase efficiency, and lower the operation cost. Using this method, it is possible to use and distribute low-sulfur and low-quality refined fuel oil more widely, improve the environment in which we live, and lower the damage caused by acid rain and air pollution.

It is an object of the present invention to provide a fuel cell which does not change the characteristics of a substance while increasing the reaction rate in an extraction process for desulfurization and denitrification using ozone (Ozone-O ₃ ) instead of conventional hydrogen peroxide (H ₂ O ₂ ) Accelerated desulfurization, denitrification, and recovery and reuse of ionic liquid.

It is an object of the present invention to provide a low-temperature, low-pressure and low-pressure, low-pressure, low-pressure, low-pressure, low- Denitrification, denitrification, and ionic liquid recovery reuse method that does not cause secondary contamination, safer operation, saves energy, and reduces manufacturing cost.

In order to achieve the above-mentioned object, the present invention provides a fuel oil treatment apparatus comprising a fuel oil extraction treatment step, an oxidation treatment step, a centrifugal separation treatment step, a fuel oil recovery treatment step, an ionic liquid recovery treatment step and a common treatment step, Is an extraction process for desulfurization and denitrification by mixing the fuel oil and an ionic liquid.

(Ozone-O ₃ ) is used as an oxidizing agent instead of the conventional hydrogen peroxide (H ₂ O ₂ ) in the oxidation treatment step, the fuel oil quickly reacts in the extraction treatment step of desulfurizing and denitrating the fuel oil. ) Does not change the physical properties of the hydrocarbon.

In the fuel oil recovery step and the ionic liquid recovery step, low-sulfur and low-quality fuel oil are recovered using a single-stage still, and the ionic liquid is recovered.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to increase the reaction rate in the desulfurization and denitrification extraction step, and to perform desulfurization and denitrification without changing the physical properties of the extract. In the low temperature and low pressure environment, Can be recovered, and the ionic liquid can be recovered and reused.

1 is a view showing a system such as a fuel oil extraction processing step, an oxidation processing step, and a centrifugal separation processing step of the present invention.
2 is a diagram showing a fuel oil recovery process step system of the present invention.
Fig. 3 is a diagram showing the ionic liquid recovery process step system of the present invention.
4 is a diagram of a common processing stage system of the present invention.

1 to 4, a preferred embodiment of the present invention includes a fuel oil extraction process 10, an oxidation process 20, a high speed centrifuge separation process A fuel oil recovery process 40, an ionic liquid recovery process 50, and a utility facility 60, This will be described in detail below.

Referring to FIG. 1, the fuel oil extraction processing step 10 is an extraction process in which the fuel oil and the ionic liquid are mixed to perform desulfurization and denitrification.

In the fuel oil extraction processing step 10, an ionic liquid OMIM BF4 (1-octyl-3-methylimidazoliumtetrafluoroborate) at room temperature or the like is filled in the fuel oil mixture heating tank 11, the plurality of transfer pumps 121, 122, 131 and 132, A room temperature ionic liquid reservoir 14, a centrifugal extractor 15 and a mixture buffer 16 of a fuel oil and an extract, each containing BMIMFeCl4 (1-butyl-3-methylimidazoliumtetrafluoroborate).

The fuel oil is first heated to 70 DEG C in the fuel oil blending heating tank 11 at the time of operation and then a plurality of feed pumps 121, 122, 131, and 132 are simultaneously The fuel oil and the ionic liquid are transferred to the centrifugal extractor 15 in accordance with the set supply ratio, and an extraction processing step for desulfurization and denitrification proceeds. The mixture of the fuel oil and the ionic liquid, which is completed through the centrifugal extractor 15, enters the mixed solution buffer tank 16 and continues the extraction reaction.

The mixture ratio of the fuel oil and the ionic liquid is set according to the nature of the fuel oil and the content of the sulfur, and the mixing ratio of the fuel oil and the ionic liquid may be different. Experiments show that the mixing ratio of different types of fuel oil and ionic liquid can range from 3: 1 to 1: 3.5, but this ratio is affected by the content of DBTs in fuel oil and the working temperature of the extraction step do.

The oxidation treatment step (20) includes the following steps.

a. In the oxidation step (20), a plurality of feed pumps (211, 212), (221, 222) are provided and a pneumatic device (231), filtration and impurity discrimination removing process (232) An ozone generator assembly 23 including an ozone generator 233; Venturi Ejector (24); A mixed liquid buffer mixer 25 including a ventilator 251; An exhaust blower 26; Activated carbon adsorption tank (27); And an acceleration reaction tank 28.

b. During the actual operation, the ozone generator 233 is first driven to generate ozone, and the ozone is compressed to a pressure of 2 to 3 kg / cm ² and stored in the cylinder. When the mixed liquid of the fuel oil and the ionic liquid in the buffer tank 16 reaches the liquid level of the predetermined height, the feed pumps 211 and 212 are driven to mix the fuel oil and the ionic liquid, which have passed through the centrifugal extractor 15, Liquid mixer (2). At the same time when the liquid passes through the venturi gas-liquid mixer 24, the compressed ozone is sucked from the lateral bypass inlet and flows into the venturi gas-liquid mixer 24 to be gas-liquid mixed with the mixed liquid. When the ozone passes through the throat of the venturi gas-liquid mixer 24, ozone gas forms a bubble-like vigorous oscillation in the venturi gas-liquid mixer 24 because the passageway narrows but suddenly increases after passing through the throat. This phenomenon can increase the mutual contact between ozone and the mixture of fuel oil and ionic liquid, thus accelerating the oxidation reaction and increasing the reaction speed in the extraction treatment step. However, the characteristics of the substance (ionic liquid or aromatic hydrocarbon) Do not. The mixed liquid after the gas-liquid mixture enters the mixed solution buffering / mixing tank 25 and reacts, and the gas discharged from the mixed solution contains the decomposed ozone and is accumulated and accumulated in the exhaust unit 251. At this time, the blower 26 is driven to pump the gas, and is discharged to the atmosphere through the activated carbon adsorption tank 27. This mechanism can prevent air pollution by inhaling air pollutant emissions that may be present first. When the liquid level of the mixed solution buffering and mixing tank 25 reaches the set height, the mixed liquid which has entered the mixed solution buffering and mixing tank 25 is continuously subjected to the extraction reaction, and the transfer pumps 221 and 222 are driven again to return the mixed solution to the acceleration reaction tank 28 ) To continue the reaction and proceed to the next step.

In the centrifugation treatment step 30, the mixed solution after the extraction reaction is rapidly separated in the acceleration reaction tank 28 of the oxidation treatment step 20 to form a mixed solution of the ionic liquid and the extract, and a mixed solution of the fuel oil and the small amount of the extract.

In the centrifugal separation step (3), a plurality of transfer pumps 311 and 312, a high speed disc separator 32, a temporary reservoir 33 of a mixture of an ionic liquid and an extract, And a temporary reservoir (34) of a mixed liquid of the extract.

In the centrifugal separation step 30, when the extraction reaction is completed within the set time period in the acceleration reaction tank 28, the feed pumps 311 and 312 are driven to mix the fuel oil and the ionic liquid, To a high-speed centrifuge 32. The high-speed centrifuge separates the two different components at high speed using the difference in specific gravity between the upper layer liquid in the mixture liquid, that is, the fuel oil and the ionic liquid-containing extract. The separated ionic liquid (containing the extract) circulates in the piping and enters the temporary storage tank 33 of the mixed liquid of the ionic liquid and the extract. The fuel oil (containing a small amount of the extract) is circulated through the piping to mix the fuel oil and the small amount of the extract Enters the temporary storage tank 34 and is processed.

The specific gravity of the ionic liquid (OMIM BF4) is about 1.10 kg / liter, the specific gravity of the ionic liquid (BMIMFeCl4) is 1.365 kg / liter, and the specific gravity of the fuel oil is determined according to the fuel oil component. Gasoline is about 0.73 to 0.76 kg / liter, high-speed diesel is 0.83 to 0.86 kg / liter, marine diesel and boiler gasoline are about 0.85 to 0.87 kg / liter. The jet fuels are about 0.75 to 0.8 kg / liter. Heavy fuel oil is determined depending on the type. In general, IFO-180 to IFO-380 or 1-6 heavy oil is used. Specific gravity is 0.86 ~ 0.991 kg / liter. However, compared to the ionic liquid, the specific gravity of the ionic liquid and fuel oil is still considerably different, and the two materials can be separated using a high-speed separator.

As shown in Fig. 2, the fuel oil recovery processing step 40 takes a single stage distillation as a working core, and includes the following steps.

a. In the fuel oil recovery processing step 40, a plurality of feed pumps 411, 412, 421, 422, 431 and 432 in the fuel oil recovery processing step, a preheater 44 in the fuel oil recovery processing step, (Short Path Evaporator) 45 in the process step, a thermal oil expansion tank 46 in the fuel oil recovery process stage, a thermal oil heating furnace 47 in the fuel oil recovery process stage, a plurality of The fuel oil temporary transfer reservoir 491 of the fuel oil recovery process stage, the byproduct temporary storage tank 492 of the fuel oil recovery process stage, the vacuum buffer tank 493 of the fuel oil recovery process stage, Liquid separator 494 in the fuel oil recovery process stage, a vacuum pump 495 in the fuel oil recovery process stage, a purified oil storage tank 496, and a byproduct storage tank 497 in the fuel oil recovery process stage.

b. In the fuel oil recovery processing step (40), the heating oil oil heating path (47) in the fuel oil recovery processing step and the heating oil oil transfer pump (481, 482) in the fuel oil recovery processing step are first driven, The heat medium oil is transferred to the intermediate wall of the cylinder wall of the single-stage still 45 in the fuel oil recovery step and to the heating medium oil heating jacket layer of the preheater 44 in the fuel oil recovery step, (47). Some other heat medium oil circulates through the branch pipe and is transferred to the thermal oil expansion tank 46 in the fuel oil recovery process stage and returns to the inlet of the heat oil transfer pumps 481 and 482 in the fuel oil recovery process stage to recover the fuel oil Stage heat-oil heating furnace 47. [0050] This preheating process continues and when the temperature of the cylinder wall intermediate layer of the single distiller 45 in the fuel oil recovery step and the heating oil heating jacket layer of the preheater 44 of the fuel oil recovery processing step reach the set working temperature, The heating medium oil heating furnace 47 stops heating until the temperature of the heat medium oil flowing backward after the heat radiation becomes lower than the set temperature, and then drives the heating medium again to heat the heating medium. That is, the heating furnace is intermittently driven again to maintain the required working temperature. The calorific value and temperature of the heating oil heating furnace 47 in the fuel oil recovery step are controlled through a heating type fluid temperature controller (not shown) disposed in the system.

c. During operation of the heating oil heating system in the fuel oil recovery process stage, the vacuum pump 495 in the fuel oil recovery process stage is simultaneously driven, and the vacuum buffer tank 493 in the fuel oil recovery process stage, The fuel oil temporary reservoir 491 and the byproduct temporary reservoir 492 of the fuel oil recovery process stage in the fuel oil recovery process step are started to be evacuated through the separator 494, The vacuum pump 495 in the fuel oil recovery processing step stops discharging the air, and when the working pressure in the single still 45 rises due to the introduction of the raw material and the vacuum in the fuel oil recovery processing step The pump 495 begins to discharge air again. In other words, the vacuum pump is intermittently driven again to maintain the required working pressure. This mechanism maintains the stability of the system by keeping the working pressure within the single-stage still 45 in the entire fuel oil recovery stage at a predetermined range in the course of work.

d. When the temporary storage tank 34 of the mixed liquid of the fuel oil and the small amount of extract reaches the high liquid level in the centrifugation treatment step 30, the transfer pump 411 of the fuel oil recovery processing stage And 412 are driven to indirectly heat the mixed liquid of the fuel oil and the small amount of extract to the preheater 44 of the fuel oil recovery step. The raw material that has passed through the preheater 44 in the fuel oil recovery process stage is supplied to the raw material distribution plate above the single-phase still 45 in the fuel oil recovery process stage and then flows from the raw material discharge port arranged diagonally to the exhaust port in the raw material distribution plate (45) of the fuel oil recovery step along the cylinder wall in the single-phase still (45) of the fuel oil recovery step. A blade module (also referred to as cages) which is driven by the motor 451 and the reducer 452 on four sides in the single stage still 45 of the fuel oil recovery process stage and can be continuously rotated, ), And a blade made of graphite is installed in front of the cage. Since the spring unit behind the graphite blade pushes the graphite blade forward to support the inner cylinder wall of the fuel oil recovery step single stage still 45, the raw material continuously rotates as it flows downward along the cylinder wall, Is about 160 to 180 RPM, a mixture of fuel oil and a small amount of extract is applied to the surface of the cylinder wall to form a thin film having a predetermined thickness. Since the position where the raw material flows from the distribution plate into the single-phase still 45 in the fuel oil recovery step has a narrow angle of 180 degrees with the exhaust port, the position where the raw material forms the thin film is directly on one side of the opposite side of the exhaust port, The fuel oil component in which the working pressure and the working temperature in the single-stage still 45 in the fuel oil recovery step have already been locked has evaporated to become the molecular phase, and the working conditions have been reached. When the fuel oil is taken along the wall of the fuel cylinder and compressed on the cylinder wall by a blade to form a thin film, and then instantly receives heat from the surface of the thin film, the fuel oil molecules aiming at all locking are immediately evaporated and discharged. The vaporized molecules begin to move along the direction of the exhaust port, where the working pressure is relatively low, since the air is continuously discharged at the exhaust port located at the opposite side of the diagonal line to form a low-pressure inlet. However, since a set of condensers (not shown) is provided from the top to the bottom in the middle of the single-stage still 45 in the fuel oil recovery process step, the evaporated fuel oil molecules are discharged through the condenser before reaching the exhaust port The temperature of the fuel oil molecules adhering to the surface of the condenser is lowered and condensed into the liquid state because the cooling water flows into the condensing pipe on the condenser, ). When the inside of the fuel oil temporary storage tank 491 reaches a high liquid level, the feed pumps 421 and 422 in the fuel oil recovery process step are automatically driven, and the recovered fuel oil is transported to the refined oil storage tank 496 .

e. In the fuel oil recovery step 40, if a small amount of the extract contains impurities such as sulfides, nitrides and aromatic hydrocarbons in the mixture of fuel oil and a small amount of extract, it is evaporated at a predetermined working pressure and operating temperature These impurities still flow down along the cylinder wall slowly in the liquid state, fall into the inclined storage hopper below the inside of the monolithic still 45 in the fuel oil recovery step, flow into the discharge pipe, and finally And flows into the by-product temporary storage tank 492 in the lower fuel oil recovery process stage. When the liquid level of the byproduct temporary storage tank 492 in the fuel oil recovery process reaches a high level, the transfer pumps 431 and 432 in the fuel oil recovery process stage are driven to separate the by-products into the byproduct storage tank 497 ) To be transported.

As shown in Fig. 3, the ionic liquid recovery processing step (50) is centered on a single still, and includes the following steps.

a. A plurality of transfer pumps 511, 512, 521, 522, 531, and 532 in the ionic liquid recovery process step, a preheater 54 in the ionic liquid recovery process step, (Short Path Evaporator) 55 in the process step, a thermal oil expansion tank 56 in the ionic liquid recovery process step, a heating oil heating furnace 57 in the ionic liquid recovery process step, a plurality of The ionic liquid temporary storage tank 591 in the ionic liquid recovery process step, the byproduct temporary storage tank 592 in the ionic liquid recovery process step, the vacuum buffer tank 593 in the ionic liquid recovery process step, A gas-liquid separator 594 in the ion-liquid recovery process stage, a vacuum pump 595 in the ion-liquid recovery process stage, an ion-liquid storage tank 596 in the ion-liquid recovery process stage, and a by-product storage tank 597 in the ion- do.

b. In the ionic liquid recovery processing step (50), in the actual operation, the heating medium oil heating furnace (57) in the ionic liquid recovery processing step and the heating medium oil transferring pumps (581, 582) in the fuel oil recovery processing step are driven, To the cylinder wall intermediate layer of the single-phase still 55 in the ionic liquid recovery step and to the heating medium oil heating jacket layer of the preheater 54 in the ionic liquid recovery processing step, and again to the heating oil heating furnace 57 ). Some of the other heat transfer fluid circulates through the branch pipe and is transferred to the thermal oil expansion tank 56 in the ionic liquid recovery process stage and returns to the inlet of the heat transfer fluid pumps 581 and 582 in the ionic liquid recovery process stage, And is sent to the heating oil heating furnace 57 in the processing step. When the temperature of the intermediate wall of the cylinder wall of the single distiller 55 in the ionic liquid recovery process and the heating medium heating jacket layer of the preheater 54 in the ionic liquid recovery process step reach the set working temperature, In the heating oil heating furnace, the heating is temporarily stopped until the temperature of the heat oil flowing backward after the heat radiation becomes lower than the set temperature, and then the heating oil is driven again and heated. The calorific value and temperature of the heating oil heating furnace 57 in the ionic liquid recovery process step are controlled through a diode type temperature controller (heating fluid controller and programmable logic controller (PLC), not shown) disposed in the system.

c. The vacuum pump 595 in the ionic liquid recovery process stage is simultaneously driven in the operation of the heating medium oil heating system in the ionic liquid recovery process step so that the vacuum buffer tank 593 in the ionic liquid recovery process step, The temporary distiller 55, the ionic liquid temporary storage tank 591, and the byproduct temporary storage tank 592 in the ionic liquid recovery process step in the fuel oil recovery process step are started to be evacuated through the pipeline 594, When the vacuum pressure reaches the set working pressure, the vacuum pump 595 of the ionic liquid recovery process stops the temporary air discharge, and when the working pressure in the single-stage still is raised by the introduction of the raw material, the vacuum pump 595) starts to exhaust air again. In other words, the heating furnace is intermittently driven again to maintain the working temperature. This mechanism maintains the stability of the system by keeping the working pressure inside the single-stage still 55 in the entire ionic liquid recovery process step in the set range at all times during the work process.

d. When the temporary reservoir 33 of the mixed liquid of the ionic liquid and the extract reaches the high liquid level in the centrifugal separation processing step 30, the transfer pumps 511 and 512 of the ionic liquid recovery processing step Is driven to transfer the mixed solution of the ionic liquid and the extract to the preheater 54 of the ionic liquid recovery step to indirectly heat it. The raw material that has passed through the preheater 54 of the ionic liquid recovery process stage is supplied to the raw material distribution plate above the single-phase still 55 in the ionic liquid recovery process stage, and again from the raw material discharge port arranged diagonally to the exhaust port in the raw material distribution plate And then enters the single-phase still 55 of the ionic liquid recovery process step along the cylinder wall in the single-phase still 55 of the ionic liquid recovery process step. A blade module (also referred to as a cage) which is driven by a motor 551 and a speed reducer 552 whose four sides are on the upper side and is capable of rotating continuously is installed in the single-phase still 55 of the ionic liquid recovery process step And the cages are provided with a blade made of graphite at the front. The spring unit behind the graphite blade continuously rotates as the raw material flows downward along the cylinder wall because the spring unit pushes the graphite blade forward to support the inner cylinder wall of the monolithic still 55 of the ionic liquid recovery process step, Is about 160 to 180 RPM, a mixture of the ionic liquid and the extract is applied to the surface of the cylinder wall to form a thin film having a predetermined thickness. Since the position where the raw material flows from the distribution plate into the single-phase still 55 in the ionic liquid recovery process step forms a narrow angle of 180 degrees with the exhaust port, the position where the raw material forms the thin film is directly on one side of the opposite side of the exhaust port. Since the working pressure and the working temperature in the single-stage still 55 in the ionic liquid recovery step are in the state where the cylinder wall is originally continuously preheated and the working conditions in which the ionic liquid component already evaporated to become the molecular phase are reached, When the raw material falls along the wall of the ionic liquid, is compressed on the cylinder wall by the blade to form a thin film, and then receives heat instantaneously from the surface of the thin film, the ionic liquid molecules aiming at all locking are immediately evaporated . The vaporized ionic liquid molecules start to move along the direction of the exhaust port in which the working pressure is relatively low because air is continuously discharged at the exhaust port located at the opposite side of the diagonal line to form a low pressure inlet. However, since a set of condensers (not shown) is provided from the top to the bottom in the middle of the monolithic still 55 in the ionic liquid recovery process step, the evaporated ionic liquid molecules are discharged through the condenser The temperature of the ionic liquid molecules attached to the surface of the condenser is lowered and condensed into the liquid state because the cooling water flows into the condensing tube on the condenser, ). When the interior of the ionic liquid temporary storage tank 591 reaches a high liquid level, the transfer pumps 521 and 522 in the ionic liquid recovery process step are automatically driven to transfer the recovered ionic liquid to the purified oil storage tank 596 .

 e. In the ionic liquid recovery step (50), when a small amount of the extract in the mixed liquid of the fuel oil and the small amount of extract contains impurities such as sulfides, nitrides and aromatic hydrocarbons, it evaporates at a predetermined working pressure and operating temperature The impurities still flow down along the cylinder wall in the liquid state, fall down into the inclined type storage hopper located inside the single-stage still 55 in the ionic liquid recovery processing stage, flow into the discharge pipe again, and finally When the liquid in the byproduct temporary storage tank 592 of the ionic liquid recovery process reaches a high liquid level after being discharged to the byproduct temporary storage tank 592 in the lower ionic liquid recovery process stage, the transfer pumps 531 and 532 Is driven to store the by-product in the by-product storage tank 597 of the ionic liquid recovery process step and transport it.

As shown in FIG. 4, the common treatment step 60 includes a cooling trap 453 disposed outside the condenser of the single-stage still 45 in the fuel oil recovery step, To the condenser of the single distiller 55 and to the cooling trap 53 disposed outside.

The common processing step 60 includes a cooling water column 1, an ice water set 62, a plurality of ice water cooling water transfer pumps 631 and 632, cooling water recovery pumps 641 and 642, cooling water transfer pumps 651 and 652, Cooling water transfer pumps 661 and 662, and the like.

The facilities included in the common processing step 60 are sequentially driven to sequentially transfer ice water and cooling water to the ice water cooling water transfer pumps 631 and 632 and the cooling water transfer pumps 651 and 652 ) To the target facility such as the single inlet still pipe 45 of the fuel oil recovery processing stage and the single inlet still pipe 55 of the ionic liquid recovery processing stage through the cooling water transfer pumps 661 and 662, The cooling water circulates again through the recovery pipe and is sent to the cooling water tower through the cooling water recovery pumps 641 and 642 to be discharged and cooled. Thus, the temperature is set when the cooling water is discharged again. Depending on the demand of the system, the temperature of the cooling water discharged is about 25 to 28 ° C, the temperature of the recovered cooling water is about 30 to 33 ° C, and the temperature difference is about 5 ° C. Therefore, the parameters such as the heat dissipation energy required for the cooling water tower, the working pressure and the flow rate of the individual cooling water transfer pump are designed according to the individual conditions and demands of the operation system,

In one embodiment, the working pressure inside the unitary still 45 of the fuel oil recovery process step is 20-25 Pa (Pascal).

In one embodiment, the working temperature inside the single still 45 of the fuel oil recovery process step is 150-180 占 폚.

In one embodiment, a mixture of the fuel oil and a small amount of the extract is applied to the cylinder wall surface of the single-phase still 45 of the fuel oil recovery step with the graphite blade of the fuel oil recovery processing step 40, To form a thin film.

In one embodiment, the working pressure inside the monolithic still 55 of the ionic liquid recovery process step is 20-25 Pa (Pascal).

In one embodiment, the working temperature inside the single-phase still 55 of the ionic liquid recovery process step is 110 to 130 占 폚.

In one embodiment, a mixture of the ionic liquid and the extract is applied to the surface of the cylinder wall of the single-phase still 55 of the ionic liquid recovery process step with the graphite blade of the ionic liquid recovery processing step 50 to form a thin film having a thickness of less than 1 mm .

In one embodiment of the present invention, the single-stage still 45 of the fuel oil recovery step in the fuel oil recovery processing step 40 is provided with a cooling trap 453 attached to the outside, a transfer pump 454 and a storage tank 455 are further connected so that light hydrocarbons generated in the single stage still 45 of the fuel oil recovery process step can be introduced into the cooling trap 453 to be condensed, The raw material condensed in the cooling trap 453 is transferred to the storage tank 455 to be transported.

In the embodiment of the present invention, the single-stage still 55 in the ionic liquid recovery processing step in the ionic liquid recovery processing step 50 is provided with the cooling trap 553 attached to the outside, the transfer pump 554 in the ionic liquid recovery processing step ) And the storage tank 555 are further connected so that light hydrocarbons generated in the single-phase still 55 of the ionic liquid recovery process step can be introduced into the cooling trap 553 and condensed again. The raw material condensed in the cooling trap 553 is transferred to the storage tank 555 through the transfer pump 554 to be transported.

10: Fuel oil extraction processing step
11: Fuel oil blending heating tank
121, 122, 131, 132: Feed pump
14: Room temperature ionic liquid storage tank
15: Centrifugal extractor
16: Mixing liquid of fuel oil and extract Buffer
20: oxidation step
211, 212, 221, 222: Feed pump
23: Ozone generator assembly
231: Pneumatic machine
232: filtration of high-pressure gas and process for removing impurities
233: Ozone generator
24: venturi gas-liquid mixer
25: Mixing liquid Buffer mixing tank
251: Exhaust system
26: Exhaust blower
27: activated carbon adsorption tank
28: Acceleration reaction tank
30: Centrifugation treatment step
311, 312: Feed pump
32: High-speed centrifuge
33: Temporary storage of a mixture of ionic liquid and extract
34: Temporary storage of mixed liquid of fuel oil and extract
40: fuel oil recovery process step
411, 412, 421, 422, 431, 432: a transfer pump
44: Preheater of the fuel oil recovery step
45: Single type distiller in fuel oil recovery step
451: Motor
452: Reducer
453: Cooling Trap
454: Feed pump in fuel oil recovery process
455: Storage tank
46: Heat oil expansion tank in the fuel oil recovery step
47: Heat oil heating furnace in the fuel oil recovery step
481, 482: Heat oil transfer pump in the fuel oil recovery step
491: Fuel oil temporary reservoir
492: By-product temporary storage of fuel oil recovery stage
493: Vacuum buffer tank in fuel oil recovery step
494: Gas-liquid separator in fuel oil recovery process
495: Vacuum pump in fuel oil recovery process
496: refined oil storage tank
497: By-product storage tank of the fuel oil recovery step
50: ionic liquid recovery step
511, 512, 521, 522, 531, 532: transfer pump of ionic liquid recovery process step
54: preheater of ionic liquid recovery process step
55: Single stage still in the ionic liquid recovery step
551: Motor
552: Reducer
553: Cooling Trap
554: Transfer pump in ionic liquid recovery process step
555: Storage tank
56: thermal oil expansion tank in ionic liquid recovery process step
57: Heating oil heating furnace in ionic liquid recovery step
581, 582: heat medium oil transfer pump in ionic liquid recovery process step
591: Temporary storage tank for ionic liquid
592: By-product temporary storage of the ionic liquid recovery step
593: Vacuum buffer tank in ionic liquid recovery process
594: a gas-liquid separator in an ionic liquid recovery step
595: Vacuum pump in ionic liquid recovery process
596: ionic liquid storage tank
597: By-product storage tank of the ionic liquid recovery step
60: common processing step
61: cooling water tower
62: Ice water set
631, 632: Ice water cooling water transfer pump
641, 642: Coolant recovery pump
651, 652: Coolant transfer pump
661, 662: Coolant transfer pump

Claims (8)

(1) a step of extracting fuel oil, which is an extraction process for desulfurization and denitrification by mixing fuel oil and ionic liquid;
(2) a. A mixing liquid buffer mixer including a plurality of transfer pumps and including a pneumatic device, a gas filtering and impurity sorting removing process, an ozone generator assembly including an ozone generator, a venturi gas-liquid mixer, and an exhaust device, An activated carbon adsorption tank, and an acceleration reaction tank,
b. The ozone generator assembly produces and stores ozone, and the mixture of the fuel oil and the ionic liquid extracted in the fuel oil extraction processing step is transferred to the venturi gas-liquid mixer through a transfer pump. The venturi gas- The ozone is sucked, the mixed liquid of the extracted fuel oil and the ionic liquid is mixed with gas-liquid to form a bubble-like oscillation,
c. The mixed liquid, which has undergone the gas-liquid mixing operation of the venturi gas-liquid mixer, enters the mixed solution buffer mixer, and the ozone discharged from the mixed solution rises and accumulates in the exhaust device. The gas is pumped by the exhaust blower, An oxidation treatment step in which the transfer pump is driven to transfer the mixed solution to the acceleration reaction tank when the mixed solution introduced into the mixed solution buffer and mixing vessel reaches a predetermined level, thereby continuing the reaction;
(3) a centrifugal separation step of centrifugally separating the mixed solution extracted and reacted in the acceleration reaction tank in the oxidation treatment step using a centrifugal separator to form a mixed solution of the ionic liquid and the extract and a mixed solution of the fuel oil and the extract;
(4) As a fuel oil recovery process step having a single-stage still as a working core,
a. A plurality of feed pumps in the fuel oil recovery step, a preheater of the fuel oil recovery step, a single-stage still of the fuel oil recovery step, a thermal oil expansion tank of the fuel oil recovery step, A plurality of thermal oil transfer pumps in the fuel oil recovery step, a fuel oil temporary storage tank in the fuel oil recovery process stage, a byproduct storage tank in the fuel oil recovery process stage, a vacuum buffer tank in the fuel oil recovery process stage, A gas-liquid separator, a vacuum pump in the fuel oil recovery step, a refinery oil reservoir in the fuel oil recovery step, and a by-product reservoir in the fuel oil recovery step,
b. Wherein the heat oil heating furnace of the fuel oil recovery process and the heat oil transfer pump of the fuel oil recovery process are connected to the intermediate wall of the cylinder wall of the fuel oil recovery process step and the preheater of the fuel oil recovery process step And then returns to the heating oil heating furnace of the fuel oil recovery processing step. Further, the other part of the heating oil is transferred to the heating oil expansion tank of the fuel oil recovery processing step, and then the heating medium of the fuel oil recovery processing step The heating oil heating furnace is intermittently driven when the cylinder wall of the single-stage still and the heating jacket layer of the preheater of the fuel oil recovery processing step reaches the set working temperature, Maintaining the temperature,
c. The vacuum pump of the fuel oil recovery process step is driven so that the vacuum buffer tank of the fuel oil recovery process stage, the single-stage still tank of the fuel oil recovery process stage through the gas-liquid separator of the fuel oil recovery process stage, A temporary storage tank for the fuel oil in the fuel oil recovery step is set to a vacuum until the set working pressure is reached and the vacuum pump is driven intermittently to maintain the required working temperature,
d. The feed pump of the fuel oil recovery process transfers the mixed fuel of the fuel oil and the extract formed in the centrifugal separation process to the preheater of the fuel oil recovery process step and heats the mixed fuel to the single stage still And a thin film is formed by applying a mixture of the fuel oil and the extract to a cylinder wall surface of a single-phase still in the fuel oil recovery step with a blade installed in a single-phase still in the fuel oil recovery step, The fuel oil molecules are evaporated by being heated by a temperature generated when the heating medium oil is heated by the cylinder wall intermediate layer of the single-stage still in the recovery process step, and the fuel oil molecules are pumped to the condenser inside the single- And the condenser has a temperature of the fuel oil molecules attached to the surface of the condenser And condensed to a liquid state Sanctuary, the fuel oil in a liquid state and re-enter into the fuel oil temporary storage tank is sent to the refined oil storage tank,
e. The extract in the mixed liquid of the fuel oil and the extract is not evaporated to become a molecular phase and becomes a liquid state and falls downward in the interior of the single-phase still in the fuel oil recovery step along the cylinder wall, A fuel oil recovering step of entering the storage tank and being sent to the byproduct storage tank;
(5) An ionic liquid recovery process step having a single-stage still as a working core,
a. A plurality of transfer pumps in the ionic liquid recovery step, a pre-heater in the ionic liquid recovery step, a single-stage still in the ionic liquid recovery step, a thermal oil expansion tank in the ionic liquid recovery step, A plurality of thermal oil transfer pumps in the ionic liquid recovery step, an ionic liquid temporary storage tank in the ionic liquid recovery process step, a byproduct storage tank in the ionic liquid recovery process step, a vacuum buffer tank in the ionic liquid recovery process step, Liquid separator, a vacuum pump in an ionic liquid recovery process step, an ionic liquid storage tank in an ionic liquid recovery process step, and a byproduct storage tank in an ionic liquid recovery process step,
b. Wherein the heat medium oil heating furnace in the ionic liquid recovery process step and the heating medium oil transfer pump in the ionic liquid recovery process step are arranged so that a part of the heating medium oil is supplied to the intermediate wall of the cylinder wall of the single- Is transferred to the heating jacket layer of the preheater and returns to the heating oil heating furnace of the ionic liquid recovery process step, and the other part of the heating oil oil is sent to the thermal oil expansion tank of the ionic liquid recovery process step, The heating oil heating furnace is driven intermittently when the cylinder wall of the single-phase still and the heating jacket layer of the preheater of the ionic liquid recovery processing step reach the set working temperature, Maintaining the temperature,
c. The vacuum pump of the ionic liquid recovery process step is driven so that the vacuum buffer tank of the ionic liquid recovery process step and the monolithic still of the ionic liquid recovery process step through the gas / liquid separator of the ionic liquid recovery process step, The temporary reservoir of the byproduct of the ionic liquid recovery process is evacuated until the set working pressure is reached and then the vacuum pump is intermittently driven to maintain the required working temperature,
d. Wherein the transfer pump in the ionic liquid recovery process step transfers the mixed liquid of the ionic liquid and the extract formed in the centrifugal separation process step to the preheater of the ionic liquid recovery process step and heats the mixed liquid to the monolithic still A mixed solution of the ionic liquid and the extract is applied to the surface of the cylinder wall of the single-phase still in the ionic liquid recovery step by a blade installed in the single-stage still in the ionic liquid recovery step to form a thin film, The temperature of the heating medium is heated by the intermediate layer of the cylinder wall to be heated to evaporate the ionic liquid molecules and the ionic liquid molecules are pumped to the condenser inside the single type still in the ionic liquid recovery step, The temperature of the ionic liquid molecules adhering to the liquid is lowered, The ionic liquid in the liquid state again enters the ionic liquid temporary storage tank and is sent to the ionic liquid storage tank,
e. The extract in the mixed solution of the ionic liquid and the extract is not evaporated to become a molecular phase and is in a liquid state and falls down into the interior of the single-phase still in the ionic liquid recovery process step along the cylinder wall, An ionic liquid recovery process step of entering the storage tank and sending it to a byproduct storage tank in the ionic liquid recovery process step; And
(6) Providing cooling water and ice water using a cooling water tower and an ice water grate, supplying cooling water and ice water to a condenser provided inside the single-phase still water recovery step of the fuel oil recovery step and cooling traps attached to the outside as condensed water, A common processing step of providing the cooling water and the ice water to the condenser provided inside the single-stage still in the ion recovery processing step and the cooling trap attached to the outside,
≪ / RTI > The method according to claim 1,
Wherein the working pressure set in the monolithic still in the fuel oil recovery step or in the monolithic still in the ionic liquid recovery step is 20 to 25 Pa. The method according to claim 1,
Wherein the working temperature set in the single-phase still in the fuel oil recovery step is 150 to 180 ° C. The method according to claim 1,
Wherein a mixture of the fuel oil and the extract is applied to the cylinder wall surface of the single-phase still in the fuel oil recovery step with the graphite blade in the fuel oil recovery step to form a thin film having a thickness of less than 1 mm. The method according to claim 1,
Wherein the working temperature set in the single-phase still in the ionic liquid recovery step is 110 to 130 占 폚. The method according to claim 1,
Wherein a mixed solution of an ionic liquid and an extract is applied to the surface of a cylinder wall of a single-phase still in the ionic liquid recovery step with a graphite blade in the ionic liquid recovery step to form a thin film having a thickness of less than 1 mm. The method according to claim 1,
A cooling trap attached to the outside of the single-phase still in the fuel oil recovery step in the fuel oil recovery process step, a transfer pump in the fuel oil recovery process step, and a storage tank are further connected,
The hydrocarbon that has been generated in the single-stage distillation unit in the fuel oil recovery process step can be introduced into the cooling trap to be condensed, and the raw material condensed in the cooling trap is transferred to the storage tank through the transfer pump in the fuel oil recovery process step And the fuel is supplied to the fuel tank. The method according to claim 1,
A cooling trap attached to the outside, a transfer pump in a fuel oil recovery process step, and a storage tank are further connected to the single-stage still in the ionic liquid recovery process in the ionic liquid recovery process,
The condensed raw material in the cooling trap is transferred to the storage tank through the transfer pump in the ionic liquid recovery process step to transfer the condensed raw material to the storage tank, And the fuel is supplied to the fuel tank.

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