JP2928466B2 - Method and apparatus for recovering organic sulfur compounds from residual oil or heavy oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for recovering organic sulfur compounds from residual oil or heavy oil.

[0002]

2. Description of the Related Art In recent years, as crude oil has become heavier worldwide, useful light distillates have been removed, and then heavy distillates, especially residual oils, are produced in large quantities as by-products. This residual oil has a high concentration due to the concentration of sulfur, nitrogen and metal. As a method of lightening this residual oil, there are hydrocracking of the residual oil, fluid catalytic cracking, etc., but if the residual oil containing a high concentration of sulfur is used as it is,
It causes catalyst poisoning and further causes air pollution. Therefore, a method of removing the sulfur content in the residual oil is important.

At present, a hydrogen reduction desulfurization method is generally employed as a method for removing sulfur from residual oil. That is, the feedstock (residual oil) is contact-treated under hydrogen pressure to remove sulfur compounds in the crude oil into hydrogen sulfide. Generally, in the hydrogen reduction desulfurization of residual oil, the conditions employed are such that the reaction pressure is 100 kg / cm ² , preferably 10 kg / cm ² .
0 to 170 kg / cm ² , a reaction temperature of 300 ° C. or higher, preferably 350 to 450 ° C., and a hydrogen / feed oil ratio of 100 to
2000 NI / NI. The catalyst used is
It is an oxide of an expensive active metal such as nickel, cobalt, molybdenum, vanadium, and tungsten.

A method for removing sulfur from fuel oil is disclosed in Japanese Patent Application Laid-Open No. 4-72387. A method for removing sulfur from the fuel oil comprises treating a fuel oil obtained from petroleum and coal liquefied oil with an oxidizing agent,
It is to separate and remove by increasing the boiling point of the contained organic sulfur.

Further, as a refining technique for coal-based heavy oil using a solvent, there is one disclosed in JP-A-56-49791. This involves refining coal-based heavy oil by blending a ketone solvent with coal-based heavy oil, removing insoluble precipitates generated in the mixture, and separating the ketones in the mixture. It is about the method.

[0006]

However, in the hydrogen reduction desulfurization method, sulfur compounds contained in a large amount in the residual oil are difficult to be desulfurized, and high reaction temperatures and pressures are required to achieve high desulfurization. However, if the reaction temperature is increased, coke is likely to be generated, and it is necessary to further increase the reaction temperature in order to compensate for a decrease in catalytic activity due to blockage of the contact pores by coke. At that time, it is known that, among the obtained products, the properties of a fraction having a boiling point of 360 ° C. or more are particularly deteriorated.

[0007] The difficulty of desulfurization in the hydrogen reduction desulfurization method is as follows.
Organic sulfur compounds contained in the residual oil and hydrocarbons,
Derived from similar chemical properties. In particular, higher pressure and higher temperature conditions are required to break down chemically stable functional groups such as benzothiophene and dibenzothiophene derivatives which are present in large amounts in residual oil. In order to recover the organic sulfur compound contained in the residual oil while maintaining the original chemical structure, no means of chemical change such as high temperature, pressure, light, or chemical reaction such as oxidation and reduction is used. Method development is required.

In the above-mentioned hydrogen reduction desulfurization method, the sulfur content in the residual oil, that is, the organic sulfur compound, has been conventionally recognized as a harmful substance. It had been converted to strong hydrogen sulfide. There is no idea of recovering the organic sulfur compound in the residual oil while maintaining the original chemical structure of the organic sulfur compound contained in the residual oil for effective utilization thereof.

However, the organic sulfur compound contained in the residual oil can be regarded as one form of the organic sulfur compound as an industrial raw material that has recently attracted attention, and promises a great contribution to human society in the near future. Is a valuable resource. For example, benzothiophene and dibenzothiophene derivatives, which are chemically stable and therefore difficult to hydrodesulfurize, are important as useful industrial raw materials.If these are to be produced from inorganic sulfur, complex chemical processes are required. It requires a large production cost.

In order to remove the organic sulfur compound from the residual oil while maintaining the original chemical structure, and to effectively use the organic sulfur compound, the hydrogen reduction desulfurization method cannot be applied.
Recovering an organic sulfur compound from a feedstock is, in other words, desulfurization of the feedstock.However, from the viewpoint of desulfurization, the hydrogen reduction desulfurization method is an operation under high temperature and high pressure. Therefore, stable operation of the apparatus requires advanced management techniques, consumes expensive rare metal catalysts, and involves a large amount of supply and consumption of hydrogen.

The method for removing sulfur from fuel oil disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 4-72387 is a method in which a fuel oil obtained from petroleum and coal liquefied oil is treated with an oxidizing agent. The method does not recover the organic sulfur compound while maintaining the original chemical structure, and requires an oxidation step and a separation step of the oxidized organic sulfur component.

Further, the method for purifying coal-based heavy oil disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 56-49791 discloses a method for refining coal-based heavy oil as a raw material for producing a carbon material such as graphitizable acicular coke. The purpose of refining and blending a ketone solvent with coal-based heavy oil is to remove inert carbon substances (quinoline-insoluble matter) in the coal-based heavy oil which are harmful to the raw material for producing the carbon material. The technical problem of recovering a useful organic sulfur compound in the coal-based heavy oil is not disclosed at all.

Accordingly, an object of the present invention is to eliminate the need to raise the temperature or pressure of the residual oil or heavy oil when recovering the organic sulfur compound from the residual oil or heavy oil. Without the need to supply hydrogen and other consumables, organic sulfur compounds can be easily, economically and efficiently recovered with high recovery efficiency while maintaining the original chemical structure contained in the residual oil or heavy oil. An object of the present invention is to provide a method and an apparatus for recovering an organic sulfur compound from oil or heavy oil. The method and apparatus for recovering an organic sulfur compound from residual oil or heavy oil are applicable to a method and an apparatus for desulfurizing an organic sulfur compound from residual oil or heavy oil.

[0014]

SUMMARY OF THE INVENTION The present invention is configured as follows in order to achieve the above object. That is, the present invention is to add a solvent having a boiling point lower than the boiling point to the residual oil or the heavy oil, and to stir and mix the residual oil or the heavy oil and the solvent at a temperature equal to or lower than the boiling point of the solvent. The residual oil or the organic sulfur compound contained in the heavy oil is transferred into the solvent while lowering the viscosity of the heavy oil, and then the mixture of the residual oil or the heavy oil and the solvent is cooled to room temperature or a temperature lower than room temperature. And separating the residual oil or heavy oil from the solvent containing the organic sulfur compound, and further distilling the separated solvent containing the organic sulfur compound to recover the organic sulfur compound in the solvent. Alternatively, the present invention relates to a method for recovering an organic sulfur compound from heavy oil.

In the method for recovering an organic sulfur compound from the residual oil or the heavy oil, the solvent may be acetone, pinacolin, methysyl oxide, acetophenone, benzophenone, acetylacetone, 2-butanone, methanol,
Ethanol, propanol, butanol, acetonitrile, propionitrile, butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene,
Substance consisting of one or more selected from dimethyl sulfoxide, N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methylpyrrolidinone, trimethyl phosphate, triethyl phosphate, hexamethyl phosphoramide, phosphorane, pyridine Or water and / or 1 in a concentration range of 20% or less with respect to the substance.
It is selected from a mixture containing 0% or less of acids.

In the method for recovering an organic sulfur compound from a residual oil or a heavy oil, the residual oil or the heavy oil mixed with the solvent is reduced in viscosity or in a liquid state within a temperature range not higher than the boiling point of the solvent. Is to be

Further, in the method for recovering an organic sulfur compound from the residual oil or the heavy oil, the recovered organic sulfur compound is maintained in a state where the original chemical structure contained in the residual oil or the heavy oil is maintained. It is.

The term "residual oil" as used herein means a residual oil obtained by distillation of crude oil at normal pressure or reduced pressure, an oil sand, or a residual oil obtained by distillation of crude oil extracted from tar sand at normal pressure or reduced pressure, or a mixture thereof. And coal tar. In addition, the heavy oil referred to here is a straight run heavy light oil (HG
O), heavy oil, vacuum gas oil (VGO) and orinoco crude oil, oil sands, tar sands, oil extracted from oil shells, and tar-like heavy oils such as primary products of coal liquefied oil.

The solvent used need not have a viscosity reducing effect at room temperature (20 ° C.) on high viscosity residual oil or heavy oil. That is, only at the time of stirring and mixing of the residual oil or heavy oil and the solvent, the swelling of the residual oil or heavy oil, the viscosity is temporarily reduced, the residual oil or the heavy oil and the solvent dissolve, When the stirring operation is stopped, it is an important component that residual oil or heavy oil is separated. Thus, the reduction in viscosity of the resid or heavy oil depends on the choice of solvent and also on the temperature of the resid or heavy oil or the ability to shear, disperse or mix the resid or heavy oil with a stirrer. ing.

It is desirable that the solvent used has a low solubility in the tar component of the residual oil or the heavy oil, a high transfer rate of the organic sulfur compound, and a high transfer rate.

For chemical functional groups which are present abundantly in residual oil or heavy oil, aprotic dipolar solvents such as acetone and acetylacetone are preferably used because they exhibit a higher partition coefficient than alcohols. Is done. In this case, the fact that the lone pair of electrons on the divalent sulfur atom of the sulfur functional group has strong nucleophilicity is applied, and the aprotic dipolar solvent having strong electron donating property is added to the alcohol-based solvent. Alternatively, by adding up to 20% of water and / or an acid selected from organic carboxylic acids, sulfonic acids, sulfuric acids, nitric acids and hydrochloric acids, the selectivity to organic sulfur compounds present in the resid or heavy oil is increased. be able to. This utilizes the nucleophilicity of the organic sulfur compound to change the original physical properties, that is, the solubility, to achieve elution and separation from other hydrocarbons.

When the organic sulfur compound in the residual oil or the heavy oil is transferred into the solvent, the solvent is at least a few percent.
It is unavoidable that the oil and / or tar content is transferred, and it is possible to remove the oil and / or tar content from the recovered solvent containing the organic sulfur compound in which the tar content is dissolved by a centrifuge. . In this case, the addition of a few percent of water and / or acids and / or the cooling of the recovered solvent promotes the separation of the oil and / or tar components.

The method for recovering the organic sulfur compound from the residual oil or the heavy oil is as follows. The residual oil or the heavy oil is mixed with the solvent at a temperature within the boiling point of the solvent and then mixed at room temperature (20 ° C.), or After cooling to room temperature or lower, the separated solvent is distilled, and the solvent is cooled and reused, and the organic sulfur compound in the distillation residue is concentrated and separated.

Alternatively, the present invention provides a reaction tank for mixing a solvent additive selected from a residual oil or a heavy oil, a solvent, water and / or an acid while heating to form a mixed solution; A separation device that cools the generated mixed solution to separate an oil component and a solvent containing an organic sulfur compound, a centrifugal separator that removes and discharges a tar component from the separated solvent containing an organic sulfur compound, A residual solvent or heavy oil, comprising: a separated solvent distillation tank that separates and recovers the solvent and the organic sulfur compound by evaporating the solvent containing the organic sulfur compound from which the tar component has been removed by the centrifugal separator. And a device for recovering organic sulfur compounds.

[0025]

The method and apparatus for recovering organic sulfur compounds from residual oil or heavy oil according to the present invention are constructed as described above, and operate as follows. That is, in the present invention, the viscosity of the residual oil or the heavy oil at room temperature is 30 to 10
The viscosity temperature characteristic of the residual oil or heavy oil which rapidly decreases at a temperature between 0 ° C. and can be stirred by a stirrer is around 35 ° C. Therefore, based on these points, a solvent having a high solubility for the organic sulfur compound contained in the residual oil or heavy oil is selected, and the selected solvent is added to the residual oil or heavy oil. By stirring and mixing at a temperature equal to or lower than the boiling point, the residual oil or heavy oil is temporarily thinned only at the time of stirring, and the organic sulfur compound present in the residual oil or heavy oil is efficiently mixed in the solvent. Is to be moved.
That is, the method for recovering the organic sulfur compound from the residual oil or the heavy oil is a method for recovering the organic sulfur compound in the residual oil or the heavy oil by mass transfer, and the method for recovering the organic sulfur compound from the residual oil or the heavy oil. It can also be applied to a desulfurization method for removing.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method and an apparatus for recovering an organic sulfur compound from a residual oil or heavy oil according to the present invention will be described below with reference to the drawings and tables. FIG. 1 is a system diagram showing a recovery apparatus for achieving a method for recovering an organic sulfur compound from residual oil or heavy oil according to the present invention, and FIG. 2 is an organic sulfur compound from residual oil or heavy oil according to the present invention. 4 is a graph showing the sulfur content in heavy oil according to the abundance ratio of water, using acetone as a solvent in a method for recovering a compound.

In the method for recovering organic sulfur compounds from residual oil or heavy oil, first, an additive is charged from the additive tank 13 to the solvent tank 2 and the additive is added from the solvent tank 2 to the reaction tank 5. Add the solvent. On the other hand, the residual oil or heavy oil is charged into the reaction tank 5 from the tank 1 containing the residual oil or heavy oil. The residual oil or heavy oil and the solvent charged in the reaction tank 5 are mixed by stirring the residual oil or heavy oil and the solvent by the stirrer 3 having the function of shearing and dispersing while heating by the heating device 4. After the mixture is liquefied and the residual oil or heavy oil is swollen and liquefied, the mixed liquid is transferred to the stationary tank 6. The solvent containing the organic sulfur compound separated from the mixed solution in the upper layer of the stationary tank 6 is transferred to the separation solvent tank 7, and the desulfurized residual oil is transferred to the desulfurized residual oil tank 12. Next, the solvent containing the separated organic sulfur compound is removed by a centrifugal separator 8 to remove the tar and the separated tar is discharged to the separation tar tank 11, and the solvent containing the organic sulfur compound from which the tar has been removed is separated. Transfer to solvent distillation tank 9. Therefore, the solvent containing the organic sulfur compound is distilled by the separation solvent distillation tank 9,
The solvent recovered by the distillation is returned to the solvent tank 2, the recovered additive is returned to the additive tank 13, and the distillation residue is recovered as an organic sulfur compound in the recovered organic sulfur compound tank 10. Further, the solvent containing the organic sulfur compound from which the tar content was removed by the centrifugal separator 8 was cooled by the cooling tank 14 to coagulate the oil dissolved in the solvent, and further separated and separated by the centrifugal separator 15. By guiding the oil to the desulfurization residual oil tank 12, the amount of oil mixed into the organic sulfur compound recovered as a distillation residue can be reduced. The addition of the additive may be performed after the residual oil and / or heavy oil and the solvent are mixed in the reaction tank, or may be added to the solvent in the cooling tank 13.

An embodiment of the method for recovering organic sulfur compounds from residual oil or heavy oil according to the present invention will be described below. [Example 1] In a reaction tank 5, a direct distillation residue (sulfur content 4420)
(0 ppm), 300 ml of acetone and 6 ml of water were added, and the mixture was heated to 50 ° C. and stirred and mixed with a propeller type stirrer 3 at 2000 rpm for 30 seconds to form a mixed solution. ), And the acetone containing the organic sulfur compound separated into the upper layer is taken out from the mixture. After repeating this operation six times, the centrifugal separator 8 is operated at 3000 rpm to remove the tar content from the separated acetone containing the organic sulfur compound for six times by centrifugation. An organic sulfur compound was recovered as a residue. The sulfur content in the treated residual oil is 1260 ppm, and the recovery of organic sulfur compounds contained in the residual oil is 97% in terms of sulfur.
Met.

Example 2 300 g of a direct distillation residue (sulfur content: 44200 ppm) was placed in a reaction vessel 5, 300 ml of ethanol and 6 ml of water were added, and these were heated to 60 ° C.
After stirring and mixing at 2000 rpm for 30 seconds with a propeller type stirrer 3 to form a mixture, the mixture was cooled still to room temperature (20 ° C.), and ethanol containing an organic sulfur compound separated into an upper layer from the mixture. Take out.
After repeating this operation seven times, the centrifuge (3000)
rpm), centrifugal separation was performed to remove tar components from the separated ethanol containing the organic sulfur compound for seven times, and then the mixture was distilled at a temperature of 80 ° C. to recover the organic sulfur compound as a distillation residue. The sulfur content in the treated residual oil is 314
It was 0 ppm, and the recovery of the organic sulfur compound contained in the residual oil was 93% in terms of sulfur.

Example 3 300 g of a direct distillation resid (44200 ppm sulfur) was placed in a reaction vessel 5 and acetone 3
Then, the mixture was heated to 50 ° C. and stirred and mixed with a propeller-type stirrer 3 at 2000 rpm for 60 seconds to form a mixed solution. Then, the mixed solution was cooled to −5 ° C. and separated into an upper layer from the mixed solution. The solvent containing the organic sulfur compound is removed. After repeating this operation seven times, the separation solvent containing the organic sulfur compound for seven times is distilled at a temperature of 80 ° C.
An organic sulfur compound was recovered as a distillation residue from the separated solvent. The sulfur content in the treated residual oil was 1550 ppm, and the recovery of organic sulfur compounds contained in the residual oil was 96.6% in terms of sulfur.

Example 4 300 g of a direct distillation residue (sulfur content: 44200 ppm) was placed in a reaction vessel 5, 270 ml of ethanol and 30 ml of methysyl oxide were added, and the mixture was heated to 60 ° C. 3000
After stirring and mixing at 60 rpm for 60 seconds to form a mixture, the mixture is cooled to 10 ° C., and a solvent containing an organic sulfur compound separated into an upper layer is removed from the mixture. This operation was repeated seven times, and the separation solvent containing the organic sulfur compound for seven times was distilled at a temperature of 130 ° C., and the organic sulfur compound was recovered as a distillation residue. The sulfur content in the treated residual oil is 1820
ppm, and the recovery of organic sulfur compounds contained in the residual oil was 96% in terms of sulfur.

Example 5 300 g of a direct distillation residue (sulfur content: 44200 ppm) was placed in a reaction vessel 5, 280 ml of ethanol, 20 ml of acetophenone and 6 ml of water were added, and these were heated to 60 ° C. After stirring and mixing at 2000 rpm for 30 seconds to form a mixed solution, the mixed solution is cooled to 10 ° C., and a solvent containing an organic sulfur compound separated into an upper layer is removed from the mixed solution. After repeating this operation seven times, centrifuge 8 is
After removing the tar content from the separation solvent containing the organic sulfur compound for 7 times by centrifugation while operating at pm,
Distillation was performed at a temperature of 210 ° C., and an organic sulfur compound was recovered as a distillation residue. The sulfur content in the treated residual oil was 1910 pp
m, and the recovery of the organic sulfur compound contained in the residual oil was 95.7% in terms of sulfur.

Example 6 300 g of a direct distillation residue (44200 ppm of sulfur) was placed in a reaction vessel 5, and 290 ml of ethanol, 10 ml of 2-butanone, 6 ml of water, and 1 ml of formic acid
The mixture was heated to 60 ° C. and mixed by stirring with a propeller-type stirrer 3 at 3000 rpm for 30 seconds to form a mixture. The mixture was allowed to stand still for 5 minutes, and the organic sulfur separated in the upper layer of the mixture was added. The solvent containing the compound is removed.
After repeating this operation seven times, centrifuge 8
After operating at 0 rpm and removing the tar component from the separation solvent containing the organic sulfur compound for seven times by centrifugation, distillation was performed at a temperature of 90 ° C. to recover the organic sulfur compound as a distillation residue. The sulfur content in the treated residual oil is 1880p
pm, and the recovery of organic sulfur compounds contained in the residual oil was 95.8% in terms of sulfur.

Example 7 A straight-run heavy gas oil (H
GO, sulfur content 17000ppm)
Heat to 0 ° C., and use propeller type stirrer 3 for 1000 r.
While stirring at pm, acetone (300 cc) was injected, and the mixture was further stirred for 30 seconds. Then, the mixture was allowed to stand still for 5 minutes, and the organic sulfur compound separated into the upper layer of the heavy oil A deposited in the lower layer, and the oil component. The solvent containing is taken out. And one more
% Of water, stirred at 1000 rpm for 30 seconds, and then stopped for 10 minutes, and the solvent containing the organic sulfur compound in the upper layer where oil B was deposited was taken out. This is further cooled to −5 ° C., and the solvent containing the organic sulfur compound in the upper layer of the oil component C deposited in the lower layer is separated. The oil component A, the oil component B, and the oil component C are each heated, injected with an equal amount of acetone, stirred and cooled five times, and then combined as a desulfurized oil component. The sulfur content in the treated HGO was 680 ppm, and the recovery of organic sulfur compounds contained in HGO was 96% in terms of sulfur.

Example 8 A vacuum gas oil (VGO,
300 g of sulfur content (24000 ppm of sulfur) was added, heated to 50 ° C., and 300 cc of acetone was injected with a propeller-type stirrer 3 while stirring at 1000 rpm. After stirring for 30 seconds, the mixture was allowed to stand still for 5 minutes and sedimented. The solvent containing the organic sulfur compound and the oil separated in the upper layer of the heavy oil A is taken out. 1% water was added thereto, and the mixture was stirred with a stirrer at 1000 rpm for 30 seconds, and then stopped for 5 minutes to take out a solvent containing an organic sulfur compound in the upper layer where oil B was deposited. This is further cooled to −5 ° C. to obtain an oil C that is slightly lighter than B in the lower layer, and the solvent containing the organic sulfur compound in the upper layer is taken out. After repeating oil A, oil B, and oil C, heating, adding an equal amount of acetone, stirring, cooling, and separating the solvent five times, the oil A, the oil B, and the oil C are combined to obtain a desulfurized VGO. The sulfur content in the treated VGO is 7
It was 20 ppm, and the recovery of organic sulfur compounds contained in VGO was 97% in terms of sulfur.

[Example 9] An example showing the ability to extract an organic sulfur compound for each solvent will be described. Fuel oil A (sulfur content 6200ppm) in 30ml female cylinder with stopper
15 ml and 15 ml of acetone were added, and the mixture was stirred at intervals of 5 minutes while irradiating ultrasonic waves for 30 minutes. Then water 0.15
After adding and stirring the mixture, the mixture was allowed to stand for a whole day and night, and then the heavy oil layer was collected, washed with water and dried. Also, N,
N′-dimethylformamide (DMF), acetonitrile, trimethyl phosphate, nitromethane, methanol, hexamethylphosphoramide (HMPA), acetic acid, pyridine,
A treatment with N-methylpyrrolidinone (NMP) was performed. Table 1 shows the results of desulfurization (recovery of organic sulfur compounds) for these solvents according to the sulfur content in the treated heavy oil A.

[Table 1]

Example 10 Heavy oil A (sulfur content 620)
When the solvent for recovering (desulfurizing) the organic sulfur compound (0 ppm) is acetone, the effect of the water content is shown in Table 2 and FIG.

[Table 2]

[0038]

The method and apparatus for recovering organic sulfur compounds from residual oil or heavy oil according to the present invention have the following effects because they are configured as described above. That is, according to the present invention, the organic sulfur compound contained in the residual oil or the heavy oil can be recovered with high efficiency using a simple facility, and the residual oil or the organic compound can be recovered at a low cost. The organic sulfur compound contained in the heavy oil can be recovered while maintaining the original chemical structure. The recovered organic sulfur compound can be used as an industrially useful raw material in the fields of manufacturing pharmaceuticals, agricultural chemicals, heat-resistant resins, and the like.

Further, the present invention is a simple recovery method and a recovery apparatus using simple equipment, from the viewpoint of desulfurization of an organic sulfur compound for recovering residual oil or heavy oil. In the process of recovering organic sulfur compounds from heavy oil, there is no need to raise the temperature or pressure of the residual oil or heavy oil, reduce the energy consumption in the recovery process, generate no coke, and It is a desulfurization method that does not require reduction, and its economic effect is remarkable.

[Brief description of the drawings]

FIG. 1 is a system diagram showing a recovery apparatus for achieving a method for recovering an organic sulfur compound from residual oil or heavy oil according to the present invention.

FIG. 2 is a graph showing the sulfur content in heavy oil according to the abundance ratio of water using acetone as a solvent in the method for recovering organic sulfur compounds from residual oil or heavy oil according to the present invention. is there.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Residual oil tank 2 Solvent tank 3 Reaction tank stirrer 4 Reaction tank heating device 5 Reaction tank 6 Stationary tank 7 Separation solvent tank 8 Centrifuge 9 Separation solvent distillation tank 10 Recovered organic sulfur compound tank as distillation residue 11 Separation tar tank 12 Desulfurization residue tank 13 Solvent additive tank such as water and / or acids 14 Solvent cooling tank containing organic sulfur compound and oil 15 Centrifuge

Claims (8)

(57) [Claims] 1. A solvent having a boiling point lower than the boiling point of a residual oil or heavy oil is added to the residual oil or heavy oil, and the residual oil or heavy oil and the solvent are stirred and mixed at a temperature lower than the boiling point of the solvent. While lowering the viscosity of the heavy oil, the residual oil or the organic sulfur compound contained in the heavy oil is transferred into the solvent, and then the residual oil or the mixture of the heavy oil and the solvent is cooled to room temperature or a temperature lower than room temperature. Separating the residual oil or heavy oil from the solvent containing the organic sulfur compound, and further distilling the separated solvent containing the organic sulfur compound to recover the organic sulfur compound in the solvent. A method for recovering organic sulfur compounds from heavy oil. 2. The solvent is acetone, pinacolin, methysyl oxide, acetophenone, benzophenone, acetylacetone, 2-butanone, methanol, ethanol, propanol, butanol, acetonitrile, propionitrile, butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene. , Dimethylsulfoxide, N, N'-dimethylformamide, N,
N'-dimethylacetamide, N-methylpyrrolidinone, trimethylphosphate, triethylphosphate, hexamethylphosphamide, phosphorane, pyridine, a substance consisting of one or more kinds, or a concentration range of 20% or less based on the substance. With water and / or 10%
The method for recovering an organic sulfur compound from residual oil or heavy oil according to claim 1, wherein the method is selected from a mixture containing the following acids. 3. The method according to claim 1, wherein the residual oil or the heavy oil mixed with the solvent is thinned or liquefied in a temperature range not higher than the boiling point of the solvent. A method for recovering an organic sulfur compound from residual oil or heavy oil according to the above. 4. The method according to claim 1, wherein the organic sulfur compound to be recovered is in a state maintaining the original chemical structure contained in the residual oil or the heavy oil. A method for recovering an organic sulfur compound from residual oil or heavy oil according to the above. 5. The method according to claim 1, wherein the nucleophilicity of the organic sulfur compound contained in the residual oil or the heavy oil is used to change the solubility which is the original physical property of the organic sulfur compound. The method for recovering an organic sulfur compound from a residual oil or a heavy oil according to any one of claims 1 and 2, wherein the separation is carried out by elution. 6. A solvent in which a residual oil or heavy oil is mixed with a solvent, and water and / or acids are added to the solvent into which the organic sulfur compound contained in the residual oil or heavy oil has been transferred. The residual oil or the heavy oil according to claim 1, wherein the difference in the cohesive energy between the dissolved oil and the solvent is enlarged, and the oil and the solvent containing the organic sulfur compound are respectively aggregated and separated. A method for recovering organic sulfur compounds from oil. 7. A solvent obtained by mixing a residual oil or heavy oil with a solvent, cooling the solvent into which the organic sulfur compound contained in the residual oil or heavy oil has been transferred, and removing the oil component dissolved in the solvent. The method for recovering an organic sulfur compound from residual oil or heavy oil according to claim 1, wherein the oil component is separated from the solvent by coagulation. 8. A reaction tank for mixing a solvent additive selected from a residual oil or heavy oil, a solvent, water and / or an acid while heating to form a mixed solution, and a mixture formed in the reaction tank. A separation device for cooling the liquid to separate the solvent containing the residual oil or heavy oil and the organic sulfur compound, a centrifugal separator for removing the tar component from the separated solvent containing the organic sulfur compound and discharging the same, From a residual oil or heavy oil characterized by comprising a separation solvent distillation tank that separates and recovers the solvent and the organic sulfur compound by evaporating the solvent containing the organic sulfur compound from which the tar component has been removed by the separator. Equipment for recovering organic sulfur compounds.