JP2928467B2 - Method and apparatus for recovering organic sulfur compounds from light oil and / 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 an organic sulfur compound from light oil and heavy oil containing the organic sulfur compound.

[0002]

2. Description of the Related Art Petroleum, oil sand, oil shale,
In addition, liquid oil obtained from coal contains various organic sulfur compounds.For example, sulfur content in fuel oil of diesel engines has recently attracted attention as one of the causes of environmental pollution. The development of effective desulfurization technology is urgent. As described above, organic sulfur components contained in liquid oils have been conventionally recognized as harmful substances, and technical development for the purpose of removing them has been made.

At present, as a method for removing sulfur from fuel oil, a hydrogen reduction desulfurization method is generally employed. That is, a technique of reacting with a hydrogen gas using a catalyst under intense reaction conditions of high temperature and high pressure, converting an organic sulfur compound into toxic hydrogen sulfide, and separating the same is becoming mainstream.

A method for removing sulfur from fuel oil is disclosed in Japanese Patent Application Laid-Open No. 4-72387. The method for removing sulfur from the fuel oil is to treat the fuel oil obtained from petroleum and coal liquefied oil with an oxidizing agent to raise the boiling point of the contained organic sulfur and separate it from the fuel oil.・ To be removed.

[0005] As a refining technique for coal-based heavy oil using a solvent, there is one disclosed in Japanese Patent Application Laid-Open No. 56-49791. The method for purifying coal-based heavy oil comprises mixing a ketone solvent with coal-based heavy oil, removing insoluble precipitates generated in the mixture, and separating the ketones in the mixture. is there.

[0006]

However, in the hydrogen reduction desulfurization method, organic sulfur compounds which are contained in gas oil, heavy oil or residual oil in a large amount are difficult to be desulfurized, and in particular, chemical compounds such as benzothiophene and dibenzothiophene derivatives are used. Since it is difficult to show activity for functionally stable functional groups, the reaction temperature and pressure are further increased, and the sulfur content is reduced to 0.05% or less in the case of light oil by improving the activity of the catalyst. Technology development is urgent.

[0007] Organic sulfur compounds, which are often contained in light oil, heavy oil or residual oil, have generally been recognized as harmful substances. The reasons include environmental problems caused by burning the liquid oil as it is, and the fact that sulfur is a causative substance of catalyst poison when refining and processing the liquid oil. However, organic sulfur compounds contained in liquid oils can be positioned as one form of organic sulfur compounds as industrial raw materials, which are gradually gaining attention recently, and promise to make a great contribution to human society in the near future. Is a valuable resource. For example, benzothiophene, a dibenzothiophene derivative, which is difficult to hydrodesulfurize because of its chemical stability, has the potential as a useful industrial raw material,
If these are to be produced from inorganic sulfur, complicated chemical processes and large production costs are required.

In order to remove the organic sulfur compound from the liquid 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. For this reason, it is necessary to develop a method that does not depend on factors of chemical change such as high temperature (temperature), high pressure (pressure), and light, and does not depend on means of chemical reaction such as oxidation and reduction.

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 or coal liquefied oil is treated with an oxidizing agent. It is not obtained while maintaining the original chemical structure.

The method for purifying heavy coal oil disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 56-49791 discloses a method for refining heavy coal oil as a raw material for producing carbonaceous materials such as easily graphitizable needle 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 that are harmful to the raw material for producing the carbon agent. This does not disclose any technical problem of recovering a useful organic sulfur compound in the coal-based heavy oil.

An object of the present invention is to provide a light oil and / or heavy oil which does not require a high temperature or high pressure, and which does not require a supply of a consumable material such as a catalyst or hydrogen. Provided is a method for recovering sulfur compounds from light oil and heavy oil easily, economically and with high recovery efficiency while maintaining the original chemical structure contained in light oil and / or heavy oil. It is to be. The method of recovering organic sulfur compounds from light oil and heavy oil can also be applied to a desulfurization method for removing organic sulfur compounds from light oil and / or heavy oil.

[0012]

The present invention is configured as follows to achieve the above object. That is, the present invention provides a light oil and / or a heavy oil containing an organic sulfur compound, and adding and mixing a solvent having low solubility in hydrocarbons and high solubility in organic sulfur compounds,
After the organic sulfur compound contained in the light oil and / or heavy oil is transferred into the solvent, sedimentation, permeation, filtration, and / or centrifugation are performed from a mixture of the light oil and / or heavy oil and the solvent. The present invention relates to a method for recovering an organic sulfur compound from light oil and heavy oil, which comprises separating a solvent containing an organic sulfur compound, evaporating the solvent, and recovering the organic sulfur compound as an evaporation residue.

In the method for recovering an organic sulfur compound from light and heavy oils, the solvent may be 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'-dimethyl Acetamide, pyridine, N-methylpyrrolidinone, trimethyl phosphate, triethyl phosphate, hexamethyl phosphoramide, one or more substances selected from phosphoranes,
Alternatively, the concentration of water and / or
Or a mixture containing 10% or less of acids or iodine.

In this method of recovering an organic sulfur compound from light oil and heavy oil, the original physical properties of the organic sulfur compound contained in the light oil and / or heavy oil are utilized by utilizing the nucleophilicity of the organic sulfur compound. It is characterized by performing elution separation from light oil and / or heavy oil by changing the solubility which is a property. In the present invention, the light oil is naphtha, gasoline, kerosene, straight-run light gas oil. Heavy oil refers to straight running heavy gas oil (HGO), heavy oil, and vacuum gas oil (VGO).

Further, in the method for recovering an organic sulfur compound from light oil and heavy oil, the recovered organic sulfur compound has the original chemical structure contained in the light oil and / or heavy oil. It has been maintained.

The solvent used is required to have low solubility in hydrocarbons and high solubility in organic sulfur compounds, that is, high selectivity. Also, when separating the organic sulfur compound, the difference in density with the raw material is large, the interfacial tension is large, it is difficult to cause emulsification, the difference in boiling point with the target component is large, and an azeotropic mixture is not generated. Desired.

The solvent used in the present invention is a polar solvent. As shown in the examples, a solvent having a strong electron donating property shows a strong extraction ability for organic sulfur compounds. Gasoline, kerosene, gas oil, aprotic dipolar solvents such as acetone are more preferably used for chemical functional groups that are present in a large amount in residual oils than alcohols. Applying the fact that the lone pair of electrons on the divalent sulfur atom of the sulfur functional group has strong nucleophilicity,
By adding an alcoholic solvent or water and / or an acid selected from organic carboxylic acid, sulfonic acid sulfuric acid, nitric acid and hydrochloric acid and iodine to the above-mentioned solvent having a strong electron donating property, the original dissolution of the organic sulfur compound is achieved. Change the gender,
Increasing the selectivity of the solvent for the organic sulfur compounds present in the liquid oil is an important component of the present invention.
As described in the examples, among them, the solvent is acetone,
The effect when water is added to acetone in an amount of 20% or less is remarkable. In this case, the solvent, water, and light oil are easily mixed by stirring and / or vibration,
The organic sulfur compounds in the light oil immediately migrate into the solvent.
The addition of water and / or acids increases the cohesive energy of the solvent, resulting in an increase in the cohesive energy difference between the liquid oil and the solvent containing the organic sulfur compound. Each particle of the light oil and the solvent containing the sulfur compound automatically starts to separate and form an aggregate. In the case of heavy oil, it is advantageous to carry out a shearing operation when mixing with a solvent. In addition, kerosene or light oil, melt oxide, 2-
By lowering the viscosity by adding butanone or the like, the transferability of the organic sulfur compound can be increased.

The mixed solution of the light oil and / or the heavy oil and the solvent is separated by cooling the mixed solution of the light oil and / or the heavy oil and the solvent. And the solvent containing the organic sulfur compound is enlarged to coagulate and coagulate the light oil and / or the heavy oil, so that the light oil and / or the heavy oil can be separated from the solvent containing the organic sulfur compound.

The method for recovering organic sulfur compounds from light oil and heavy oil is based on oils obtained by dry distillation of coal tar, ie, naphthalene, phenol,
The present invention can also be applied to the recovery of organic sulfur compounds contained in aromatic compounds such as naphthol, anthracene, and phenanthrene.

Further, regarding the problem of separation due to the fact that the density difference between the solvent and the liquid oil employed is not so large, the separation of the oil component and the solvent is advanced in advance by the above-described method and the recent centrifugation. In the case of liquid-liquid separation, the separator focuses on a phenomenon in which a specific gravity difference can be separated within a range of about 0.1 to 0.03. It is applied to a method for recovering a compound.

In the method of recovering organic sulfur compounds from light oil and heavy oil, a solvent containing an organic sulfur compound separated by a centrifuge is distilled, the solvent is reused, and an organic residue is used as a distillation residue. It recovers sulfur compounds.

Alternatively, the present invention provides a mixing tank for mixing an additive selected from light oil and / or heavy oil, a solvent, water and / or an acid, and iodine to form a mixed solution, A separator for separating a solvent containing an organic sulfur compound from light oil and / or heavy oil by centrifugation and / or sedimentation and permeation separation of the produced mixture, and evaporating the separated solvent containing the organic sulfur compound And a solvent distillation tank for separating and recovering the solvent and the organic sulfur compound from the light oil and / or the heavy oil.

[0023]

The method and apparatus for recovering organic sulfur compounds from light oil and heavy oil according to the present invention are constructed as described above, and operate as follows. That is, the present invention relates to a light oil and / or heavy oil containing an organic sulfur compound, in which the solute organic sulfur compound is dissolved in a kind of light oil and / or heavy oil,
Based on the fact that the organic sulfur compound selectively shifts to a solvent having low solubility in hydrocarbons and high solubility in organic sulfur compounds, a solvent having low solubility in hydrocarbons and high solubility in organic sulfur compounds is selected. By combining the effective extraction method and separation method with this, the organic method by mass transfer does not depend on chemical changes such as high temperature, high pressure, light, etc. and does not depend on the means of reduction or oxidation chemical reaction. It separates (extracts) and recovers (desulfurizes from the light oil and / or heavy oil side) sulfur compounds. That is, the feature of the present invention is to utilize the nucleophilicity of an organic sulfur compound to change its inherent physical property, solubility, and to use a solvent containing an organic sulfur compound, light oil and / or heavy oil. It is intended to increase the cohesion energy difference with heavy oil to achieve elution separation from light oil and / or heavy oil.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A method and an apparatus for recovering organic sulfur compounds from light oil and heavy oil according to the present invention will be described below with reference to the drawings and tables. FIG. 1 is a block diagram illustrating processing steps for achieving a method for recovering organic sulfur compounds from light oil and heavy oil according to the present invention.

The apparatus for recovering an organic sulfur compound from light oil and heavy oil is prepared by adding an additive such as water and / or acids from the additive tank 8 to the solvent in the solvent tank 2.
The solvent is put into the mixing tank 3 and liquid oil such as kerosene, light oil, heavy oil, etc. as light oil and heavy oil is put into the mixing tank 3 from the liquid oil tank 1. After the liquid oil and the solvent are stirred and mixed in the mixing tank 3 by the stirrer 9 to form a liquid mixture, the liquid mixture is separated into the liquid oil and the solvent containing the organic sulfur compound by the centrifugal separator 4. The desulfurized liquid oil from which the organic sulfur compound has been separated is transferred to the desulfurized liquid oil tank 7, and the solvent containing the organic sulfur compound is sent to the distillation tank 5. Next, the solvent containing the organic sulfur compound is distilled in the distillation tank 5, the distilled solvent is returned to the solvent tank 2, and the additive is returned to the additive tank 8. Thus, the recovered organic sulfur compound is recovered in the recovered organic sulfur compound tank 6 as an evaporation residue. Further, a pipe for recovering the volatile solvent into the solvent tank 2 is provided from the upper portion of the mixing tank 3, and the solvent which is volatilized by stirring by the stirrer 3 can be recovered. With the volatilization of this solvent by stirring, the heat of the mixture is taken away,
The temperature is lowered, the mixture is automatically cooled, and the oil dissolved in the solvent aggregates, whereby the separation by the centrifugal separator 4 can be promoted. In addition, light oil and / or heavy oil are heated to about 50 ° C. to 60 ° C. in the tank 1, mixed with a solvent, and further cooled, whereby separation by the centrifuge 6 is easily performed. Can be. In this case, the solvent containing the organic sulfur compound and the oil can be separated without using a solvent additive.

An embodiment of the method for recovering organic sulfur compounds from light oil and heavy oil according to the present invention will be described below. Example 1 Light oil (boiling point 300 to 360)
300 ml of flammable sulfur content 4250 ppm), acetone 300 ml and water 6 ml were added, and the propeller type stirrer 9 was operated at 300 rpm for 10 seconds. After stirring for 10 seconds, the mixture was cooled to 5 ° C. Then, the centrifuge 4 is operated at a rotation speed of 3000 rpm, and the mixture is separated into light oil and a solvent containing an organic sulfur compound by centrifugation. After this operation was repeated six times, the solvent containing the organic sulfur compound was collected six times, and the solvent containing the organic sulfur compound was distilled at a temperature of 60 ° C to obtain an organic sulfur compound as a distillation residue. The combustible sulfur content in the treated light oil is 3
It was 30 ppm, and the recovery of the organic sulfur compound was 92.9% in terms of sulfur.

Example 2 Light oil (boiling point 30
0-360 ° C, flammable sulfur content 4,250 ppm) 300
Then, 300 ml of acetone was added, and the propeller type stirrer 9 was operated at 2000 rpm and mixed and stirred for 60 seconds to form a mixed solution, and then the mixed solution was cooled to -5 ° C.
Next, the centrifugal separator 4 is operated at a rotation speed of 3000 rpm, and separated into light oil and a solvent containing an organic sulfur compound by centrifugation. After this operation was repeated six times, the solvent containing the organic sulfur compound was collected six times, and the solvent containing the organic sulfur compound was distilled at a temperature of 70 ° C. to obtain an organic sulfur compound as a distillation residue. The combustible sulfur content in the treated light oil was 360 ppm, and the recovery of organic sulfur compounds was 91.5% in terms of sulfur.

Example 3 Kerosene (boiling point 22
0-300 ° C, flammable sulfur content 45 ppm), 300 ml, acetone 30 ml, ethanol 270 ml, water 6
The mixture was stirred and mixed for 10 seconds while the propeller-type stirrer 9 was operated at 300 rpm to form a mixture. The mixture was cooled to 5 ° C., and the centrifuge 4 was operated at a rotation speed of 3000 rpm to perform centrifugation. To separate the mixture into kerosene and a solvent containing an organic sulfur compound. After repeating this operation six times, the solvent containing the organic sulfur compound is collected six times, and the solvent containing the organic sulfur compound is distilled at a temperature of 80 ° C.,
An organic sulfur compound was obtained as a distillation residue. The combustible sulfur content in the treated light oil was 6.2 ppm, and the recovery of organic sulfur compounds was 86% in terms of sulfur.

[Example 4] Light oil (boiling point 30
0-360 ° C, flammable sulfur content 4,250 ppm) 300
Then, 300 ml of ethanol was added, and the propeller type stirrer 9 was operated at 300 rpm and stirred and mixed for 20 seconds to form a mixed solution. The mixed solution was cooled to 10 ° C.
The centrifugal separator 4 is operated at a rotation speed of 3,000 rpm, and the mixture is separated into light oil and a solvent containing an organic sulfur compound by centrifugation. After this operation was repeated six times, the solvent containing the organic sulfur compound was collected six times, and the solvent containing the organic sulfur compound was distilled at a temperature of 80 ° C. to obtain an organic sulfur compound as a distillation residue. The combustible sulfur content in the treated light oil was 680 ppm, and the recovery of organic sulfur compounds was 84% in terms of sulfur.

Example 5 Light oil (boiling point 30
0-360 ° C, flammable sulfur content 4,250 ppm) 300
280 ml of ethanol, 20 ml of methysyl oxide and 6 ml of water.
After the mixture was stirred and mixed at 20 rpm for 20 seconds to form a mixture, the mixture was cooled to 5 ° C., and the rotation speed was 3000 rpm.
The centrifuge 4 is operated at pm, and the mixture is separated into light oil and a solvent containing an organic sulfur compound by centrifugation. After this operation was repeated six times, the solvent containing the organic sulfur compound was collected six times, and the solvent containing the organic sulfur compound was heated to a temperature of 130 ° C.
To obtain an organic sulfur compound as a distillation residue. The combustible sulfur content in the treated light oil was 550 ppm, and the recovery of organic sulfur compounds was 87% in terms of sulfur.

[Example 6] In the mixing tank 3, light oil (boiling point 30
0-360 ° C, flammable sulfur content 4,250 ppm) 300
285 ml of ethanol, acetophenone 1
5 ml and water 6 ml were added, and the propeller type stirrer 9 was
After the mixture was stirred and mixed at 20 rpm for 20 seconds to form a mixture, the mixture was cooled to 5 ° C., and the rotation speed was 3000 rpm.
The centrifuge 4 is operated at pm, and the mixture is separated into light oil and a solvent containing an organic sulfur compound by centrifugation. After this operation was repeated six times, the solvent containing the organic sulfur compound was collected six times, and the solvent containing the organic sulfur compound was heated to a temperature of 210 ° C.
To obtain an organic sulfur compound as a distillation residue. The combustible sulfur content in the treated light oil was 530 ppm, and the recovery of organic sulfur compounds was 88% in terms of sulfur.

Example 7 A fuel oil A (boiling point 3
60 ° C ~, combustible sulfur content 6,280ppm) 300ml
Put, ethanol 120ml, acetone 180ml,
While adding 6 ml of water and 2 ml of formic acid and heating to 45 ° C., the propeller type stirrer 9 was operated at 1000 rpm and stirred and mixed for 30 seconds to form a mixed solution. The mixed solution was cooled to 5 ° C. The centrifuge 4 is operated at 3000 rpm, and the mixture is separated into heavy oil A and a solvent containing an organic sulfur compound by centrifugation. After repeating this operation seven times, the solvent containing the organic sulfur compound was collected seven times, and the solvent containing the organic sulfur compound was distilled at a temperature of 80 ° C. to obtain an organic sulfur compound as a distillation residue. The combustible sulfur content in the treated heavy oil A was 325 ppm, and the recovery of organic sulfur compounds was 99.48% in terms of sulfur.

Example 8 Heavy oil (sulfur content: 6200 p
pm) for each solvent, 15 ml of heavy oil A in a 30 ml stoppered measuring cylinder,
15 ml of acetone was added, and the mixture was stirred at intervals of 5 minutes while irradiating ultrasonic waves for 30 minutes. Thereafter, 0.15 ml of water was added and the mixture was stirred, left to stand all day and night, and then the heavy oil layer was collected, washed with water and dried. In the same manner, treatment with N, N'-dimethylformamide (DMF), acetonitrile, trimethyl phosphate, nitromethane, methanol, hexamethylphosphoramide (HMPA), acetic acid, pyridine, N-methylpyrrolidinone (NMP) is performed. went. Table 1 shows the results of desulfurization (recovery of organic sulfur compounds) for each of these solvents, based on the sulfur content in the treated heavy oil A.

[Table 1]

Example 9 Heavy oil A (sulfur content 6200)
When the solvent for recovering (desulfurizing) the organic sulfur compound in (ppm) is acetone, the effect of the water content ratio is shown in Table 2 and FIG.
Shown in It can be seen that the smaller the water content, the more organic sulfur compounds are recovered.

[Table 2]

Example 10 In the recovery operation using each solvent (of heavy fuel oil A) shown in Example 9, 4.75 g of iodine having a stronger electron-withdrawing property was added, and the mixture was stirred and left overnight. The heavy oil layer was collected, washed with an aqueous solution of sodium thiosulfate, washed with water, and dried.

Example 11 Heavy oil A (sulfur content 620)
0 ppm) 200 ml of formic acid 20 ml, hydrogen peroxide 20
After the reaction, the heavy oil layer was separated, washed with water, allowed to cool, and dried (sulfur content: 500
0 ppm), and the effect of the abundance ratio of water using acetone as a solvent is shown in Table 3 and FIG. It is clear that the oxidized organic sulfur compounds have higher recovery.

[Table 3]

Example 12 15 ml of light oil (sulfur content: 1800 ppm) and 15 ml of acetone were added to a 30 ml measuring cylinder with a stopper, and the mixture was stirred at intervals of 5 minutes while irradiating ultrasonic waves for 30 minutes, and then water was added. After stirring overnight, the gas oil layer was collected, washed with water, and dried. The relationship between the water abundance ratio and the recovery (desulfurization) is shown in Table 4 and FIG.
It is understood that the effect is greater as the amount of added water is smaller, as in the case of Fuel Oil A.

[Table 4]

Example 13 When the solvent acetone in Example 12 was changed to DMF, the sulfur content of the treated light oil was 993 ppm. The recovery (desulfurization) rate is 44.8%.

Example 14 When the water added to the solvent acetone in Example 12 was changed to 4.75 g of iodine, the sulfur content of the treated gas oil was 1030 ppm. The recovery (desulfurization) rate is 42.8%.

Example 15 Light oil (1800 sulfur content)
(ppm) 200 ml formic acid 20 ml, hydrogen peroxide 20 m
and stirred vigorously for 90 minutes. After the reaction, the gas oil layer was separated, washed with water, allowed to cool, and dried (sulfur content: 1500
ppm), and the effect of the abundance ratio of water using acetone as a solvent is shown in Table 5 and FIG.

[Table 5]

Example 16 15 ml of kerosene (sulfur content 210 ppm) and 15 ml of acetone were added to a 30 ml measuring cylinder with a stopper and irradiated with ultrasonic waves for 30 minutes.
Stir at 5 minute intervals. Thereafter, water was added and the mixture was stirred. After standing overnight, the oil layer was collected, washed with water, and dried. The effect of the water abundance is shown in Table 6 and FIG.

[Table 6]

Example 17 Gasoline (sulfur content: 52.31 ppm) 15 m in a 30 ml measuring cylinder with a stopper
l, 15 ml of acetone was added, and the mixture was stirred at 5 minute intervals while irradiating ultrasonic waves for 30 minutes. Thereafter, water was added and the mixture was stirred. After standing overnight, the oil layer was collected, washed with water, and dried.
The effect of the water abundance is shown in Table 7 and FIG.

[Table 7]

[0043]

The method and the apparatus for recovering organic sulfur compounds from light oil and heavy oil according to the present invention are constituted as described above and have the following effects. That is, the present invention includes an organic sulfur compound contained in light oil and / or heavy oil in light oil and / or heavy oil with high efficiency and low cost using simple equipment. Can be recovered while maintaining the original chemical structure. The recovered organic sulfur compound can be used as an industrially useful resource in the fields of manufacturing pharmaceuticals, agricultural chemicals, heat-resistant resins, and the like. In addition, this method of recovering from light oil and heavy oil can be applied as a desulfurization method for removing organic sulfur compounds from light oil and / or heavy oil, and by a simple method using simple equipment. It can be applied to a desulfurization method that does not require high temperature and high pressure, consumes little energy, does not generate coke, does not require hydrogen reduction, and has a remarkable economic effect.

[Brief description of the drawings]

FIG. 1 is a system diagram showing a processing apparatus for achieving a method for recovering organic sulfur compounds from light oil and 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 present invention.

FIG. 3 is a graph showing the sulfur content in heavy oil when iodine is added in the present invention.

FIG. 4 is a graph showing the sulfur content in oxidized heavy oil according to the abundance ratio of water using acetone as a solvent in the present invention.

FIG. 5 is a graph showing the sulfur content in light oil according to the abundance ratio of water using acetone as a solvent in the present invention.

FIG. 6 is a graph showing the sulfur content in oxidized light oil according to the abundance ratio of water using acetone as a solvent in the present invention.

FIG. 7 is a graph showing the sulfur content in kerosene according to the abundance ratio of water using acetone as a solvent in the present invention.

FIG. 8 is a graph showing the sulfur content in gasoline according to the abundance ratio of water using acetone as a solvent in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Liquid oil tank 2 Solvent tank 3 Mixing tank 4 Centrifuge 5 Solvent distillation tank containing organic sulfur 6 Recovered organic sulfur compound tank 7 Desulfurized liquid oil tank 8 Additive tank such as water and / or acids 9 Stirrer

Claims (7)

(57) [Claims] 1. A light oil containing an organic sulfur compound and / or
Alternatively, a solvent having low solubility in hydrocarbons and high solubility in organic sulfur compounds is added to and mixed with heavy oil, and the organic sulfur compounds contained in light oil and / or heavy oil are transferred to the solvent. After that, the solvent containing the organic sulfur compound is separated from the mixture of the light oil and / or the heavy oil and the solvent by sedimentation, permeation, filtration and / or centrifugation,
Subsequently, the solvent is evaporated, and the organic sulfur compound is recovered as an evaporation residue. A method for recovering an organic sulfur compound from light oil and / or 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, pyridine, N, N'-dimethylformamide, N, N'-dimethylacetamide, N-methylpyrrolidinone, trimethyl phosphate, triethyl phosphate, hexamethyl phosphate, hexamethyl phosphoramide, or one or more kinds of substances selected from phosphoranes Or 2 for the substance
The organic sulfur compound from light oil and / or heavy oil according to claim 1, characterized in that it is selected from a mixture containing water and / or 10% or less of acids or iodine in a concentration range of 0% or less. How to collect. 3. The use of nucleophilicity of an organic sulfur compound contained in a light oil and / or a heavy oil to change the solubility, which is an intrinsic physical property, of a light oil and / or a heavy oil. The method for recovering an organic sulfur compound from light oil and / or heavy oil according to any one of claims 1 and 2, wherein the method is carried out by elution and separation from heavy oil. 4. The recovered organic sulfur compound is in a state where the original chemical structure contained in light oil and / or heavy oil is maintained. The method for recovering an organic sulfur compound from a light oil and / or a heavy oil according to the above item. 5. A solvent is added to light oil and / or heavy oil,
Further, by adding and mixing water and / or acids, the solubility of the solvent in the organic sulfur compound contained in the light oil and / or the heavy oil is increased, and the cohesive energy of the solvent is also increased, so that the light The coagulation energy difference between oil and / or heavy oil and a solvent containing an organic sulfur compound is enlarged, and light oil and / or heavy oil and a solvent containing an organic sulfur compound are respectively coagulated and separated. The method for recovering an organic sulfur compound from a light oil and / or a heavy oil according to claim 1. 6. A solution in which a solvent is added to light oil and / or heavy oil, and the light oil and / or heavy oil dissolved in the solution is coagulated and coagulated to form a light oil and / or heavy oil. The method for recovering an organic sulfur compound from light oil and / or heavy oil according to claim 1, wherein the heavy oil is separated from a solvent containing the organic sulfur compound. 7. A mixing tank for producing a liquid mixture by mixing an additive selected from light oil and / or heavy oil, a solvent, water and / or an acid, and iodine, and a mixture produced in the mixing tank. A separator for separating a solvent containing an organic sulfur compound from light oil and / or heavy oil by centrifugal separation and / or sedimentation and permeation separation of the liquid; and evaporating the separated solvent containing the organic sulfur compound to remove the solvent and the organic solvent. An apparatus for recovering an organic sulfur compound from light oil and / or heavy oil, comprising: a solvent distillation tank for separating and recovering a sulfur compound.