WO2002081597A1

WO2002081597A1 - Method and device for separating sulfuric compound contained in oil

Info

Publication number: WO2002081597A1
Application number: PCT/JP2002/002871
Authority: WO
Inventors: Yoshihide Takino; Saburo Nozawa; Issei Yamanishi
Original assignee: Ohtix Inc.
Priority date: 2001-03-30
Filing date: 2002-03-25
Publication date: 2002-10-17
Also published as: JP2005023090A

Abstract

A method and a device for separating sulfuric compound contained in oil; the method, comprising the step of feeding fog oil into an ozone atmosphere to perform a treatment for catalytic reaction to ozone so as to oxidize the sulfuric compound contained in the oil; the device, characterized by comprising at least a catalytic reaction tank (4) forming the ozone atmosphere in an internal space, a means (1) for feeding ozone into the catalytic reaction tank (4), and means (2, 3) for feeding the treated oil into the catalytic reaction tank (4) by spraying.

Description

Method and apparatus for separating sulfur compounds from petroleum

Technical field

The present invention relates to a method and a method for separating sulfur compounds contained in petroleum such as kerosene and light oil.

Related to the device.

Field background technology

Recently, the demand for reforming petroleum products such as kerosene and gas oil, which is required worldwide, is considered to be a causative substance to regulate the emission of acid gases such as SO _x and NO x from the viewpoint of environmental protection. The purpose is to reduce the components containing heteroatoms in these petroleum products.

As a method for removing sulfur compounds in petroleum, a hydrogen reduction desulfurization method is conventionally known. This method uses an expensive catalyst to react organic sulfur compounds in petroleum with hydrogen under the conditions of high temperature and high pressure to produce hydrogen sulfide (poisonous).

) Is to separate it from petroleum.

Japanese Patent Application Laid-Open No. 417,287 / 87 discloses that fuel oil is contained by subjecting petroleum oil to an oxidizing agent such as hydrogen peroxide or ozone by bubbling or adding the oxidizing agent or the like as a liquid. There is disclosed a method of utilizing the change in the boiling point, solubility, and melting point of the organic sulfur compound to separate the organic sulfur compound from the fuel oil.

In addition, Japanese Patent Application Laid-Open No. 7-197036 describes a method for extracting and separating an organic sulfur compound of a fuel oil using an extraction solvent.

However, the above-mentioned hydrogen reduction desulfurization method has a problem that it requires at least a high temperature and a high pressure. Further, the method described in the above-mentioned Japanese Patent Application Laid-Open No. 417,877 has a major problem in the reaction between petroleum and the oxidizing agent, and cannot be oxidized sufficiently effectively. The efficiency was so poor that separation could not be performed effectively. In addition, there is a problem that an oxidizing agent such as hydrogen peroxide is required for a long time and in a large amount.

Further, the extraction method described in Japanese Patent Application Laid-Open No. 7-197036 has a problem that the extraction efficiency is very insufficient.

Therefore, the present invention solves the above-mentioned drawbacks of the conventional method for separating sulfur compounds, does not use high temperature and high pressure, and does not require expensive catalysts, etc. It is an object of the present invention to provide a new method and apparatus capable of separating a sulfur compound contained in water. Disclosure of the invention

In order to solve the above problems, a method for separating sulfur compounds contained in petroleum according to the present invention is a method for separating sulfur compounds contained in petroleum from petroleum. The first characteristic is that the catalytic reaction is performed to oxidize sulfur compounds in petroleum.

Further, the method for separating a sulfur compound contained in petroleum according to the present invention, in addition to the first feature described above, further comprises solid-liquid separation of a solid product generated in petroleum by a catalytic reaction treatment in an ozone atmosphere. This is the second feature.

Further, the method for separating sulfur compounds contained in petroleum according to the present invention, in addition to the first or second feature, further comprises an extraction solvent or water as an extraction solvent for petroleum subjected to a catalytic reaction treatment in an ozone atmosphere. The third feature is that residual sulfur compounds are extracted by using water or water itself. Further, the method for separating sulfur compounds contained in petroleum of the present invention, in addition to the first or second feature, further comprises using an adsorbent to remove residual oil from petroleum that has been subjected to a catalytic reaction treatment in an ozone atmosphere. The fourth feature is to adsorb the sulfur compounds that are present.

Further, the method for separating sulfur compounds contained in petroleum according to the present invention, in addition to the above first or second feature, further comprises an extraction solvent and an adsorbent for petroleum that has been subjected to a contact reaction treatment in an ozone atmosphere. The fifth feature is that the remaining sulfur compounds are separated by combining with the adsorption treatment by the method. Further, the apparatus for separating sulfur compounds contained in petroleum according to the present invention comprises: a contact reaction tank that forms an ozone atmosphere in an internal space; a means for supplying ozone to the contact reaction tank; The sixth feature is that it has at least means for spraying and supplying treated oil.

According to the method for separating sulfur compounds contained in petroleum according to the first feature, the ozone is not injected into the petroleum but supplied to the formed ozone atmosphere in the form of a mist and the ozone is separated from the ozone. The contact reaction treatment is performed. By performing such treatment, it becomes possible to bring oil and gaseous ozone into contact with a sufficient contact area, and to oxidize sulfur compounds in petroleum with sufficient reaction efficiency and reaction rate. It becomes possible. By supplying petroleum into the ozone atmosphere in the form of a spray as described above, the oxidation of organic sulfur compounds, which are the main sulfur compounds in petroleum, proceeds at a sufficient reaction efficiency and reaction rate, and the oxidized organic sulfur compounds As its solubility in petroleum decreases, its polarity increases. Therefore, the oxidized organic sulfur compounds are precipitated in petroleum and can be separated. Even if the organic sulfur compound is not directly precipitated, the polarity of the oxidized organic sulfur compound is sufficiently increased, so that the oxidized organic sulfur compound can be easily separated from petroleum by a subsequent treatment. Therefore, according to the first feature, by oxidizing sulfur compounds by a very effective catalytic reaction by spraying petroleum into an ozone atmosphere, it is possible to use very high temperatures, high pressures, and without using expensive catalysts. It is possible to separate sulfur compounds from petroleum at low cost and with sufficient efficiency.

Even when ozone is used, the method of injecting ozone into petroleum does not sufficiently increase the reaction efficiency and reaction rate between ozone and sulfur compounds in petroleum, so that sulfur compounds in petroleum It is practically difficult to achieve the effect of facilitating the separation.

In the method in which an oxidizing aqueous solution is reacted with petroleum, most of the oxidized products are water-soluble, so that oxidized organic sulfur compounds and other oxidized products migrate into the aqueous solution and are separated. Becomes difficult.

In the second feature, when the oxidation of organic sulfur compounds and the like in petroleum proceeds by the catalytic reaction treatment in an ozone atmosphere, the oxidation lowers the solubility of the organic sulfur compounds and the like in petroleum. Precipitates as a solid product. Other compounds with heteroatoms also precipitate as oxidized solid products if they cause a decrease in solubility due to oxidation. In addition, ozonide, which is a reaction intermediate produced in the contact reaction, also precipitates as a solid product. Therefore, sulfur compounds and other hetero compounds contained in petroleum can be easily separated by solid-liquid separation of these solid products generated in petroleum.

Most of the solid products generated by oxidation with the contact with ozone are water-soluble, and thus, in an oxidation reaction using an aqueous solution, the generated oxide cannot be precipitated and separated as a solid.

Therefore, according to the method for separating sulfur compounds contained in petroleum according to the second feature, in addition to the action according to the first feature, by performing the catalytic reaction treatment in an ozone atmosphere, the sulfur compound in the petroleum is solidified. Other processing as a product It can be separated directly without going through.

Further, according to the method for separating sulfur compounds contained in petroleum according to the third aspect, in addition to the action according to the first or second aspect, petroleum that has been subjected to a catalytic reaction treatment in an ozone atmosphere can be used. Effective extraction and separation of sulfur oxides remaining in petroleum by extracting the remaining sulfur compounds using the extraction solvent, or an extraction solvent with water, or water itself. can do. That is, the sulfur compound oxidized by the contact reaction treatment in the ozone atmosphere may be precipitated as a solid product or may remain in petroleum, depending on the solubility. The ratio can be adjusted by adjusting the temperature or other conditions. The precipitate as the solid product can be separated by solid-liquid separation as described in the second feature. On the other hand, the organic sulfur compounds remaining in petroleum can be extracted very easily by using an extraction solvent, as a result of the oxidation, the polarity is sufficiently increased without precipitation. It becomes. As the extraction solvent, a polar solvent can be used. In addition, water obtained by adding water to the extraction solvent or water itself can be used. However, as long as it is an extraction solvent that can easily extract the oxidized organic sulfur compound remaining in the petroleum oil, its type and combination are not particularly limited. If water is used, costs can be reduced and handling is easy.

In addition, in the case of petroleum that has not undergone contact reaction by spraying in an ozone atmosphere, a sufficient extraction effect cannot be obtained even if an extraction solvent is used, since the organic sulfur compound is not sufficiently polarized.

Therefore, according to the third feature, in addition to the action of the first or second feature, the sulfur compound remaining in the petroleum can be removed by using an extraction solvent, water added thereto, or water itself. It can be effectively extracted and separated. According to the method for separating sulfur compounds contained in petroleum according to the fourth aspect, in addition to the action according to the first or second aspect, an adsorbent is applied to petroleum that has been subjected to a contact reaction treatment in an ozone atmosphere. By adsorbing the remaining sulfur compounds using, the sulfur oxides remaining in the petroleum can be effectively adsorbed and separated.

That is, in petroleum that has been subjected to a catalytic reaction in an ozone atmosphere, the organic sulfur compounds remaining therein are sufficiently oxidized by sufficient contact with the ozone, and the polarity thereof is sufficiently increased. ing. Therefore, the use of the adsorbent makes it very easy to adsorb and separate. As the adsorbent, a solid adsorbent such as silica such as silica gel, charcoal, and metal can be mainly used.

Therefore, according to the fourth feature, in addition to the action of the first or second feature, sulfur compounds remaining in petroleum can be effectively adsorbed and separated using an adsorbent. .

According to the method for separating sulfur compounds contained in petroleum according to the fifth aspect, in addition to the action according to the first or second aspect, the extraction solvent is applied to the petroleum that has been subjected to the contact reaction treatment in an ozone atmosphere. Separation of sulfur compounds remaining in petroleum more effectively and more effectively than combining the extraction and adsorption treatments alone by combining the extraction treatment with water and the adsorption treatment with an adsorbent Can be. The order of the extraction process and the adsorption process does not matter.

According to the apparatus for separating sulfur compounds contained in petroleum according to the sixth aspect, when ozone is supplied to the contact reaction tank by means of supplying ozone, an ozone atmosphere is formed inside. When the petroleum to be treated, that is, the petroleum to be treated, is sprayed and supplied by the spray supply means into the contact reaction tank in which the ozone atmosphere is formed, the contact reaction between the petroleum and the ozone is started. Contact Since the contact reaction is performed with a sufficiently large contact surface area and contact time secured on the surface of the fine particles, sulfur compounds in petroleum may be oxidized with significantly improved reaction efficiency and reaction speed. And the polarity can be increased sufficiently.

Petroleum treated in the catalytic reactor is discharged from the catalytic reactor and used for the subsequent sulfur compound separation process. The contact reaction treatment in the contact reaction tank can be performed by batch or continuous treatment.

Therefore, according to the apparatus for separating sulfur compounds contained in petroleum according to the sixth feature, the petroleum can be contact-reacted in a spray state in an ozone atmosphere in the contact reaction tank, and the oxidation of the sulfur compounds contained in the petroleum can be sufficiently performed. The reaction can be performed with high reaction efficiency and reaction speed. In addition, the polarity of the contained sulfur compound can be sufficiently increased. In addition, it does not require costly equipment such as high temperature and high pressure and complicated mechanisms, etc.It is possible to efficiently separate sulfur compounds from petroleum at low cost with relatively simple and compact equipment. Becomes BRIEF DESCRIPTION OF THE FIGURES

Hereinafter, the method of the present invention will be further described with reference to the drawings.

FIG. 1 is a schematic configuration diagram showing an example of the separation device of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Referring to FIG. 1, an ozone generator 1 is provided as a means for supplying ozone, and the ozone generated by the ozone generator is supplied to a contact reaction tank 4. This forms an ozone atmosphere in the contact reaction tank 4. On the other hand, an oil tank 2 and a spraying means 3 are provided as means for spraying and supplying the oil to be treated to the contact reaction tank 4, and the oil to be treated from the oil tank 2 is supplied to the spraying means 3. The mist is supplied into the contact reaction tank 4 in the form of a mist, whereby the contact reaction between the gaseous ozone and the particulate oil to be treated is performed.

Generation of ozone in the ozone generator 1 can be easily performed at a low cost by, for example, discharge using oxygen contained in the air. On the other hand, the petroleum to be supplied from the oil tank 2 may be pre-fractionated petroleum such as light oil or kerosene, or may be a mixed petroleum, in other words, any liquid petroleum that can be sprayed and supplied.

The contact reaction in the contact reaction tank 4 may be of a batch type or a continuous reaction type.

The ambient temperature and pressure are not particularly limited, but the reaction can be performed at normal temperature and normal pressure, for example, by reacting at a temperature of 60 ° C. or lower and normal pressure. Of course, in order to adjust the reaction speed, the temperature and pressure should be adjusted appropriately by increasing or decreasing.

The ozone atmosphere can be a mixture with air, and its concentration can be as low as 1.5%, for example. However, the ozone concentration should be set to an appropriate concentration in relation to other conditions. It will be decided by experiment. By performing the contact reaction treatment by spraying the petroleum into the ozone atmosphere, the petroleum is brought into contact with the ozone with a sufficient contact area and contact time, and as a result, the reaction efficiency and the reaction rate are greatly improved. Organic sulfur compounds contained in petroleum are sufficiently oxidized and their polarity is sufficiently increased. Other heteroatom compounds in petroleum are also oxidized. In addition, ozone is generated.

The petroleum that has undergone the contact reaction treatment with ozone is sent to the solid-liquid separation tank 5 batchwise or continuously. In the solid-liquid separation tank 5, a solid product generated by the contact reaction treatment with ozone is separated. The separated solid products include oxidized organic sulfur compounds, ozonides, and other hetero compounds. Organic sulfur compounds in petroleum are oxidized and precipitate as sulphoxides or sulphone compounds due to the increased polarity of the molecules. Orefin compounds in petroleum are oxidized and precipitate as ozonides.

Some of the oxidized organic sulfur compounds and ozonides are dissolved in hydrocarbon components, and not all of them are precipitated. By appropriately cooling the petroleum after the above-mentioned contact reaction treatment, the solubility of these oxidized compounds can be reduced, and precipitation can be promoted.

The solid product separated in the solid-liquid separation tank 5 is further oxidized so that ozonide becomes a liquid compound (ketone and carboxylic acid), and is separated from the oxidized organic sulfur compound which is a solid compound by sedimentation or the like. Can be separated through

Most of the oxidized solid products are water-soluble, but the present invention uses gaseous ozone and does not oxidize with an aqueous solution, so that the generated oxides are easily precipitated and separated as solids. can do.

The oil from which the solid product has been separated in the solid-liquid separation tank 5 is sent to an extraction tank 6. Of course, in the contact reaction treatment in the ozone atmosphere in the contact reaction tank 4, the solid product may not be precipitated depending on the conditions. Therefore, in this case, the petroleum after the contact reaction treatment may be supplied to the extraction tank 6 as it is without performing solid-liquid separation in the solid-liquid separator 5. On the other hand, the extraction tank 6 is supplied with an extraction solvent from a solvent tank 7. As the extraction solvent, alcohols such as methanol, ketones such as acetone, and other polar solvents can be used alone or in combination of two or more in one or more extraction tanks 6. Alternatively, water obtained by adding water to the extraction solvent or water itself may be used.

The organic sulfur compound remaining in the petroleum is sufficiently oxidized by the contact reaction treatment in the ozone atmosphere, and has a sufficient polarity compared to other hydrocarbon components. Therefore, it is possible to easily and efficiently extract to the extraction solvent side. Ozonide remaining in petroleum is also extracted. Of course, other highly polar hetero compounds are also extracted.

In the case where the extraction treatment is performed without performing the contact reaction treatment in an ozone atmosphere, even if a polar solvent such as methanol is used, almost no sulfur compound is extracted.

The petroleum and the extraction solvent that have been subjected to the extraction treatment in the extraction tank 6 are sent to the separator 8 where they are separated into the extraction solvent and petroleum, and the extraction solvent containing organic sulfur compounds and extracts such as ozonide is sent to the distillation column 9. Can be The separated oil is sent to the adsorption tank 10. The separation of the petroleum and the extraction solvent in the separator 8 can use a known separation technique.

In the distillation column 9, the two are separated by distillation such as vacuum distillation by utilizing the difference between the boiling point of the extraction solvent and the boiling point of the extracted oxidizing compound (organic sulfur compound, ozonide, etc.).

The oxidized compound (organic sulfur compound, ozonide, etc.) oxidized by the contact reaction treatment in an ozone atmosphere has a higher boiling point because the molecular weight and polarity are increased compared to before the reaction. . On the other hand, polar solvents such as methanol used as the extraction solvent have a much lower boiling point. For this reason, by distilling both under reduced pressure, it is possible to separate them without heating. Since low-temperature distillation is possible, unstable ozonide can also be prevented from running away and decomposing.

The extraction solvent can be returned to the solvent tank 7. The oxidized compounds (organosulfur compounds, ozonides, etc.) from which the extraction solvent has been separated are further oxidized to convert ozonides into liquid compounds (ketones and carboxylic acids) and separated from the remaining solid compounds, such as oxidized organic sulfur compounds. can do.

The extraction solvent separated from petroleum by the separator 8 was distilled. Before the distillation in the column 9, the hydrocarbon compound mixed in the extraction solvent may be separated in advance by adding water. Hydrocarbon compounds are less soluble in water than the aforementioned oxidized compounds (organic sulfur compounds, ozonides, etc.) and can be separated.

Further, water is added to the petroleum separated from the extraction solvent by the separator 8 before being sent to the adsorption tank 10 so that the extraction solvent such as methanol partially remaining in the petroleum can be removed from the water side. And may be separated. This allows the sulfur to be further separated from petroleum along with the extraction solvent. The adsorption tank 10 can be provided with a solid adsorbent such as silica gel, charcoal, and metal. Oxidizing compounds (organic sulfur compounds, ozonides, etc.) remaining in petroleum are adsorbed by the adsorbent and separated by the oil being sufficiently contacted with the adsorbent while passing through the adsorption tank 10. You.

The polarity of the oxidized compounds (organic sulfur compounds, ozonides, etc.) oxidized by the contact reaction treatment by spraying petroleum under an ozone atmosphere is sufficiently increased compared to before the reaction. Therefore, the adsorption of the oxidized compound in petroleum can be performed very efficiently and smoothly.

When the adsorption treatment is performed without performing the contact reaction treatment in the ozone atmosphere, the efficiency of adsorption and separation of sulfur components from petroleum is very low, but the contact reaction treatment in an ozone atmosphere is performed in advance. As a result, the efficiency of adsorption and separation is dramatically improved.

The petroleum that has undergone the adsorption separation treatment in the adsorption tank 10 is sent to the refined petroleum tank 11.

The oxidized organic sulfur compounds and the like adsorbed in the adsorption tank 10 are collected and further separated for each compound and used as a useful resource in the fields of manufacturing pharmaceuticals, agricultural chemicals, heat-resistant resins and the like. Similarly, the oxidized organic sulfur compounds and the like obtained through the solid-liquid separation tank 5 and the distillation column 9 are further separated and recovered, thereby providing useful resources. Used as a source.

In the operation described above, it is premised that the contact reaction treatment is carried out by spraying oil into the ozone atmosphere in the contact reaction tank 4, and then the oil subjected to the treatment is extracted in the extraction tank 6. Although the sulfur content was separated by a combination of the treatment and the adsorption treatment in the adsorption tank 10, a combination of the contact reaction treatment and the extraction treatment may be used. Also, a combination of the contact reaction treatment and the adsorption treatment can be used.

Of course, the petroleum that has been subjected to the catalytic reaction treatment by spraying and supplying the petroleum into the ozone atmosphere, together with the extraction treatment and the adsorption treatment, or separately, the organic sulfur compounds and other heteroatoms contained in the petroleum Operations for separating compounds, such as adjusting solubility by adding water or other liquids, heating, cooling, pressurizing, solid-liquid separation, centrifugation, and distillation. Target or chemical operation may be combined. Such treatment combined with the contact reaction treatment in the ozone atmosphere also falls within the technical scope of the present invention.

Example 1

The ozone generated by the ozone generator 1 using air as a raw material is supplied as a mixture with air to the contact reaction tank 4 having a volume of 200 m1, thereby forming an ozone atmosphere in the contact reaction tank 4. did. Then, commercially available kerosene (sulfur content: 33.4 ppm) 5 Om1 was sprayed and supplied to the contact reaction tank 4 by the spraying means 3, and the contact reaction treatment was performed with the spray kerosene in the ozone atmosphere. The temperature in the contact reaction tank 4 was set to 20 ° C or less.

(1) After the contact reaction treatment, solid products such as precipitated organic sulfur compounds were separated.

(2). The kerosene after separating the solid product in (1), methanol The extraction was performed by adding an extraction solvent consisting of%, and organic sulfur compounds and the like were separated from kerosene.

(3) The kerosene after the solid product was separated in (1) was subjected to adsorption treatment with silica gel.

The sulfur content in the kerosene obtained in (1) to (3) was measured to obtain a desulfurization rate. Table 1 shows the results.

As is clear from Table 1, the original kerosene had a sulfur content of 33.4 ppm, whereas the kerosene after the contact reaction treatment in the ozone atmosphere of (1) had a lower sulfur content. 8. Opm was reached, and the desulfurization rate was about 76.0%. The kerosene after the extraction treatment of (2) had a sulfur content of 1.0 ppm and a desulfurization rate of about 97.0%. Furthermore, the kerosene after the adsorption treatment of (3) had a sulfur content of 0.2 ppm and a desulfurization rate of about 99.4%. table 1

Content (PPHO

(1). Contact angle with ozone ¾®S 8.0 About 76.0

Kerosene after difficulty

(2). Who extracts MS 1.0 about 97.0

After kerosene

(3). Action 0.2 0.2 99.4

Kerosene after treatment 4 From the above, it was clarified that the spraying of kerosene in an ozone atmosphere and the contact reaction treatment allowed the subsequent separation of sulfur compounds from kerosene to be performed very smoothly and with a sufficient desulfurization rate. Example 2

The ozone generated by the ozone generator 1 using air as a raw material is supplied as a mixture with air to the contact reaction tank 4 having a volume of 200 m1, thereby forming an ozone atmosphere in the contact reaction tank 4. did. Then, 50 ml of commercially available light oil (sulfur content: 250 ppm) was sprayed and supplied to the contact reaction tank 4 by the spray means 3, and the contact reaction treatment with the spray light oil was performed in the ozone atmosphere. The temperature in the contact reaction tank 4 was set to 40 ° C or less.

(2) An extraction solvent consisting of 100% methanol was added to the light oil after separating the solid product in (1) to extract organic sulfur compounds and the like from the light oil.

(3) The light oil after the solid product was separated in (1) was subjected to adsorption treatment with silica gel.

The sulfur content in the light oil obtained in the above (1) to (3) was measured to obtain the desulfurization rate. Table 2 shows the results.

As is clear from Table 2, while the sulfur content of the original diesel oil was 250.Oppm, the diesel oil after the contact reaction treatment in the ozone atmosphere of (1) The sulfur content was 234. Oppm, and the desulfurization rate was 6.4%. In addition, the light oil after the extraction treatment of (2) had a sulfur content of 205.Oppm and a desulfurization rate of 18.0%. Furthermore, in the light oil after the adsorption treatment of (3), the sulfur content is 176.Oppm, Table 2 shows that the desulfurization rate was 29.6%

From the above, it is clear that by performing a contact reaction treatment by spraying kerosene in an ozone atmosphere, the subsequent separation of sulfur compounds from light oil can be performed smoothly and with a reasonable desulfurization rate, although not as much as in the case of kerosene. It became. Industrial applicability

According to the method for separating sulfur compounds contained in petroleum according to claim 1 comprising the above constitution and function, the present invention provides a method for separating sulfur compounds contained in petroleum from petroleum, comprising the steps of: By supplying petroleum to the atmosphere in a mist state, a contact reaction treatment with ozone is performed, thereby oxidizing sulfur compounds in petroleum.

Oxidation of sulfur compounds in petroleum is achieved by supplying mist of petroleum into the ozone atmosphere. 6 that can be carried out in an environment that is novel and has a very high catalytic reaction effect. Therefore, it does not require high-temperature, high-pressure, expensive catalysts, etc. Can be separated. Further, according to the method for separating sulfur compounds contained in petroleum according to claim 2, in addition to the effect of the configuration according to claim 1, petroleum can be obtained by a catalytic reaction treatment in an ozone atmosphere. The solid product generated inside is separated into solid and liquid,

The water-soluble sulfur compounds generated by the contact reaction treatment in an ozone atmosphere are precipitated as solid products in petroleum without dissolving them, and are directly separated from petroleum without any other separation treatment can do.

According to the method for separating sulfur compounds contained in petroleum described in claim 3, in addition to the effect of the structure described in claim 1 or 2, the catalytic reaction treatment in an ozone atmosphere is performed. The remaining petroleum compounds were extracted from the applied petroleum using the extraction solvent, or the extraction solvent plus water, or water itself.

Sulfur compounds that are oxidized by the catalytic reaction treatment in an ozone atmosphere and remain in petroleum with their polarities increased can be effectively extracted and separated.

According to the method for separating sulfur compounds contained in petroleum described in claim 4, in addition to the effect of the structure described in claim 1 or 2, the catalytic reaction treatment in an ozone atmosphere is performed. Adsorbents were used to adsorb residual sulfur compounds to the conducted petroleum,

Sulfur compounds that are oxidized by the catalytic reaction treatment in an ozone atmosphere and remain in petroleum with their polarities increased can be effectively adsorbed and separated. (7) According to the method for separating sulfur compounds contained in petroleum described in claim 5, in addition to the effect of the structure described in claim 1 or 2, a catalytic reaction treatment in an ozone atmosphere is provided. The remaining sulfur compounds were separated from the petroleum that was subjected to the extraction process using an extraction solvent and the adsorption process using an adsorbent.

Sulfur compounds that are oxidized by the contact reaction treatment in an ozone atmosphere and remain in the petroleum in a state of increased polarity are more easily effected than when the extraction treatment and the adsorption treatment are performed alone. Can be separated. According to the apparatus for separating sulfur compounds contained in petroleum according to claim 6, a contact reaction tank that forms an ozone atmosphere in an internal space; a unit that supplies ozone to the contact reaction tank; At least means for spraying and supplying the oil to be treated into the reaction tank.

Petroleum can be contact-reacted in a spray state in an ozone atmosphere in a contact reaction tank, and oxidation of sulfur compounds contained in petroleum can be performed with sufficient reaction efficiency and reaction speed. In addition, the polarity of the contained sulfur compound can be sufficiently increased. Moreover, it does not require costly equipment such as high temperature and high pressure or complicated mechanisms, and it is relatively easy and compact equipment to efficiently and efficiently separate sulfur compounds from petroleum at low cost. It becomes possible.

Claims

The scope of the claims

1. A method for separating sulfur compounds contained in petroleum from petroleum. The petroleum is supplied into the ozone atmosphere in a mist state to perform a contact reaction treatment with ozone, thereby oxidizing the sulfur compounds in the petroleum. A method for separating sulfur compounds contained in petroleum.

2. The method for separating sulfur compounds contained in petroleum according to claim 1, wherein a solid product generated in petroleum is subjected to a solid-liquid separation by a catalytic reaction treatment in an ozone atmosphere.

3. It is characterized by extracting residual sulfur compounds from petroleum that has been subjected to catalytic reaction treatment in an ozone atmosphere, using an extraction solvent, water added to the extraction solvent, or water itself. 3. The method for separating sulfur compounds contained in petroleum oil according to claim 1 or 2.

4. The petroleum that has been subjected to the catalytic reaction treatment in an ozone atmosphere is subjected to adsorption of a residual sulfur compound using an adsorbent, and is contained in petroleum according to claim 1 or 2, wherein the sulfur compound is adsorbed. Method for separating sulfur compounds.

5. The residual sulfur compound is separated from petroleum that has been subjected to catalytic reaction in an ozone atmosphere by combining extraction with an extraction solvent and adsorption with an adsorbent. Item 4. The method for separating sulfur compounds contained in petroleum according to Item 1 or 2.

6. A contact reaction tank (4) having an ozone atmosphere in the inner space, a means (1) for supplying ozone to the contact reaction tank (4), and spraying of petroleum to be treated into the contact reaction tank (4). A device for separating sulfur compounds contained in petroleum, characterized by comprising at least means (2, 3) for supplying sulfur.