JP2003193066A - Method for oxidative desulfurization of liquid petroleum product and oxidative desulfurization plant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxidative desulfurization method for diminishing the sulfur content of a liquid petroleum product by efficiently separating sulfur components in the petroleum product such as kerosene, light oil, naphtha or gasoline, and to provide a plant for the method. <P>SOLUTION: The oxidative desulfurization method comprises the following process: an ozone-containing gas is contacted with the sulfur-containing liquid petroleum product to oxidize the sulfur components in the petroleum product and the resultant oxidized sulfur compounds is separated by extraction, or the like, using a solvent containing a lower alcohol such as methanol. The resulting solvent containing the oxidized sulfur compounds can be refined, as necessary, by using a means such as distillation and reused. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oxidative desulfurization method for petroleum products and an oxidative desulfurization apparatus for oxidizing and separating sulfur compounds contained in petroleum products such as kerosene, light oil, naphtha and gasoline to remove them.

[0002]

2. Description of the Related Art Hydrodesulfurization is generally used as a desulfurization technology for petroleum products. In this method, the processing pressure is 100 kg /
cm ² g, the processing temperature was around 350 ° C., which was severe, and the equipment was heavy equipment.

On the other hand, as a desulfurization technique using an oxidizing agent,
Method and apparatus for oxidizing and recovering organic sulfur compounds of liquid oil and refining and recovering liquid oil
No. 07059) has been proposed. This method is intended to purify the liquid oil by oxidizing and recovering the organic sulfur compound present in the liquid oil with an oxidizing agent containing hydrogen peroxide solution.

The method disclosed in the above publication is a technique which enables desulfurization at a low temperature, but since formic acid or the like is used as an oxidizing agent, facility corrosion is a serious problem, and the oxidizing agent is a liquid (hydrogen peroxide solution). + Formic acid), it is difficult to separate the oxidizing agent and the petroleum product after the reaction, and there is a drawback that the petroleum product loses about 3% by volume.

Further, in this technique, when the oxidizing agent and the liquid oil are reacted, a stirring device for stirring the oxidizing agent at a high speed and a atomizing and injecting device for feeding the liquid oil are required, which requires a large facility. There is also the problem that it has to be something.

[0006]

DISCLOSURE OF THE INVENTION The present invention is desulfurization capable of reducing the sulfur concentration of petroleum products by efficiently separating the sulfur content in liquid petroleum products such as kerosene, light oil, naphtha and gasoline. It is an object to provide a method and a device therefor.

[0007]

In order to solve the above-mentioned problems, the invention of the method for oxidative desulfurization of liquid petroleum products according to claim 1 is to bring a gas containing ozone into contact with a liquid petroleum product containing sulfur. Is used to oxidize the sulfur content in the liquid petroleum product and separate the produced sulfur oxide compound.

According to this feature, by bringing the gas containing ozone into contact with the liquid petroleum product, the sulfur content in the liquid petroleum product can be oxidized and separated as a sulfur oxide compound, so that the petroleum product can be efficiently used. Can be desulfurized.

That is, when ozone is applied to sulfur components such as various sulfur compounds contained in petroleum products to oxidize them, the physical properties such as boiling point, solubility and adsorption capacity of the sulfur oxide compounds produced are higher than those of the original sulfur components. It can be easily separated from petroleum products by treatments such as distillation, extraction and adsorption.

Further, as an advantage of using ozone in particular, since the oxidation reaction of the sulfur content is carried out between the gas ozone and the gas oil and the liquid petroleum product, the reaction proceeds promptly and the treatment efficiency is improved. Is high. Further, since ozone, which is a gas, is easily separated from the liquid petroleum product after the reaction, no special operation or treatment is required for the separation after the oxidation step. That is, liquid-
In a liquid reaction or a gas-gas reaction, a complicated operation is required for separation after contact and mixing, or separation becomes difficult and a petroleum product as a raw material is lost. Since it can be easily separated / removed, it can be immediately transferred to the next step and there is almost no loss of raw materials.

The invention of the method for oxidative desulfurization of liquid petroleum products according to claim 2 is characterized in that, in claim 1, the sulfur oxide compound is extracted and extracted with a solvent containing a lower alcohol. According to this feature, the produced sulfur oxide compound can be efficiently extracted by using the solvent containing the lower alcohol. Separation by extraction is advantageous in that it consumes less energy than separation by distillation and requires a simpler device configuration than separation by adsorption.

The invention of the method for oxidative desulfurization of a liquid petroleum product described in claim 3 is characterized in that, in claim 2, the solvent containing a lower alcohol is a solvent containing a lower alcohol and water. According to this feature, by using a solvent containing lower alcohol such as methanol and water in a predetermined ratio as the solvent containing lower alcohol, the separability between the oil layer (petroleum product) and the solvent layer is improved, and the loss of the petroleum product is reduced. Can be separated while minimizing.

Further, the invention of the method for oxidative desulfurization of a liquid petroleum product according to a fourth aspect is the method according to any one of the first to third aspects, wherein the gas containing ozone and the liquid petroleum product containing a sulfur component are used. The contact is performed in the presence of a precipitation inhibitor. According to this feature, by oxidizing the sulfur component in the presence of the precipitation inhibitor, it is possible to prevent the generated sulfur oxide compound from being precipitated in the reactor. As a result, it is possible to reduce the probability of causing obstacles such as clogging due to deposits during long-term operation in a desulfurization process of petroleum products or implementation on an industrial scale.

According to the invention of an oxidative desulfurization apparatus for petroleum products described in claim 5, gas-liquid contacting means for bringing a gas containing ozone into contact with liquid petroleum product containing sulfur, and treatment with the gas-liquid contacting means. A liquid petroleum product containing the sulfur oxide compound thus obtained, a mixing means for mixing an extraction solvent, and a mixture of the liquid petroleum product and the extraction solvent mixed by the mixing means,
Separation means for separating a refined petroleum product and an extraction solvent containing a sulfur oxide compound are provided.
The apparatus provided with the gas-liquid contacting means, the mixing means, and the separating means is most suitable for carrying out the oxidative desulfurization method for petroleum products described in claims 2 to 4.

Further, the invention of the oxidative desulfurization apparatus for petroleum products according to claim 6 is the same as in claim 5, wherein the extraction solvent containing a sulfur oxide compound is further separated into a sulfur oxide compound and an extraction solvent. It is characterized by having two separating means. According to this feature, by providing the second separation means for separating the sulfur oxide compound and the extraction solvent,
It is possible to reuse the extraction solvent and recover the sulfur oxide compound. Therefore, effective use of resources and reduction of processing cost can be achieved.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The oxidative desulfurization method of the present invention is a method for oxidizing a sulfur content in a liquid petroleum product by bringing a gas containing ozone into contact with a liquid petroleum product containing a sulfur content, thereby producing a sulfur oxide compound. Is carried out by separating

The liquid petroleum products to be subjected to oxidative desulfurization in the present invention include, for example, petroleum products such as kerosene, light oil, naphtha and gasoline, or their raw materials. These liquid petroleum products have, for example, R-S-R 'or R-SH as sulfur content (wherein R and R'represent an alkyl group).
It contains various sulfur compounds, including organic sulfur compounds such as sulfides and thiols represented by. And
By subjecting liquid petroleum products to ozone, they can be converted into sulfur oxide compounds such as sulfoxide and sulfone in the above-mentioned example of sulfide (R—S—R ′).

Examples of the "gas containing ozone" used in the present invention include ozone gas itself, air containing ozone, oxygen gas containing ozone, and the like.

The contact between the gas containing ozone and the liquid petroleum product can be carried out by using a normal gas-liquid contact means.
That is, as a general gas-liquid contact device, for example, a packed tower system for enhancing gas-liquid contact efficiency by a lattice-shaped packing material, a spray tower system for spraying or atomizing liquid petroleum products into droplets or fine particles, An apparatus such as a wetting wall tower system that forms a liquid film can be used. In the case of such a system, the introduction direction of the gas containing ozone may be countercurrent or parallel to the liquid petroleum product. In addition to these, for example, in a liquid petroleum product filled in a container,
Alternatively, a method in which a gas containing ozone is introduced as bubbles into the liquid petroleum product flowing in the pipe is also possible.
Among the above methods, as a method capable of obtaining a large contact area with ozone, for example, a packed tower system or a spray tower system is preferable.

When a liquid petroleum product and a gas containing ozone are contacted with each other, the required gas amount and ozone concentration can be appropriately set according to the sulfur concentration in the desulfurized petroleum product. For example, the ozone concentration in the gas to be supplied is 0. It may be from 01 to 10.0% by volume, preferably from 0.1 to 1.0% by volume.

The superficial velocity of the gas in the reactor is SV.
Value is 0.1 to 6.0 / hour, preferably 1.0 to 2.5
Generally, the operating temperature is room temperature, the operating pressure is normal pressure, the temperature is about 10 ° C to 60 ° C, and the pressure is atmospheric pressure to
It is preferable to set it appropriately within the range of about 3 kg / cm ² g.

In the method of the present invention, it is preferable that the gas containing ozone and the liquid petroleum product containing sulfur are contacted with each other in the presence of a precipitation inhibitor. The oxidative desulfurization reaction by the gas-liquid contact method adopted in the present invention has advantages that desulfurization efficiency is good and ozone can be easily separated after the oxidation reaction because the gas containing ozone is used as described above. It is feared that the deposition of the sulfur oxide compound generated by the reaction is more likely to occur than in the liquid-liquid reaction. Precipitation of sulfur oxide compounds in the reactor may hinder the flow of liquid petroleum products and gases containing ozone, resulting in a decrease in treatment efficiency and a failure due to clogging. Therefore, by carrying out the oxidative desulfurization reaction in the presence of a precipitation inhibitor, it is possible to effectively prevent the precipitation of the sulfur oxide compound in the reaction device, which enables long-term operation and implementation on an industrial scale. The desulfurization process of highly reliable petroleum products can be realized.

The precipitation inhibitor is not particularly limited as long as it is a substance capable of dissolving the produced sulfur oxide compound and having no effect on the oxidation reaction by ozone, and the extraction solvent described later. It is preferable to use the same substances as above, for example, lower alcohols such as methanol, ethanol and propanol.

The precipitation inhibitor may be added in advance to the liquid petroleum product which is a raw material, or may be added continuously or intermittently in the process of the oxidative decomposition reaction. In any case, the required amount may be added according to the predicted production amount of the sulfur oxide compound or the sulfur content contained in the liquid petroleum product. The amount of addition is, for example, about 1% to 30% by volume, preferably about 1% to 5% by volume, based on the liquid petroleum product.

The above-mentioned step of contacting the gas containing ozone and the liquid petroleum product containing sulfur may be repeated. By repeating the gas-liquid contact step a plurality of times (for example, about 2 to 5 times), the sulfur content contained in the liquid petroleum product can be more reliably oxidized, and thus the final degree of refinement can be increased.

Separation of the sulfur oxide compound from the liquid petroleum product can be carried out by a usual separation means such as solvent extraction, distillation and adsorption. Among these, the treatment by solvent extraction, which consumes less energy and has a simple apparatus configuration, is preferable. Hereinafter, separation by solvent extraction will be described in detail as an example.

As the extraction solvent, any substance can be used without limitation as long as it can dissolve the produced sulfur oxide compound and can be separated from the liquid petroleum product. For example, a solvent containing a lower alcohol such as methanol, ethanol or propanol. The use of is preferable because the produced sulfur oxide compound can be efficiently transferred to the solvent side and separated from the liquid petroleum product. When a solvent containing water in a predetermined ratio (for example, methanol + water) is used as the solvent containing lower alcohol, the separability between the oil layer (petroleum product) and the solvent layer is improved, and the boundary between both layers is clear. Therefore, the oil product can be separated with almost no loss. In this case, for example, it is preferable to add about 1 to 20% by volume of water to methanol or the like, and 1 to 15% by volume depending on the type of petroleum product.
Optimum separability can be obtained by blending to some extent.

In the extraction and separation with a solvent, it is preferable to carry out a mixing operation such as stirring in order to effectively carry out the extraction. This may be a mixing method such as stirring or the like, for example, mixing with a static mixer, a spray nozzle, a throttle valve, or the like. The well-mixed liquid petroleum product, the extraction solvent and the sulfur oxide compound are separated into the liquid petroleum product and the extraction solvent containing the sulfur oxide compound by the extraction operation. As described above, the sulfur oxide compound is moved from the petroleum product to the solvent side by the extraction, and the liquid petroleum product from which the sulfur oxide compound is removed is recovered as a desulfurized petroleum product after the post-treatment as necessary. This solvent extraction step and separation step also
Liquid petroleum products can be refined to a higher degree by repeating the process as necessary.

The above processes from the gas-liquid contact step to the step of separating the sulfur oxide compound by solvent extraction or the like can be repeated a plurality of times (for example, about 2 to 5 times) as a series of steps. As in the case where the above steps are individually repeated as described above, the degree of refinement of the liquid petroleum product can be increased.

On the other hand, the extraction solvent containing the sulfur oxide compound is
By separating the sulfur oxide compound, it is preferable to reuse it as an extraction solvent. For example, methanol (or methanol water) containing a sulfur oxide compound can be recovered as a purified solvent by performing a separation operation such as distillation. In the case of distillation, the operating pressure is generally normal pressure. In the above example, methanol is taken out from the top of the column and sulfur oxide compound or sulfur oxide compound + water is taken out from the column bottom and discharged to the outside of the system. To be done. This sulfur oxide compound can also be recovered and used effectively if necessary.

Although the case of solvent extraction has been described above as an example, the same refined desulfurized petroleum product can be recovered by treating in accordance with a conventional method for distillation and adsorption separation.

FIG. 1 is a diagram showing an outline of an oxidative desulfurization apparatus 100 according to an embodiment of the present invention. In FIG.
The oxidative desulfurization apparatus 100 includes a reactor 1 as a gas-liquid contact means.
1. A mixer 31 as a mixing means and a separation tank 41 as a first separating means are provided. Further, this oxidative desulfurization apparatus 100 is equipped with a distillation column 42 as a second separating means for purifying and reusing the recovered extraction solvent 53. First, the reactor 11 is filled in the reactor. It is a packed tower type filled with the material 12, and the introduction part 1 of the liquid petroleum product 51 is provided on the upper part.
5. A countercurrent system having an ozone gas 52 introduction section 14 at the bottom is adopted. The countercurrent method is preferable because it allows sufficient gas-liquid contact. As the filler 12, a usual filler 12 suitable for refining petroleum products can be used. As the reactor 11, in addition to a countercurrent system as shown in FIG. 2 (a), a parallel flow system can be used. For example, as shown in FIG. Petroleum products 51
And a gas-liquid separator 19 is provided downstream of the reactor 11 having the introduction part 15 of the ozone gas, the introduction part 14 of the ozone gas 52 at the top, and the discharge part 18 at the bottom.

The reactor 11 is not limited to the packed tower system, and the spray tower system illustrated in FIGS. 3 (a) and 3 (b) can also be used. In the spray tower type reactor 11, the liquid petroleum product 51 is diffused as fine particles from the spraying device 13 in the upper portion, so that gas-liquid contact with the ozone gas 52 can be efficiently performed. Also in the spray tower system, in addition to the countercurrent system [Fig. 3 (a)] in which the ozone gas 52 is introduced from the lower part of the reactor 11, ozone gas is supplied to the reactor 11 as well.
It is possible to use the parallel flow system [FIG. 3 (b)] which is introduced from the top of the and is equipped with the gas-liquid separator 19.

Further, as the reactor 11, an ejector type spray nozzle 61 and a filler 1 as illustrated in FIG.
It is also possible to use a device provided with 2. In this reactor 11, the liquid petroleum product 51 is dispersed as fine particles by the ejector-type spray nozzle 61 that mixes the liquid petroleum product 51 and the ozone gas 52, and the ozone gas 52
The liquid petroleum product 51, which is separately supplied from the lower part of the reactor 11 through the distributor 62 and is dispersed, and the liquid petroleum product 51 flowing down through the filler 12 can be brought into contact with each other. It becomes possible to efficiently proceed the oxidation reaction by. In addition to the above, for example, a wet wall system (not shown) can be used as the reactor 11.

In FIG. 1, the reactor 11 has a structure of only one tower, but a plurality of reactors 11 can be connected in series if necessary for the purpose of more reliably promoting the oxidation reaction of the sulfur content. Is. Further, for the same purpose, it is possible to provide a path for introducing a part or all of the liquid petroleum product (after the oxidation reaction) 51 ′ once discharged from the reactor 11 into the reactor 11 again.

In FIG. 1, a mixer 3 as a mixing means.
1 uses a static mixer 32 [see FIG. 5 (a)]. As the static mixer 32, a general structure can be used. The mixer 31 is not limited to the static mixer 32.
The throttle valve 33 shown in (b) and the stirring tank 3 shown in FIG.
4 etc. can also be used. Among them, the static mixer 32 and the throttle valve 33 are advantageous in that they do not require power and can perform continuous processing in a space-saving manner. Particularly, the static mixer 32 which has high stirring performance and is capable of uniform mixing is preferable.

The separation tank 41 as the first separating means is for allowing the liquid petroleum product 51 and the extraction solvent 53 to stand and separate them into layers for separate collection, and each has an upper and a lower discharge part. . Although an independent separation tank 41 is provided as the first separation means in FIG. 1, when the stirring tank 34 shown in FIG. 5C is used as the mixing means, for example, it is integrated with the mixer 31. It may be configured.

Further, in the above apparatus configuration, the reactor 1
It is also possible to integrate 1 and the mixer 31 into an integrated reaction / mixer 71 as shown in FIG. The reaction / mixing device 71 is divided into a reaction part 72 for performing gas-liquid contact and a mixing / extracting part 73 for mixing an extraction solvent. Further, the reaction part 71 includes, for example, a filler (not shown here). Have been deployed. In this system, the liquid petroleum product 51 is introduced from the liquid introduction section 74 above the reaction section 71 and flows down while contacting the ozone gas 52 introduced from the gas introduction section 75 below the reaction section 71. The mixing / extracting unit 73 is provided with a solvent introducing unit 76 for the extracting solvent 53 such as methanol, and the extracting solvent 53 introduced therein and the liquid petroleum product 51 ′ after the oxidation reaction are, for example, by means such as stirring. Mix well. The mixture is discharged from the discharge part 77 at the bottom of the reaction / mixer 71 and sent to the next step (separation tank 41). By using such an integrated reaction / mixer, the device configuration can be simplified. Further, in the reaction / mixer 71 of FIG.
The mixing / extracting unit 73 may be provided with a separation function so that the extraction solvent 53 and the liquid petroleum product 51 can be separated. In this case, since the separation tank 41 shown by a virtual line can be omitted, the device structure can be further simplified.

In the apparatus shown in FIG. 1 described above, the reactor 11 as the gas-liquid contact means, the mixer 31 as the mixing means, and the first separation are provided for the purpose of ensuring the oxidation reaction and separation of the sulfur content. If necessary, a plurality of separation tanks 41 as a unit may be connected in series. Further, for the same purpose, it is possible to provide a path for introducing a part or all of the desulfurized petroleum product (after separation) 54 once discharged from the separation tank 41 into the reactor 11 again.

The distillation column 42 as the second separating means is for separating the extraction solvent 53 and the sulfur oxide compound dissolved therein by utilizing the difference in vapor pressure, and has a general structure. Distillation equipment can be used.

Based on the above, the oxidative desulfurization apparatus 100 shown in FIG.
The processing procedure using will be described. First, in the petroleum product 51 introduced from the upper part of the packed tower type reactor 11, the reactor 11
By contacting the ozone gas 52 introduced from the lower part as a counter flow, the gas-liquid contact is efficiently performed, and the oxidation reaction of the sulfur content proceeds. The reaction conditions are as described above. The liquid petroleum product 51 ′ containing the sulfur oxide compound produced by the oxidation reaction is discharged from the discharge part 17 at the bottom of the reactor and transferred to the next step.

In FIG. 1, the extraction solvent 53 (for example, methanol or methanol water) is predetermined in the liquid petroleum product 51 ′ treated in the reactor 11 in the introduction section 21 on the upstream flow path of the static mixer 32. Introduced in proportion. The liquid petroleum product 51 and the extraction solvent 53 are sufficiently mixed by the static mixer 32, and the sulfur oxide compound in the liquid petroleum product 51 moves to the extraction solvent 53 side.

The extraction solvent 53 and the liquid petroleum product 51 'are allowed to stand in the separation tank 41, the extraction solvent 53 is recovered from the lower part, and the desulfurized petroleum product 54 is recovered from the upper part.

In order to repeatedly perform the steps from the introduction of the extraction solvent to the mixing and separation, the introduction section 21, the mixer 31 and the separation tank 41 may be repeatedly connected in series or a circulation path may be provided. It is possible.

Next, the extraction solvent 53 containing the sulfur oxide compound 55 is sent to the distillation column 42, and the sulfur oxide compound 55 is separated by distillation here. The gaseous extraction solvent 53 recovered from the top of the distillation column 42 is used in the heat exchanger 4
It is cooled in 3 and stored in the recovery solvent tank 44 for reuse. The sulfur oxide compound 55 recovered from the bottom of the distillation column 42 can be used in various chemical industries by refining it if necessary.

Although the present invention has been described with reference to various embodiments, the present invention is not limited to the above embodiments, and other embodiments are also possible within the scope of the invention described in the claims. Of course, it is applied.

[0047]

EXAMPLES Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the invention.

Example 1 Measurement of desulfurization rate (kerosene): As the starting kerosene, the one having the properties shown in Table 1 was used, and oxidative desulfurization treatment was carried out by the method of the present invention. Oxidation reaction by gas-liquid contact is 0.67g / oz
It carried out by Hr and SV = 0.5. Next, the kerosene after the oxidation reaction was mixed with the extraction solvent (methanol and water) in the ratio shown in Table 2, mixed for 5 minutes, allowed to stand for 10 minutes, and separated into kerosene. After repeating the operations of to 3 times, washing with water was performed. When the sulfur content in the kerosene after the treatment was measured, Table 2
It was as shown in.

[0049]

[Table 1]

[0050]

[Table 2]

Example 2 Measurement of desulfurization rate (light oil): As the light oil as a raw material, those having the properties shown in Table 3 were used and subjected to oxidative desulfurization treatment by the method of the present invention. Oxidation is 0.65 g /
It carried out by Hr and SV = 1.0. Then, the extraction solvent (methanol and water) was mixed with the gas oil after the oxidation reaction in the ratio shown in Table 4, mixed for 5 minutes, allowed to stand for 10 minutes, and gas oil separated. After repeating the operations of to 3 times, washing with water was performed. When the sulfur content in the treated gas oil was measured, Table 4
It was as shown in.

[0052]

[Table 3]

[0053]

[Table 4]

Example 3 Measurement of desulfurization rate (naphtha): Raw material naphtha having the properties shown in Table 5 was used and subjected to oxidative desulfurization treatment by the method of the present invention. Oxidation is 0.66 for oxidation reaction by gas-liquid contact
It carried out by g / Hr and SV = 0.5. Next, the naphtha after the oxidation reaction was mixed with the extraction solvent (methanol and water) in the ratio shown in Table 6, mixed for 5 minutes, allowed to stand for 10 minutes, and naphtha separated. After repeating the operations of to 3 times, washing with water was performed. When the sulfur content in the naphtha after the treatment was measured, it was as shown in Table 6.

[0055]

[Table 5]

[0056]

[Table 6]

Example 4 Extraction effect by mixed solvent (methanol + water): As the starting kerosene, the same properties as shown in Table 1 as in Example 1 were used, and oxidative desulfurization treatment was carried out by the method of the present invention. Oxidation reaction by gas-liquid contact, ozone amount 0.4g / Hr, SV = 2
It was carried out in. Next, the kerosene after the oxidation reaction was mixed with the extraction solvent (methanol and water) in the ratio shown in Table 7, mixed for 5 minutes, allowed to stand for 10 minutes, and separated into kerosene. After repeating the operations of to 3 times, washing with water was performed. When the sulfur content in the kerosene after the treatment was measured, it was as shown in Table 7.

[0058]

[Table 7]

As is clear from Table 7, when a mixed solvent of methanol and water is used as the extraction solvent, the separability from the liquid petroleum product (kerosene) is improved and the loss in the extraction operation can be reduced. .

Example 5 Desulfurization rate when a precipitation inhibitor was simultaneously flown into the reactor: As the starting kerosene, the same properties as shown in Table 1 as in Example 1 were used, and the oxidative desulfurization treatment was carried out by the method of the present invention. It was Oxidation reaction by gas-liquid contact is 0.67g / Hr, SV
= 0.5, methanol as precipitation inhibitor 0.5 ml / min (1/10 of kerosene) or 1.0 m
It was performed by injecting 1 / min (1/5 of kerosene). Also,
It carried out also when not injecting methanol on the same conditions.

After the oxidation reaction, methanol was mixed or additionally mixed, and water was further added (kerosene: methanol: water = 5).
(0: 20: 1), mixed for 5 minutes, allowed to stand for 10 minutes, and separated kerosene. After repeating the operations of to 3 times, washing with water was performed. When the sulfur content in the kerosene after the treatment was measured, it was as shown in Table 8.

[0062]

[Table 8]

As is clear from Table 8, even if the catalytic oxidation reaction was carried out in the presence of methanol as a precipitation inhibitor, the desulfurization rate was hardly affected. Therefore, the effectiveness of coexisting a substance capable of dissolving a sulfur oxide compound as a precipitation inhibitor in the oxidation reaction process was shown.

[0064]

According to the method of the present invention, by bringing a gas containing ozone into contact with a liquid petroleum product, the sulfur content in the liquid petroleum product can be oxidized and separated as a sulfur oxide compound. Can desulfurize petroleum products. That is, when ozone is applied to the sulfur components such as various sulfur compounds contained in petroleum products to oxidize them, the physical properties such as boiling point, solubility, and adsorption capacity of the sulfur oxide compounds that are produced are significantly different from the original sulfur components. Therefore, it can be easily separated from petroleum products by treatments such as distillation, extraction and adsorption.

Further, as an advantage of using ozone in particular, the oxidation reaction of the sulfur content is carried out between the gas ozone and the gas oil and the liquid petroleum product, so that the reaction proceeds promptly and the treatment efficiency is improved. Is high. In addition, since ozone, which is a gas, is easily separated from the liquid petroleum product after the reaction, no special operation or treatment is required for the separation after the oxidation reaction step. That is,
In a liquid-liquid reaction or a gas-gas reaction, a complicated operation is required for separation after contact and mixing, or separation at the boundary becomes difficult and a loss occurs in a petroleum product as a raw material, but it is a gas. Since some ozone can be easily separated and removed from the reaction system, it can be immediately transferred to the next step and there is almost no loss of raw materials.

Further, the oxidative desulfurization apparatus of the present invention is most suitable for carrying out the above-mentioned oxidative desulfurization method for petroleum products of the present invention.

[Brief description of drawings]

FIG. 1 is a schematic configuration drawing of an oxidative desulfurization apparatus according to an embodiment of the present invention.

FIG. 2 is a drawing for explaining an embodiment of a reactor.

FIG. 3 is a drawing for explaining another embodiment of the reactor.

FIG. 4 is a view for explaining still another embodiment of the reactor.

FIG. 5 is a view for explaining an aspect of a mixer.

FIG. 6 is a diagram illustrating an example of an integrated reaction / mixer.

[Explanation of symbols]

11 reactor 12 Filling material 13 Spraying device 14 Introduction 15 Introduction 16 Discharge part 17 Discharge part 18 Discharge part 19 Gas-liquid separator 31 Mixer 32 static mixer 33 Throttle valve 34 stirring tank 35 Stirrer 41 Separation tank 42 distillation column 43 heat exchanger 44 Recovery solvent tank 51,51 'Liquid petroleum products 52 Ozone gas 53 Extraction solvent 54 Desulfurized petroleum products 55 Sulfur oxide compounds 61 Ejector type spray nozzle 62 distributor 71 Integrated reaction / mixer 72 Reaction part 73 Mixing / extracting section 74 Liquid introduction part 75 Gas introduction section 76 Solvent introduction part 77 Discharge part

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinyasu Kanda             Mitsui Shipbuilding No. 1 Hachiman Kaigan Dori, Ichihara City, Chiba Prefecture             Chiba office (72) Inventor Tatsuya Kusakabe             3-4-1 Yahama, Owase-shi, Mie Tohoishi             Owase Factory of Oil Co., Ltd. (72) Inventor Naoto Kitagawa             3-4-1 Yahama, Owase-shi, Mie Tohoishi             Owase Factory of Oil Co., Ltd. (72) Inventor Tomohiro Yamamoto             2-chome, Surugadai, Kanda, Chiyoda-ku, Tokyo             Toho Oil Co., Ltd.

Claims (6)

[Claims] 1. A liquid, characterized in that a gas containing ozone is brought into contact with a liquid petroleum product containing sulfur to oxidize the sulfur content in the liquid petroleum product and to separate the produced sulfur oxide compound. Oxidative desulfurization method for petroleum products. 2. The method for oxidative desulfurization of a liquid petroleum product according to claim 1, wherein the sulfur oxide compound is extracted with a solvent containing a lower alcohol and separated. 3. The method for oxidative desulfurization of a liquid petroleum product according to claim 2, wherein the solvent containing a lower alcohol is a solvent containing a lower alcohol and water. 4. The method according to any one of claims 1 to 3, wherein the gas containing ozone and the liquid petroleum product containing sulfur are contacted in the presence of a precipitation inhibitor. Oxidative desulfurization method for liquid petroleum products. 5. A gas-liquid contact means for contacting a gas containing ozone with a liquid petroleum product containing sulfur, and a liquid petroleum product containing a sulfur oxide compound treated by the gas-liquid contact means with an extraction solvent. Mixing means for mixing, and a separation means for separating the mixture of the liquid petroleum product and the extraction solvent mixed by the mixing means into a refined petroleum product and an extraction solvent containing a sulfur oxide compound, Characteristic oxidative desulfurization equipment for petroleum products. 6. The petroleum product according to claim 5, further comprising a second separation means for separating the extraction solvent containing the sulfur oxide compound into the sulfur oxide compound and the extraction solvent. Oxidative desulfurization equipment.