JPH0672227B2 - Hydrocarbon oil desulfurization method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is used as a modifier for a paint, an adhesive, a rubber and the like having a light color and good weather resistance and / or a raw material for a hydrogenated hydrocarbon resin of a base polymer. The present invention also relates to a desulfurization and refining method for hydrocarbon oils, and further relates to a desulfurization and refining method for hydrocarbon olefins useful as raw materials for medicines and perfumes.

[Prior Art] Conventionally, as a method of desulfurizing hydrocarbon oil, the
Hydrofining, in particular hydrogen, comprising treating a hydrocarbon fraction with hydrogen in the presence of a catalyst complex containing Group VI and Group VIII metals or compounds thereof under a wide range of elevated hydrogen pressures and temperatures. There are numerous publications on chemical desulfurization. In such a reaction, the carbon-sulfur bonds of the molecules that make up the feedstock are cleaved, and the sulfur-containing moieties react with hydrogen to produce hydrogen sulfide. Also, the resulting hydrocarbon stream is separated from the residual mixture of hydrogen and hydrogen sulfide gas.

However, since the desulfurization reaction is carried out under high hydrogen pressure and high temperature, it is present in this hydrocarbon oil, and the hydrocarbon resin, medicine,
The olefins useful as a raw material for perfumes also have the drawback that they are saturated by hydrogenation.

In addition, when a hydrocarbon oil containing both an organic sulfur compound and a hydrocarbon olefin is polymerized by adding a catalyst without reducing the content of the organic sulfur compound, the organic sulfur compound is chained to the hydrocarbon olefin growth chain. A transfer reaction occurs, and a hydrocarbon resin having a high sulfur content is produced. Even if hydrogenation modification is performed to improve the heat resistance and weather resistance of this resin, the organic sulfur compound becomes a catalyst poison of the hydrogenation catalyst such as nickel, palladium, ruthenium, and platinum, and the reaction proceeds. However, there is a problem that the hydrogenated hydrocarbon resin cannot be produced, or even if it is produced, a large amount of catalyst is required due to poisoning, which is extremely disadvantageous in terms of production cost.

And, in the past, from the hydrocarbon oil containing both the organic sulfur compound and the hydrocarbon olefin, the loss of industrially useful hydrocarbon olefins is prevented as much as possible, and more than 90% of the organic sulfur compound is produced by a simple method. I can't find a way to remove it.

[Problems to be Solved by the Invention] The present inventor has conducted research to solve the above-mentioned problems, and obtained after distilling a hydrocarbon oil containing both an organic sulfur compound and a hydrocarbon olefin. By carrying out a mild polymerization reaction by adding an acid catalyst to the obtained middle distillate, industrially useful hydrocarbon olefin loss is reduced, and more than 90% of organic sulfur compounds are removed to obtain a hydrocarbon oil. The inventors have found that they can be achieved and completed the present invention.

Therefore, an object of the present invention is to remove an organic sulfur compound as much as possible from a hydrocarbon oil containing both an organic sulfur compound and a hydrocarbon olefin without losing the hydrocarbon olefin as much as possible. The object is to obtain a low-sulfurized hydrocarbon useful as a raw material for a small amount of hydrocarbon resin or a raw material for olefin such as coumarone and indene.

[Means for Solving the Problems] That is, the present invention is mainly composed of a fraction having a boiling point of 100 to 250 ° C., and a hydrocarbon oil containing both an organic sulfur compound and a hydrocarbon olefin is distilled to obtain a front fraction. It is a method for desulfurizing a hydrocarbon oil, which comprises a distillation treatment for removing a rear distillate and a light polymerization treatment for adding an acid catalyst to a middle distillate obtained by this distillation treatment to carry out a light polymerization reaction.

The hydrocarbon oil to be subjected to the desulfurization method of the present invention, for example, gas light oil produced in coal carbonization, 130 ~ 200 ° C. fraction obtained by distillation of coal tar, produced during petroleum refining or petroleum cracking. There is a hydrocarbon oil containing both an organic sulfur compound such as a C _{8 to} C ₁₀ fraction and a hydrocarbon olefin, and the hydrocarbon olefin is 20% by weight or more, preferably
It is desirable to contain 30% by weight or more. Further, it is desirable that the saturated hydrocarbon and the aromatic hydrocarbon having no olefin bond are contained in an amount of 20% by weight or more, preferably 30% by weight or more. For example, when a coumarone-indene resin is produced, these are used as a solvent. To work.

When the hydrocarbon olefin is vinyltoluene, coumarone, indene, etc., as the organic sulfur compound that can be removed by distillation treatment, for example, thiophene, monomethylthiophene, vinyltoluene such as dimethylthiophene, coumarone, those having a higher vapor pressure than indene, Further, it has a lower vapor pressure than vinyltoluene such as benzothiophene, coumarone, indene and the like. Further, as an organic sulfur compound that can be removed by a mild polymerization treatment using an acid catalyst, for example, chain transfer reactivity to a hydrocarbon olefin growing chain such as thiophene, monomethylthiophene, dimethylthiophene, trimethylthiophene, thiophenol, and methylthiophenol. Is to have.

The steam distillation treatment may be carried out under normal pressure or reduced pressure, but reduced pressure distillation is preferred because it reduces the loss of hydrocarbon olefins due to thermal polymerization. When recovering coumarone and indene as hydrocarbon olefins reduced in sulfur by this distillation treatment, the column top temperature range of the collected fraction in the distillation is preferably 160 to 180 ° C in the case of normal pressure, and 100 mmHg reduced pressure. In this case, the range of 100 to 120 ° C is preferable.

Further, in the method of the present invention, the mild polymerization treatment means that the polymerization of hydrocarbon olefins such as coumarone and indene contained in the raw material hydrocarbon oil is 40% by weight or less, preferably 10 to 30% by weight. It refers to some degree of polymerization. Examples of the acid catalyst used for this mild polymerization treatment include:
Examples thereof include Bronsted acids such as sulfuric acid, phosphoric acid, hydrochloric acid and nitric acid, boron trifluoride and its complex, Lewis acids such as aluminum chloride, and solid acids such as acid clay, activated clay and acid ion exchange resins. . The conditions of this mild polymerization treatment vary depending on the type of the hydrocarbon oil to be treated and the type of the acid catalyst used, but the amount of the acid catalyst used is 0.1 to 50% by weight, preferably 0.1 to 30%. %, The reaction temperature is 0 to 150 ° C., preferably 0 to 100 ° C., and the reaction time is 0.1 to 10 hours, preferably 0.1 to
A good range is 7 hours.

Hydrocarbon oil containing a hydrocarbon olefin desulfurized by the above-mentioned distillation treatment and light polymerization treatment, becomes a hydrocarbon resin having a low sulfur content by polymerizing this, and this low-sulfurized hydrocarbon resin is nickel, Hydrogenated hydrocarbons that are less toxic to hydrogenation catalysts such as palladium, lithium, and platinum, can be hydrogenated in the presence of these hydrogenation catalysts, and are colorless and transparent and have good weather resistance and heat discoloration resistance. It is extremely useful as a raw material for resins.

[Operation] According to the desulfurization method of the present invention, part of the organic sulfur compound is fractionally removed in the distillation step, and the remaining organic sulfur compound is separated and removed as a polymerization reaction product in the light polymerization step. This reduces the loss of industrially useful hydrocarbon olefins while minimizing the loss of organic sulfur compounds.
90% or more can be separated and removed.

There is a difference in vapor pressure between hydrocarbon olefins such as coumarone and indene and organic sulfur compounds such as thiophene, motomethylthiophene and dimethylthiophene, and these organic sulfur compounds can be removed by distillation. Organic sulfur compounds such as thiophene, dimethylthiophene, and trimethylthiophene have chain transfer reactivity to a hydrocarbon olefin growing chain in an acid-catalyzed cationic polymerization reaction, and these organic sulfur compounds are used as products of this polymerization reaction. It is thought that it can be removed.

[Examples] Hereinafter, the method of the present invention will be specifically described based on Examples, Reference Examples and Comparative Examples.

Example 1 Obtained by distilling gas light oil produced in coal carbonization 13
The 0-200 ° C fraction was pickled with 40% dilute sulfuric acid. The obtained hydrocarbon oil after detarring base treatment was used as an original sample and
2,000 g was charged into a two-necked flask, and using a batch-type vacuum distillation tower for experiments with a theoretical plate number of 17.8, pressure 100 mmHg, reflux ratio (reflux / release) 7/1, collected fraction 95-120 ° C (yield 54 wt. %) And distilled under reduced pressure to obtain 1,08
I got 0g.

The olefin composition of the original sample and the obtained distilled oil was examined by gas chromatography, and the total sulfur concentration was determined by the oxidative decomposition coulometric titration method to examine the sulfur removal rate in this distillation treatment. The results are shown in Table 1. As a result of examining the organic sulfur compounds removed by this distillation treatment by gas chromatography (FPD detector), monomethylthiophene and dimethylthiophene were the main components.

Next, in a 24-neck separable flask equipped with a stirring blade, a reflux condenser, a thermometer and a temperature controller, 1,080 g of the above-mentioned distilled treatment oil was charged, 0.2% by weight of BF ₃ / Et ₂ O catalyst, reaction temperature 45 ° C. And a slight polymerization treatment was carried out under the conditions of a reaction time of 3 hours. After the reaction was completed, 26 g of slaked lime was added and stirred, and the decomposition reaction of the catalyst was carried out at 60 ° C. for 15 minutes. afterwards,
The catalyst decomposition product and excess slaked lime are separated by filtration from the polymerized oil, and the filtrate oil is subsequently steam distilled using an experimental steam distillation apparatus until the liquid temperature reaches 220 ° C, and the solvent is removed to give a polymerized oil 21.6. got g.

With respect to the polymerized oil thus obtained, the olefin composition was examined in the same manner as above, and the total sulfur concentration was measured to examine the sulfur removal rate. The results are shown in Table 1. As a result of examining the organic sulfur compound removed by this polymerization treatment by gas chromatography (EPD detector), dimethylthiophene and trimethylthiophene were the main components.

The removal rate of the organic sulfur compound through the distillation treatment and the polymerization treatment was 93.2% by weight, and the polymerization rate of the polymerized oil was 2.0% by weight.

Example 2 The column top temperature range of the collected fraction is 108 to 112 ° C (yield 32% by weight).
Distillation under reduced pressure was carried out under the same conditions as in Example 1 except that the above was used to obtain 640 g of distilled treated oil as an intermediate fraction. Example 1
Table 1 shows the olefin composition, the total sulfur concentration and the sulfur removal rate measured in the same manner as in. As a result of examining the organic sulfur compound removed by this distillation treatment in the same manner as in Example 1, monomethylthiophene, dimethylthiophene and benzothiophene were the main components.

Next, in a 24-neck separable flask equipped with a stirring blade, a reflux condenser, a thermometer and a temperature controller was charged 640 g of the above distilled oil, and 64 g of activated clay (10% by weight).
Is added and heated with stirring in a water bath at 45 ° C.
And reacted for 3 hours. After the reaction was completed, the activated clay was separated by filtration, and the obtained filtrate was steam distilled under the same conditions as in Example 1 to remove the polymerization product and obtain 467.2 g of a polymer-treated oil. With respect to the polymerized oil thus obtained, the olefin composition was examined in the same manner as above, and the total sulfur concentration was measured to examine the sulfur removal rate. The results are shown in Table 1. The organic sulfur compound removed by this polymerization treatment was examined in the same manner as in Example 1, and as a result, trimethylthiophene was the main component.

The removal rate of the organic sulfur compound through the distillation treatment and the polymerization treatment was 99.2% by weight, and the polymerization rate of the polymerized oil was 27.0% by weight.

Example 3 A C _{8 to} C ₁₀ fraction produced during petroleum cracking was used as an original sample and charged into a 3-necked flask of 3 at 2,000, and the theoretical plate number was 1
Using a 7.8-stage batch batch vacuum distillation column, pressure 100 mmHg,
Reflux ratio (reflux / release) 7/1, collection fraction 108-112 ℃ (yield 2
Distillation under reduced pressure was carried out under the conditions of 5% by weight) to obtain 500 g of distilled treated oil as an intermediate fraction. Table 1 shows the olefin composition, the total sulfur concentration, and the sulfur removal rate, which were measured in the same manner as in Example 1. The organic sulfur compound removed by this distillation treatment was examined in the same manner as in Example 1, and as a result, monomethylthiophene and dimethylthiophene were the main components.

Then, the same polymerization treatment as in Example 2 was performed to obtain 377 g of a polymerized oil. With respect to the polymerized oil thus obtained, the olefin composition was examined in the same manner as above, and the total sulfur concentration was measured to examine the sulfur removal rate. First result
Shown in the table. The organic sulfur compound removed by this polymerization treatment was examined in the same manner as in Example 1, and as a result, trimethylthiophene was the main component.

The removal rate of the organic sulfur compound through the distillation process and the polymerization process was 97.0% by weight, and the polymerization rate of the polymerized oil was 24.6% by weight.

Reference example 3 equipped with stirring blade, reflux condenser and thermometer
1,000 g of low-sulfurized hydrocarbon oil obtained by subjecting a 4-neck separable flask to the distillation treatment and the polymerization treatment in Example 1 above.
Then, 1,000 g of toluene as a solvent and 270 g of styrene as a supplement of the styrene lost in Example 1 were charged,
BF ₃ / Et ₂ O catalyst 1.0% by weight, reaction temperature 60 ° C. and reaction time 2
The polymerization reaction was carried out under the condition of time. After the reaction, slaked lime 45g
Was added, and the catalyst was decomposed at 60 ° C. for 15 minutes while stirring. After that, the catalyst decomposition products and excess slaked lime are separated by filtration, and then the steam oil is steam-distilled using an experimental steam distiller until the liquid temperature reaches 220 ° C, and the solvent is distilled off to reduce the sulfur-containing carbonization. 900 g of hydrogen resin was obtained.

50 g of the low-sulfurized hydrocarbon resin thus obtained was dissolved in the same amount of cyclohexane, and the pressure resistance was 300 kg / c.
Prepared in a magnetic stirring autoclave with m ² and a capacity of 200 ml,
The hydrogenation reaction was carried out under the conditions of 5.0 g of stabilized nickel catalyst, hydrogen pressure of 100 to 145 kg / cm ² , reaction temperature of 220 ° C. and reaction time of 6 hours. After the reaction was completed, the nickel catalyst and the resin solution were separated by filtration, and the filtered oil was charged into a rotary evaporator,
The temperature was gradually raised to 5 mmHg at 50 ° C. and cyclohexane was distilled off under reduced pressure to obtain 40 g of hydrogenated hydrocarbon resin.

Regarding the above low-sulfurized hydrocarbon resin and hydrogenated hydrocarbon resin, the total sulfur concentration (oxidative decomposition coulometric titration method), softening point (JIS K 2531), nuclear hydrogenation rate, and weather resistance were measured, and commercially available carbonization was conducted. It was compared with hydrogen resin (trade name: Macron V-120 manufactured by Nippon Steel Chemical Co., Ltd.). The results are shown in Table 2.

Regarding the nuclear hydrogenation rate, Ar appearing at 7 ppm of ¹ H-NMR
From the area of -H spectrum, the nuclear hydrogenation rate (%) = (1-a /
b) × 100 (where a is the spectral area of the hydrogenated hydrocarbon resin and b is the spectral area of the hydrogenated raw material hydrocarbon resin), and the weather resistance is calculated based on the Helie-Gardner colorimetric Using a meter, the Gardner number of the 50 wt% toluene solution of each sample was measured before the weather resistance test, after the heat resistance test at 180 ° C. for 3 hours, and after the ultraviolet resistance test under the condition of 10 cm for 17 hours.

Comparative Example Using 50 g of a commercially available hydrocarbon resin shown in Table 2, a hydrogenation reaction was carried out under the same conditions as the hydrogenation reaction of Reference Example, but the reaction did not proceed at all.

[Effect of the Invention] According to the method of the present invention, a hydrocarbon oil containing a hydrocarbon olefin such as coumarone or indene in which 90% or more of the organic sulfur compound contained in the original sample is removed can be obtained.
It is possible to easily produce a raw material oil for producing a hydrogenated hydrocarbon resin as a base polymer, which is a light-colored improver having good heat resistance and weather resistance against an adhesive, rubber and the like.
Furthermore, coumarone, indene and the like are hydrocarbon olefins useful as raw materials for medicines and fragrances, and are extremely useful as a desulfurization refining method for these raw materials.

Claims (6)

[Claims] Claims: 1. A distillation treatment in which a hydrocarbon oil mainly composed of a fraction having a boiling point of 100 to 250 ° C and containing both an organic sulfur compound and a hydrocarbon olefin is distilled to remove a front fraction and a rear fraction. A method for desulfurizing a hydrocarbon oil, which comprises a light polymerization process in which an acid catalyst is added to the middle distillate obtained by the distillation process to carry out a light polymerization reaction. 2. A hydrocarbon oil obtained by distillation of gas light oil or coal tar produced during coal carbonization at 130 to 200 ° C.
The method for desulfurizing hydrocarbon oil according to claim 1, which is a fraction. 3. The method for desulfurizing a hydrocarbon oil according to claim 1, wherein the hydrocarbon oil is a C _{8 to} C ₁₀ fraction produced during petroleum refining or petroleum cracking. 4. The hydrocarbon olefin is vinyltoluene,
Claim 1 which is one kind or a mixture of two or more kinds selected from aromatic olefins such as coumarone and indene.
A method for desulfurizing a hydrocarbon oil according to the item. 5. The organic sulfur compound is one kind or a mixture of two kinds or more selected from thiophene, monomethylthiophene, dimethylthiophene, trimethylthiophene, benzothiophene, thiophenol, and methylthiophenol. A method for desulfurizing a hydrocarbon oil as described. 6. An acid catalyst used in a light polymerization treatment is a Bronsted acid such as sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid, boron trifluoride and its complex, a Lewis acid such as aluminum chloride, or an acid clay or an active material. A solid acid such as clay, acidic ion exchange resin, etc., wherein the amount of the acid catalyst used is 0.1 to 50% by weight, and the reaction temperature is in the range of 0 to 150 ° C. Desulfurization method.