JPS63308092A - Desulfurization of hydrocarbon oil - Google Patents

Abstract

PURPOSE:To carry out desulfurization of a hydrocarbon oil containing an organic sulfur compound as well as a hydrocarbon olefin and having a boiling point falling within a specific range, in high efficiency, by distilling the hydrocarbon oil, adding an acid catalyst to the obtained middle cut and carrying out slight polymerization reaction. CONSTITUTION:A hydrocarbon oil composed mainly of fractions having a boiling point of 100-250 deg.C, preferably 130-200 deg.C and containing an organic sulfur compound as well as a hydrocarbon olefin is distilled to remove a fore-running and an after-running. The middle cut obtained by the distillation is added with an acid catalyst and subjected to slight polymerization reaction to effect the desulfurization of the objective hydrocarbon oil. The hydrocarbon oil is preferably a 8-10C fraction produced by petroleum refining or petroleum cracking.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention is useful as a light-colored, weather-resistant modifier for paints, adhesives, rubber, etc., and/or as a hydrogenated hydrocarbon resin raw material for base polymers. The present invention relates to a method for desulfurizing and refining hydrocarbon oils that are used, and more particularly to a method for desulfurizing and refining hydrocarbon olefins that are useful as raw materials for medicines and fragrances.

[Prior Art] Conventionally, as a method for desulfurizing hydrocarbon oil, the method using element V! Hydrofining, especially hydrogenation, consisting of treating a hydrocarbon fraction with hydrogen under a wide range of elevated hydrogen pressures and temperatures in the presence of a catalytic complex containing Group and Group I metals or their compounds. There are many publications on desulfurization. In such reactions, the carbon-sulfur bonds of the molecules that make up the feedstock are broken, and the sulfur-containing moieties react with hydrogen to produce hydrogen sulfide. The resulting hydrocarbon stream is also separated from the residual mixture of hydrogen and hydrogen sulfide gas.

However, because the desulfurization reaction is carried out under high hydrogen pressure and high temperature, hydrocarbons are present in this oil and are used in hydrocarbon resins, pharmaceuticals, etc.
Olefins that are useful as raw materials for fragrances and the like also have the disadvantage of being saturated by hydrogenation.

Furthermore, when polymerizing hydrocarbon oil containing both organic sulfur compounds and hydrocarbon olefins by adding a catalyst without reducing the content of the organic sulfur compounds, the organic sulfur compounds are linked to the growing chain of the hydrocarbon olefins. A transfer reaction occurs, producing a hydrocarbon resin with a high sulfur content. Even if hydrogenation modification is attempted to improve the heat resistance and weather resistance of this resin, organic sulfur compounds act as catalyst poisons for hydrogenation catalysts such as nickel, palladium, ruthenium, and platinum, and the reaction progresses. Therefore, there is a problem that hydrogenated hydrocarbon resin cannot be produced, or even if hydrogenated hydrocarbon resin can be produced, a large amount of catalyst is required due to poisoning, which is extremely disadvantageous in terms of production cost.

Conventionally, the loss of industrially useful hydrocarbon olefins from hydrocarbon oil containing both organic sulfur compounds and hydrocarbon olefins has been prevented as much as possible, and moreover, more than 90% of the organic sulfur compounds can be contained by a simple method. I can't find any way to remove it.

[Problems to be Solved by the Invention] The present inventor conducted research in order to solve the above-mentioned problems, and developed a method for producing a hydrocarbon oil obtained by distilling a hydrocarbon oil containing both an organic sulfur compound and a hydrocarbon olefin. By adding an acid catalyst to the obtained middle distillate and performing a mild polymerization reaction, a hydrocarbon oil with less loss of industrially useful hydrocarbon olefins and from which 90% or more of organic sulfur compounds have been removed is obtained. They discovered that it is possible to do this, and completed the present invention.

Therefore, an object of the present invention is to remove organic sulfur compounds as much as possible from hydrocarbon oil containing both organic sulfur compounds and hydrocarbon olefins without losing as much hydrocarbon olefins as possible, and to reduce the sulfur content. The object of the present invention is to obtain a low-sulfur hydrocarbon oil useful as a raw material for hydrocarbon resins or olefins such as coumaron and indesi.

[Means for Solving the Problems] That is, the present invention distills a hydrocarbon oil mainly consisting of a fraction with a boiling point of 100 to 250°C and containing both an organic sulfur compound and a hydrocarbon olefin to obtain a pre-distillate. This is a method for desulfurizing hydrocarbon oil, which includes a distillation process to remove the residual oil fraction, and a light polymerization process to perform a mild polymerization reaction by adding an acid catalyst to the middle distillate obtained in the distillation process.

Hydrocarbon oils to be subjected to the desulfurization method of the present invention include, for example, gas light oil produced in coal carbonization, 130 to 200"C fraction obtained by distillation of coal tar, and produced during oil refining or oil cracking. There is a hydrocarbon oil that also contains C8-b olefins, the hydrocarbon olefins being at least 20% by weight, preferably 30% by weight.
It is desirable to contain the above amount. In addition, for saturated hydrocarbons and aromatic hydrocarbons without olefinic bonds, 2
It is desirable that the content is 0% by weight or more, preferably 30% by weight or more, and for example, when producing coumaron-indesi resin, these act as a solvent.

When the hydrocarbon olefin is vinyltoluene, coumaron, indesi, etc., sulfur-containing compounds that can be removed by distillation include those whose vapor pressure is higher than that of vinyltoluene, coumaron, indesi, etc., such as thiophene, monomethylthiophene, and dimethylthiophene. , and has a lower vapor pressure than vinyltoluene, coumaron, indesi, etc., such as benzothiophene. In addition, organic sulfur compounds that can be removed by mild polymerization using an acid catalyst include, for example, thiophene, monomethylthiophene, dimethylthiophene, trimethylthiophene, thiophenol, and methylthiophenol, which have chain transfer reactivity to hydrocarbon olefin growing chains. It has the following.

The above-mentioned distillation treatment may be performed at normal pressure or reduced pressure, but vacuum distillation is preferable in order to reduce loss of hydrocarbon olefin due to thermal polymerization. When coumaron and indesi are recovered as hydrocarbon olefins with low sulfur content through this distillation process, the top temperature range of the collected fraction in the distillation is preferably in the range of 160 to 180°C at normal pressure, and
0AllIH (in the case of 1 reduced pressure, the range is preferably 100 to 120°C.

Furthermore, in the method of the present invention, mild polymerization treatment means that the hydrocarbon olefins such as coumaron and indesi contained in the raw material hydrocarbon oil are polymerized in an amount of 40% by weight or less, preferably in the range of 10 to 30% by weight. It refers to a certain degree of polymerization within. Examples of acid catalysts used in this mild polymerization treatment include Brønsted acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid;
Examples include boron trifluoride and its complexes, Lewis acids such as aluminum chloride, and solid acids such as acid clay, activated clay, and acidic ion exchange resins. The conditions for this mild polymerization treatment vary depending on the type of hydrocarbon oil to be treated and the type of acid catalyst used, but the amount of acid catalyst used is 0.1 to 50% by weight, preferably 0. .1
-30% by weight, the reaction temperature is 0 to 150°C, preferably 0 to 100°C, and the reaction time is 0.1% by weight.
-10 hours, preferably 0.1-7 hours.

The hydrocarbon oil containing hydrocarbon olefins desulfurized by the above distillation treatment and light polymerization treatment becomes a hydrocarbon resin with a low sulfur content by polymerizing it, and this low sulfur hydrocarbon resin contains nickel, nickel, A hydrogenated hydrocarbon that is less poisonous to hydrogenation catalysts such as palladium, ruthenium, platinum, etc., can be hydrogenated in the presence of these hydrogenation catalysts, is colorless and transparent, and has good weather resistance and thermal discoloration resistance. It is extremely useful as a raw material for resin.

[Function] According to the desulfurization method of the present invention, part of the organic sulfur compounds is fractionally removed in the distillation step, and the remaining organic sulfur compounds are separated and removed as a polymerization reaction product in the light polymerization step. This makes it possible to separate and remove 90% or more of organic sulfur compounds while minimizing the loss of industrially useful hydrocarbon olefins.

There is a difference in vapor pressure between hydrocarbon olefins such as coumaron and indesi and organic sulfur compounds such as thiophene, monomethylthiophene, and dimethylthiophene, and these organic sulfur compounds can be removed by distillation. Organic sulfur compounds such as , dimethylthiophene, and trimethylthiophene have chain transfer reactivity to hydrocarbon olefin growing chains in acid-catalyzed cationic polymerization reactions, and these organic sulfur compounds are removed as products of this polymerization reaction. It is considered possible to do so.

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

Example 1 Gaseous light oil produced by coal carbonization was distilled, and 1q of the 130-200°C fraction was pickled with 40% dilute sulfuric acid. The resulting detarred base-treated hydrocarbon oil was used as an original sample, and 2.000 g of this was charged into a 3423 Tulo flask, using an experimental batch vacuum distillation column with 17.8 theoretical plates, at a pressure of 11005 t1 and a reflux ratio. Vacuum distillation was carried out under the conditions of (reflux/discharge>7/1, collected fraction 95-120°C (54 weight percent of collected fraction), and 1.080 g of distilled oil was obtained as a middle distillate.

The olefin composition of the original sample and the obtained distilled oil was investigated by gas chromatography, and the total sulfur concentration was measured by oxidative decomposition coulometric titration to investigate 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 process using gas chromatography (FPD detector), it was found that monomethylthiophene and dimethylthiophene were the main components.

Next, 1,080 g of the above distilled oil was charged into a No. 2, 04 Tulo separable flask equipped with a stirring blade, a reflux condenser, a thermometer, and a temperature controller, and BF3/Et2
A light polymerization treatment was carried out under the conditions of 0.2% by weight of catalyst, a reaction temperature of 45° C., and a reaction time of 3 hours. After the reaction was completed, 26 g of slaked lime was added and stirred to carry out a catalyst decomposition reaction at 60° C. for 15 minutes. Thereafter, the catalytic decomposition products and excess slaked lime are separated from the polymerized oil by filtration, and then the filtrate oil is steam-distilled using an experimental steam distillation device until the liquid temperature reaches 220°C, the solvent is removed, and the polymerization process is carried out. 21.6 g of oil was obtained.

Regarding 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 its sulfur removal rate. The results are shown in Table 1. As a result of examining the organic sulfur compounds removed by this polymerization treatment using gas chromatography (FPD detector), it was found that dimethylthiophene and trimethylthiophene were the main components.

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

Example 2 The top temperature range of the collected fraction was set at 108 to 112°C (yield 3
Distillation under reduced pressure was carried out under the same conditions as in Example 1, except that the concentration was 2% by weight) to obtain distilled oil 6409 as a middle distillate. Table 1 shows the olefin composition, total sulfur concentration, and sulfur removal rate measured in the same manner as in Example 1. As a result of examining the organic sulfur compounds removed by this distillation treatment in the same manner as in Example 1, it was found that monomethylthiophene, dimethylthiophene, and benzothiophene were the main compounds.

Next, 640 g of the distilled oil was charged into a 2U4 separable flask equipped with a stirring blade, a reflux condenser, a thermometer, and a temperature controller, and 64 g of activated clay (10
% by weight), heated in a water bath while stirring, and reacted at 45° C. for 3 hours. After the reaction, the activated clay was separated by filtration, and the resulting filtrate was steam distilled under the same conditions as in Example 1 to remove the polymerization product and obtain polymerized oil 467.
゜2g was obtained. Regarding 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 its sulfur removal rate. Results first
Shown in the table. As a result of examining the organic sulfur compounds removed by this polymerization treatment in the same manner as in Example 1, it was found that trimethylthiophene was the main component.

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

Example 3 The 08-C10 fraction produced during petroleum cracking was used as an original sample and the 3.1! 2.000g was charged into a 3-meter flask, and using an experimental batch vacuum distillation column with 17.8 theoretical plates, the pressure was 1007III! IMCI, reflux ratio (fast flow/
Release>7/L Collection Fraction Distillation under reduced pressure was performed under conditions of 108 to 112° C. (yield: 25% by weight) to obtain 500 y of distilled oil as a middle distillate. Table 1 shows the olefin composition, total sulfur concentration, and sulfur removal rate measured in the same manner as in Example 1. As a result of examining the organic sulfur compounds removed by this distillation treatment in the same manner as in Example 1, it was found that monomethylthiophene and dimethylthiophene were the main compounds.

Next, the same polymerization treatment as in Example 2 was performed to obtain 377 g of polymerized oil. The olefin composition of the polymerized oil thus obtained was investigated in the same manner as above, and
The total sulfur S degree was measured and the sulfur removal rate was investigated. The results are shown in Table 1. As a result of examining the organic sulfur compounds removed by this polymerization treatment in the same manner as in Example 1, it was found that trimethylthiophene was the main component.

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

Reference example 3 with stirring blade, reflux condenser and thermometer attached
, low sulfur hydrocarbon oil 1 obtained by distillation and polymerization in Example 1 above in a 114-tube separable flask.
000g, 1.000g of toluene as a solvent, and 2.0g of styrene as a replenishment valve for the styrene lost in Example 1.
70g and 1.0% by weight of BF3/Et20 catalyst
The polymerization reaction was carried out at a reaction temperature of 60° C. and a reaction time of 2 hours. After the reaction was completed, 45 g of slaked lime was added, and the catalyst was decomposed at 60° C. for 15 minutes with stirring. Thereafter, the catalytic decomposition products and excess slaked lime are separated by filtration, and then the filtrate oil is steam distilled using an experimental steam distillation device until the liquid temperature reaches 220°C, and the solvent is distilled off to produce low sulfur hydrocarbons. 900g of resin is 1q.

After dissolving 50 g of the low sulfur hydrocarbon resin obtained in this way in the same amount of cyclohexane, this was dissolved at a pressure resistance of 300
9/ci, into a 1200 d electromagnetic stirring autoclave, stabilized nickel catalyst 5.0 g, hydrogen pressure 10
The hydrogenation reaction was carried out under the conditions of 0 to 145 kg/i, reaction temperature of 220° C., and reaction time of 6 hours. After the reaction, the nickel catalyst and resin solution were separated by filtration, the filtrate oil was charged into a rotary evaporator, the temperature was gradually raised to 150°C and 5a++Hg, and cyclohexane was distilled off under reduced pressure to obtain 40 g of hydrogenated hydrocarbon resin. Ta.

Regarding the above-mentioned low sulfurized hydrocarbon resins and hydrogenated hydrocarbon resins, their total sulfur concentration <V precoulometric titration method>, softening point (J
IS K 2531), nuclear hydrogenation rate, and weather resistance were measured and compared with a commercially available hydrocarbon resin (product name: Kumaron V-120, manufactured by Nippon Steel Chemical Co., Ltd.).The results are shown in Table 2.

Regarding the nuclear hydrogenation rate, the nuclear hydrogenation rate (%) is determined from the area of the Ar-H spectrum that appears at 7 ppm in 'H-NMR.
= (1-a/b)xlOO (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 regarding weather resistance, Before the weather resistance test, after the heat resistance test at 180℃ for 3 hours, and at 10C using a Herryge Gardner colorimeter.
The Gardner number of a 50% by weight toluene solution of each sample was measured after an ultraviolet resistance test under IR conditions for 17 hours.

Table 1 upper row: 0lefin composition (GC area %) Total sulfur lower row:
Yield of original sample (wt%) (ST VT CU IN Total Removal 1 Original sample 11.0 3.4 3.1 26.9 44
．． 4 87E distilled oil 1.6 5.4 5.7 5
5.2 67.9 4627.3 82.4 96.8
100 81.3 7'.

Polymerized oil 0.7 5.6 6.0 51゜1 63
．． 4 13'.

2.7 73.5 87.1 86.2 65.3 9
S2 Original sample 13.1 3.0 3.5 30.
5 50.1 70E distilled oil 0.4 4.8 4
．． 8 68.3 78.3 18-〇, 1 50,0
42.9 11.8 48.8 9-Polymerization treated oil 0
．． 3 3.5 5.8 60.8 70.4 220, 1 26.7 31.4 44.6 31.3 9
C3 Original sample 3.4 22.5 0 15.6
41゜5 53100 100 - 100 10
0 C distilled oil 0.2 28.9 - 2
2.3 51.4 322.9 51.6 - 5
7.7 49.9 7-polymerized oil 0.1 23.
2 - 16.8 40.1 5 Table 2 # ----■ Comparative example Using 50 g of the commercially available hydrocarbon resin shown in Table 2, a hydrogenation reaction was carried out under the same conditions as the hydrogenation reaction of the reference example. However, the reaction did not proceed at all.

[Effects of the Invention] According to the method of the present invention, a hydrocarbon oil containing hydrocarbon olefins such as coumaron and indesi from which 90% or more of the organic sulfur compounds contained in the original sample have been removed can be obtained. It is possible to easily produce a raw material oil for producing hydrogenated hydrocarbon resin as a light-colored improver for rubber, etc., and good heat resistance and weather resistance, and as a base polymer. In general, coumaron, indesi, etc. are hydrocarbon olefins useful as raw materials for medicines and fragrances, and are extremely useful as a desulfurization and purification method for these raw materials.

Claims (6)

[Claims] (1) A distillation process in which a hydrocarbon oil containing mainly a fraction with a boiling point of 100 to 250°C and both an organic sulfur compound and a hydrocarbon olefin is distilled to remove a pre-distillation fraction and a post-distillation fraction, and this distillation treatment 1. A method for desulfurizing hydrocarbon oil, comprising a mild polymerization treatment in which an acid catalyst is added to the middle distillate obtained in step 1 to perform a mild polymerization reaction. (2) Hydrocarbon oil is obtained by distillation of gas light oil or coal tar produced during coal carbonization at 130-200°C.
A method for desulfurizing hydrocarbon oil according to claim 1, which is a fraction. (3) The method for desulfurizing hydrocarbon oil according to claim 1, wherein the hydrocarbon oil is a C_8 to C_1_0 fraction produced during petroleum refining or petroleum cracking. (4) The method for desulfurizing hydrocarbon oil according to claim 1, wherein the hydrocarbon olefin is one or a mixture of two or more selected from aromatic olefins such as vinyltoluene, coumaron, and indesi. (5) The organic sulfur compound is thiophene, monomethylthiophene, dimethylthiophene, trimethylthiophene,
The method for desulfurizing hydrocarbon oil according to claim 1, wherein the method is one or a mixture of two or more selected from benzothiophene, thiophenol, and methylthiophenol. (6) The acid catalyst used in the light polymerization treatment is a Brønsted acid such as sulfuric acid, phosphoric acid, hydrochloric acid, or nitric acid, a Lewis acid such as boron trifluoride and its complex, aluminum chloride, or acid clay or activated clay. Solid acids such as acidic ion exchange resins,
The method for desulfurizing hydrocarbon oil according to claim 1, 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.