JP3227521B2 - Method for recovering organic sulfur compounds from liquid oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to the production of pharmaceuticals, agricultural chemicals, heat-resistant resins, etc. from liquid oil (hereinafter referred to as mineral oil) obtained from petroleum, oil sands, oil shale, and coal liquefied oil. The present invention relates to a method for recovering a useful organic sulfur compound.

[0002]

2. Description of the Related Art It has long been known that various organic sulfur compounds are contained in liquid oil obtained from petroleum, oil sands, oil shale, and coal liquefied oil. For example, the sulfur content in fuel oil of diesel engines has recently attracted attention as one of the causes of environmental pollution, and the development of effective desulfurization technology has been urgently required. As described above, organic sulfur contained in mineral oil has been recognized as a harmful substance, and technology has been developed mainly for the purpose of removing it.

Conventionally, techniques for recovering organic sulfur compounds from industrial gas such as waste gas have been disclosed in JP-B-53-2657.
No. 7, there is a method for recovering organic sulfur compounds from the industrial gas. The method involves recovering the waste gas containing the organic sulfur compound under pressure with mineral oil and then converting the organic sulfur compound into a high-concentration gas. It is to be collected. That is, the recovery method is to wash the industrial gas containing the organic sulfur compound with mineral oil under pressure, depressurize the mineral oil that has absorbed the organic sulfur compound, and then disperse the organic sulfur compound by steam and send it to the absorption tower. While being recycled, the mixed vapor consisting of the released organic sulfur compounds, mineral oil and water vapor is condensed and separated into an oil layer and an aqueous layer, and the gas generated during depressurization is brought into contact with the oil layer to achieve high concentration. To obtain a gas containing an organic sulfur compound.

[0004]

However, the organic and sulfur compounds contained in mineral oil are very similar in physical and chemical properties to the mineral oil itself, and are generally used for distillation and solvent extraction. Means for efficient separation and purification are not effective.
At present, high temperature,
The mainstream technology is to use a catalyst to react with hydrogen gas under violent reaction conditions of high pressure to convert organic sulfur compounds into toxic hydrogen sulfide and separate it. As much as possible, the organic sulfur compound is kept in its original chemical structure,
Such hydrogen reduction desulfurization cannot be applied to take out the organic sulfur compound from the mineral oil and use it effectively.

Conventionally, Japanese Patent Publication No. 53-26577 discloses a method for recovering an organic sulfur compound from waste gas. However, this method does not recover an organic sulfur compound from mineral oil.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to remove an organic sulfur compound from a mineral oil while maintaining the original chemical structure contained in the mineral oil as much as possible. An object of the present invention is to provide a method for easily and economically recovering an organic sulfur compound from a mineral oil by using an oxidizing agent to separate the organic sulfur compound in an oxidized state by distillation or the like.

According to the present invention, a liquid oil containing an organic sulfur compound obtained from petroleum, oil sand, oil shale and coal is treated with an oxidizing agent to convert the organic sulfur compound into a sulfoxide compound and / or a sulfone compound. Separating the sulphoxide compound and / or the sulphone compound as the oxidized organic sulfur compound from the liquid oil by separation by means of distillation, solvent extraction and / or adsorption. The present invention relates to a method for recovering a sulfur compound.

[0008] Since this method for recovering an organic sulfur compound is constituted as described above, a liquid oil, that is, a mineral oil is pre-treated with various oxidizing agents to oxidize the organic sulfur compound while maintaining its molecular skeleton substantially. Of industrially useful organic sulfur compounds from mineral oils efficiently, easily and at low cost by utilizing the changes in physical, chemical properties such as molecular polarity, boiling point, melting point, etc. of the resulting molecules. It is to be collected.

The method for recovering organic sulfur compounds is as follows.
An organic sulfur compound consisting of divalent valent sulfur atoms contained in mineral oil is reacted with various oxidizing agents having different oxidizing powers to convert it into a sulfoxide compound and / or a sulfone compound. Next, the chemical product is separated from other components by utilizing the change in the chemical and physical properties of the reaction product generated by the chemical conversion. For example, if the fact that the boiling point is significantly increased is used, these can be easily separated and purified by a distillation operation. Selective extraction of organic sulfur compounds,
It becomes possible to purify.

[0010] Furthermore, the above-mentioned change in chemical properties significantly improves the adsorbing power to an adsorbent such as silica gel or alumina, so that adsorption, separation and purification using the adsorbent can be performed extremely efficiently and easily. Will be able to do it.
Further, a more preferable result can be obtained by performing the treatment in combination with the above separation and purification methods.

Further, the method for recovering an organic sulfur compound from liquid oil according to the present invention utilizes the difference in reactivity of the organic sulfur compound in mineral oil itself to the oxidation reaction,
It is possible to carry out the reaction while appropriately selecting an oxidizing agent, and to selectively take out only a specific organic sulfur compound group. That is, when an oxidizing agent capable of selectively oxidizing an organic sulfur compound containing a divalent sulfur atom only to a sulfoxide compound is used, the extracted organic sulfur compound is obtained in the form of a sulfoxide, and is further converted to a sulfone compound. If an oxidizing agent having the ability to oxidize to the maximum is used, it can be obtained in the form of sulfone. In addition, by utilizing the property that the reactivity changes significantly due to steric hindrance based on the structural change in the organic sulfur compound molecule, a special group of organic sulfur compounds having these steric hindrances can be obtained by selectively using the reactivity of the oxidizing agent. Can be selectively extracted.

In the method for recovering an organic sulfur compound from a liquid oil according to the present invention, the mineral oil containing the organic sulfur compound may be a crude oil, an oil shale, an oil sand, a coal tar, a liquefied oil of coal, or a liquefied oil thereof. From naphtha, gasoline, kerosene, light oil, heavy oil, pitch or indirect oil refined products obtained by chemically decomposing them.

In the method for recovering an organic sulfur compound from a liquid oil according to the present invention, the oxidizing agent may be oxygen gas, air, nitrogen tetroxide gas, ozone gas, chlorine gas, bromine, sodium metaperiodate, heavy hydrogen, Potassium chromate, potassium permanganate, chromic anhydride, hypochlorous acid, hydrogen peroxide, peracetic acid, mixture of hydrogen peroxide and acetic acid, formic acid, mixture of hydrogen peroxide and formic acid, metachloroperbenzoic acid Mixture of hydrogen peroxide and metachlorobenzoic acid, perchloroacetic acid, mixture of hydrogen peroxide and chloroacetic acid, perdichloroacetic acid, mixture of hydrogen peroxide and dichloroacetic acid, pertrichloroacetic acid, hydrogen peroxide and trichloroacetic acid A mixture of acetic acid, pertrifluoroacetic acid, a mixture of aqueous hydrogen peroxide and trifluoroacetic acid, a mixture of aqueous methanesulfonic acid, aqueous hydrogen peroxide and methanesulfonic acid Things, can be used those selected from persulfate, mixture of hydrogen peroxide and sulfuric acid.

The method for recovering an organic sulfur compound from a liquid oil according to the present invention comprises reacting a mineral oil with an organic peracid oxidizing agent or an inorganic oxidizing agent while stirring at a temperature of 0 to 100 ° C. Then, the oil containing the oxidation reaction product is removed,
Water is added to this, and after washing | cleaning and drying, the produced organic sulfur oxide can be collect | recovered from mineral oil.

Alternatively, the method of recovering an organic sulfur compound from a liquid oil according to the present invention is a method of treating a mineral oil with an oxidizing agent and then acetonitrile, propionitrile, butyronitrile, nitromethane, nitroethane, nitropropane, nitrobenzene, dimethyl. Sulfoxide, N, N '
-Dimethylformamide, N, N'-dimethylacetamide, N-methylpyrrolidinone, trimethyl phosphate, triethyl phosphate, hexamethyl phosphoramide, or phosphorane, or in a concentration range of 0 to 50% based on these solvents. By performing an extraction operation using an extract selected from a mixture containing water as an extraction solvent, the generated organic sulfur oxides can be recovered from the mineral oil.

Alternatively, the method of recovering an organic sulfur compound from a liquid oil according to the present invention comprises treating a mineral oil with an oxidizing agent and then activating clay, silica gel, alumina or
Once the organic sulfur oxide produced by passing through an adsorption tower filled with an adsorbent selected from these mixtures is adsorbed, methanol, ethanol, propanol, butanol, acetone, acetonitrile, nitromethane, or a mixture thereof The organic sulfur oxide can be recovered from the mineral oil by desorption and separation with a solvent selected from the group consisting of:

Further, a method for recovering an organic sulfur compound from the liquid oil is to react a mineral oil fraction distilled in a boiling point range as narrow as possible using a precision distillation column with an oxidizing agent.
The oil containing the oxidation reaction product is removed, washed with water, dried, and then distilled again in the same boiling point range as the mineral oil before being treated with the oxidizing agent. Is concentrated and separated.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a method for recovering an organic sulfur compound from a liquid oil according to the present invention will be described.

(Example 1) 2 with a homogenizer stirrer, a reflux condenser and a gas inlet tube
Light oil (boiling range 220-300 ° C, flammable sulfur content 0.53% by weight)
0 ml is cooled to 0 ° C., and stirring is performed for 1 hour while passing air containing ozone (about 1.0%). Then, after stopping the ozone and passing only air for another hour, stirring is continued for another hour while gradually raising the temperature of the entire flask to 20 ° C. The obtained reaction solution was washed by adding 50 ml of a 2N aqueous solution of sodium sulfite, and further washed with water. The light oil layer and the tar layer were separated, and the light oil layer was distilled with a precision distillation apparatus to give a boiling point of 220 to 330 ° C. 92 ml of distillate and 8 ml of distillation residue are obtained. The sulfur content in the distillate is 0.32%
The main components are benzothiophene and dibenzothiophene derivatives, and the total sulfur content in the distillation residue and tar content is 1.7% and 7.8%, respectively, and the main components are their oxidation products, ie, , Sulfoxide, and sulfone.

(Example 2) Light oil (boiling point range: 220 to 300) was placed in a 200 ml hard glass round bottom flask equipped with a homogenizer stirrer and a reflux condenser.
Temperature, flammable sulfur content 0.53% by weight)
10 ml of hydrogen peroxide (30%) and 10 ml of formic acid
And stirred at 20 ° C for 1 hour.
And continue stirring for an additional hour. After the reaction, the reaction mixture was cooled to 0 ° C. and allowed to stand. The tar component and the gas oil layer were separated, washed with a 2N aqueous sodium sulfite solution, and further washed with water. 220-33
86 ml of a 0 ° C. distillate and 12 ml of distillation residue are obtained. The sulfur content in the distillate is 0.04%, and the main components are benzothiophene and dibenzothiophene derivatives. The total sulfur content in the distillation residue and tar content is 2.1% and 8.4%, respectively. The main component was a mixture of their oxidation products, namely sulfoxides and sulfones.

(Example 3) Light oil (boiling point range: 220 to 300) was placed in a 200 ml hard glass round bottom flask equipped with a homogenizer stirrer and a reflux condenser.
Temperature, flammable sulfur content 0.53% by weight)
10 ml of aqueous hydrogen peroxide (30%) and 10 ml of dichloroacetic acid are added thereto, and the mixture is stirred at 40 ° C. for 1 hour. Then, the reaction temperature is raised to 70 ° C., and stirring is further continued for 1 hour. After the reaction,
Cool to 0 ° C and separate tar and light oil layer. After washing with a 2N aqueous sodium sulfite solution and further washing with water, the light oil layer was separated again, and 10 ml of nitromethane was added thereto.
And vigorously stirred at room temperature for 1 hour, then stand still, and separate the gas oil layer and the nitromethane layer. The sulfur content in the gas oil reservoir is
At 0.03%, the main components are benzothiophene and dibenzothiophene derivatives, and the total sulfur content in the nitromethane solution and tar content is 0.21% and 6.5%, respectively.
The main component was a mixture of their oxidation products, ie, sulfoxide and sulfone.

Example 4 100 ml of heavy oil (flammable sulfur content: 1.87% by weight) was placed in a 200 ml hard glass round bottom flask equipped with a homogenizer stirrer and a reflux condenser, and hydrogen peroxide (30%) was added thereto.
%) And 10 ml of formic acid, and the mixture is stirred at 30 ° C. for 1 hour. Then, the reaction temperature is raised to 50 ° C., and stirring is further continued for 1 hour. After the reaction, the upper layer separated into two layers was separated with a separating funnel, washed with a 2N aqueous sodium sulfite solution, further washed with water, and then the heavy oil layer was separated again, and 10%
N, N'-dimethylformamide solution containing water
0 ml is added, the mixture is vigorously stirred at room temperature for 1 hour, and then allowed to stand. Then, the heavy oil layer and the N, N'-dimethylformamide layer containing 10% water are separated. The sulfur content in the heavy oil reservoir is
At 0.21%, the main components are benzothiophene and dibenzothiophene derivatives, and the total sulfur content in the N, N'-dimethylformamide solution and tar component is 1.10%, respectively.
At 60%, the main component was a mixture of their oxidation products, namely sulfoxide, sulfone.

(Example 5) With homogenizer stirrer, reflux condenser, gas inlet tube 2
100 ml of heavy oil (flammable sulfur content: 1.87% by weight) and 20 ml of distilled water are placed in a 00 ml hard glass round bottom flask, and the mixture is stirred and reacted at 0 ° C. for 1 hour while bubbling chlorine gas. After the reaction, the heavy oil layer was separated with a separating funnel, washed with a 2N aqueous sodium sulfite solution, and further washed with water. Then, the heavy oil layer was separated, and 5 ml of a 10% water-containing trimethyl phosphate solution was added thereto. And vigorously stirred at room temperature for 2 hours, and then allowed to stand, and separated into a layer of mineral oil and a layer of trimethyl phosphate containing 10% water.
The sulfur content in the heavy oil layer is 0.35% each, and the main components are benzothiophene and dibenzothiophene derivatives. The total sulfur content in the trimethyl phosphate solution is 1.53%, respectively. Their oxidation products,
That is, it was a mixture of sulfoxide and sulfone.

Example 6 In a 200 ml hard glass round bottom flask equipped with a homogenizer stirrer and a reflux condenser, 50 g of coal tar (combustible sulfur content: 0.67% by weight) and benzene 10 as a viscosity reducing agent were used.
Then, 5 ml of aqueous hydrogen peroxide (30%) and 10 ml of formic acid are added thereto, and the mixture is reacted at 40 ° C. for 3 hours while stirring. After the reaction, the coal tar layer was separated and washed with a 2N aqueous sodium sulfite solution. Then, the coal tar layer was separated, and 100 ml of a 10% water-containing N-methylpyridinone solution was added thereto. The mixture is stirred vigorously for a period of time and then allowed to stand, and separated into a coal tar layer and an N-methylpyridinone layer. The sulfur content in the N-methylpyridinone solution was 0.25%, and the main component was an oxidation product of benzothiophene and a dibenzothiophene derivative, that is, a mixture of sulfoxide and sulfone.

(Example 7) Light oil (boiling point range: 220 to 300) was placed in a 200 ml hard glass round bottom flask equipped with a homogenizer stirrer and a reflux condenser.
Temperature, flammable sulfur content 0.53% by weight)
After adding 10 ml of acetonitrile, 10 ml of water and 5 g of sodium periodate, and stirring vigorously at 20 ° C. for 1 hour,
The reaction temperature is raised to 50 ° C. and stirring is continued for another hour.
After the reaction, the light oil layer was separated and washed with water.
The mixture is passed through a column filled with an adsorbent obtained by mixing 0 g and 10 g of silica gel. The sulfur content in the obtained light oil was 0.0
5%. On the other hand, acetone 50ml
The sulfur content in the solution obtained through was 0.44%. The main components in the gas oil were benzothiophene and dibenzothiophene derivatives, and the main component of the sulfur content in the acetone solution was a mixture of their oxidation products, ie, sulfoxide and sulfone.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C10G 21/00 C10G 21/00 25/00 25/00 27/00 27/00 (58) Fields surveyed (Int.Cl. ⁷ , DB name) C07B 63/02 C07C 303/42 C07C 315/06 C07C 319/26 C10G 7/00 C10G 21/00 C10G 25/00 C10G 27/00

Claims (1)

(57) [Claims] 1. A liquid oil containing an organic sulfur compound obtained from petroleum, oil sand, oil shale, and coal is treated with an oxidizing agent to sulfoxide the organic sulfur compound.
Compound and / or a sulfone compound , which is separated by means of distillation, solvent extraction and / or adsorption to obtain the oxidized organic sulfur compound , the sulfoxide compound and / or
A method for recovering an organic sulfur compound from a liquid oil , comprising separating and recovering a sulfone compound from the liquid oil.