CN1331987C - Oxidation and desulfurization method of petroleum oil product - Google Patents

Abstract

The present invention relates to a method for desulfurizing petroleum products. The present invention characterized in that the present invention adopts a high shear dispersed emulsification technique to strengthen the reaction of a petroleum product and an oxidizing agent, and the organic sulfur compounds in the petroleum product are oxygenized into sulfone; then the oxygenized petroleum product is treated by an extraction method, or an adsorption method or a reaction with the hydroxides of alkali metal or alkaline earth metal at a certain temperature, and thereby, the purpose of desulfurization is realized. The present invention is suitable for the petroleum products, such as kerosene, diesel oil (comprising straight-run diesel oil and catalyzed diesel oil), vacuum gas oil (VGO), atmospheric residuum, vacuum residuum and crude oil.

Description

Method for Oxidative Desulfurization of Petroleum Oil Products

technical field

The invention belongs to the field of petrochemical industry, and relates to a method for oxidative desulfurization of petroleum oil products, in particular to a technology for enhancing the oxidation effect of organic sulfides in petroleum oil products and improving desulfurization efficiency by using high-speed shear dispersion and emulsification technology.

Background technique

Oxidative desulfurization method is a process for removing sulfides in petroleum oil products in the field of petrochemical industry. This method mainly oxidizes the sulfides in oil products into sulfones with strong polarity through oxidation reaction, and then through post-treatment The technology separates the sulfone in the oil, so as to achieve the purpose of desulfurization of petroleum oil.

Oil desulfurization technology has been extensively studied and applied in the petrochemical industry. Because the desulfurization effect directly affects the quality and use value of oil products, the highest possible desulfurization rate is an important indicator pursued by the industry. In order to obtain a higher desulfurization rate, most of the research methods that have been implemented or reported at present focus on improving the oxidation effect and effectively separating sulfur-containing substances from oil products. The analysis and research of these prior technologies can be found in It is pointed out that people mainly focus on the research of oxidation process, including the selection of oxidant or catalyst, and various post-treatment methods are proposed at the same time.

US Patent No. 6,500,219 (2002) discloses a method for oxidative desulfurization of liquid mineral oil using ultrasonic waves. The method comprises the steps of: (a) reacting liquid mineral oil with peroxide, surfactant and aqueous solution to form an oil-water two-phase reaction medium; (b) passing the above reaction medium continuously through an ultrasonic generating chamber for a time sufficient to make the above mineral The sulfide in the oil is oxidized into sulfone; (c) the reaction oil flowing out from the ultrasonic generating chamber is immediately divided into a water phase containing a large amount of sulfide and an oil phase containing part of the sulfide; (d) the oil phase is treated with adsorption or extraction method for further desulfurization. The surfactant used in the method is aliphatic hydrocarbons containing 15-20 carbon atoms, and the use of an ultrasonic generating chamber is used to achieve the purpose of improving the oxidation efficiency of sulfide in mineral oil.

U.S. Patent No. 6,402,939 (2002) also discloses a method for oxidative desulfurization of mineral oil using ultrasonic waves. Phase reaction medium, the pH value of the acidic aqueous solution of the above-mentioned peroxide is equal to the pH value of the hydrogen peroxide aqueous solution of 1～30v%; Oxidation to sulfone; (c) extraction of the above sulfone to obtain an organic phase substantially free of sulfone. The method particularly includes the use of a halide quaternary ammonium salt cationic phase transfer agent combined with mineral oil and acidic peroxide solution to form a heterogeneous reaction medium for the purpose of promoting oxidation.

The use of ultrasonic technology to realize the oxidation of oil, theoretically speaking, is conducive to the full contact of materials to oxidize all the sulfides in the oil into sulfones. However, the implementation of ultrasonic technology in industrial production is difficult and will bring high costs. It can also be seen from the above disclosure that the use of ultrasonic technology also requires the cooperation of emulsification and phase transfer technologies.

US Patent No. 6,406,616 (2002) discloses a method for oxidative desulfurization of gasoline using hydrogen peroxide as an oxidant and formic acid as a catalyst. The process is that the sulfur-containing liquid oil is mixed with the water phase carrying the oxidant and the catalyst in the reactor, and the thiophene sulfur-containing compounds are oxidized to sulfones under the conditions of close to normal pressure and a very mild temperature (less than 120°C); The water phase of the catalyst and sulfone is separated from the oil phase and sent to the regeneration system to remove the sulfone and regenerate the catalyst; the oil phase containing sulfone is sent to the adsorption system, which contains a solid adsorbent that can be regenerated with methanol.

French patent FR2802939 (2001) discloses a selective desulfurization process for thiophene compounds contained in hydrocarbons derived from crude oil. By using a turbulent hydrocarbon/water two-phase system containing an oxidant, the sulfur atoms in the thiophene compounds are oxidized into sulfones , the oxidizing agent is a peroxide or persulfate selected from hydrogen peroxide, organic peroxides, persalts and persulfates of alkali metals or alkaline earth metals. It is also recorded that the desulfurization process can be applied to the desulfurization of gasoline, kerosene and petroleum fractions derived from catalytic cracking process.

However, these methods are mainly applicable to the oxidation treatment of thiophene and thiophene compounds in oil products. FR2802939 only mentions that the turbulent hydrocarbon/water two-phase system should be applied, and there is no specific record on how to achieve the turbulent state in the processing of oil products. Therefore, for systems with different properties, the conditions and operations for realizing turbulent flow have different requirements, and reaching the turbulent state is a very broad description. The system changes and the specific shape of the turbulent state has different effects on the system.

Japanese Patent JP2001354978 (2001) discloses an oxidative desulfurization process for fuel oil, which records that fuel oil containing sulfur compounds is treated with an oxidant and a transition metal catalyst in the presence of a polar organic solvent to remove sulfur compounds.

US Patent US6277271 (2001) discloses an oxidative desulfurization method. The method comprises the following steps: (a) desulfurizing the fuel oil by catalytic hydrogenation to initially reduce the sulfur content in the oil product; (b) oxidizing the above oil product with an oxidizing agent to obtain the oxidized oil and the remaining oxidizing agent mixture; (c) separating off the remaining oxidant and desulfurizing the oxidized oil by extraction, distillation or adsorption. The above-mentioned oxidizing agent can be oxygen, ozone, hydrogen peroxide, organic peroxide, metal superoxide.

U.S. Patent No. 5,961,820 (1999) discloses a desulfurization process using oxidants, carbonyl compounds and hydroxides. The process is used to remove sulfides in petroleum fractions and coal. The oxidant used is hydrogen peroxide, and the carbonyl compounds are ketones. Compounds, such as acetone, etc., the hydroxide is an alkali metal hydroxide. In this process, sulfur-containing petroleum fractions or mixtures of coal, hydrogen peroxide, acetone and sodium hydroxide are reacted at a temperature range from room temperature to 121 ° C, and the reaction pressure is 1 to 2 atmospheres. After the reaction is completed, after desulfurization Petroleum distillates or coal, and recovery of ketones.

U.S. Patent No. 5,935,421 (1999) discloses the research of desulfurizing heavy oil with sodium hydroxide. The reaction steps are: 1. heavy oil is mixed with aqueous sodium hydroxide solution (concentration 5m%-60m%), hydrogen gas is passed, and the desulfurization process is carried out at high temperature. (380°C-450°C) to react to generate partially desulfurized heavy oil, water and sodium sulfide; ②Convert sodium sulfide into sodium hydroxide through stripping process and recover hydrogen sulfide; ③Recycle the recovered sodium hydroxide;④ Partially desulfurized heavy oil is reacted with metallic sodium under anhydrous, anaerobic high temperature (340°C-450°C) and high pressure (345Kpa) to generate final desulfurized oil and sodium sulfide.

US Patent No. 5,958,224 (1999) discloses a method for oxidative desulfurization of oil after hydrotreating. The method comprises the following steps: (a) using a metal peroxide compound as an oxidant to oxidize the hydrotreated oil; (b) desulfurizing the oxidized oil by means of adsorption; (c) using hydrogen peroxide to The above oxidants are regenerated and recycled. The metal peroxide compound used is LMO(O ₂ ) ₂ , LMO(O ₂ ) ₂ .2H ₂ O or a mixture thereof, L is an alkyl phosphoric triamide, and M is nickel, chromium or tungsten.

US Patent No. 5,310,479 (1994) discloses a method for oxidative desulfurization of sulfide sulfides in crude oil. The method is to mix and react crude oil with formic acid and peroxide. After the reaction, the sulfide sulfides in the crude oil are oxidized to water-soluble sulfides, and the crude oil is washed with water to obtain desulfurized oil.

EP0565324 (1993) discloses the method for reclaiming organosulfur compounds from liquid oil products, comprising: (a) treating oil products derived from petroleum, oil sands, shale oil or coal with a kind of oxidizing agent, the oxidation reaction is at -20～ Carried out at 140°C, the oxidant is selected from oxygen, air, ozone, chlorine, H ₂ O ₂ , peracetic acid, a mixture of H ₂ O ₂ and water, performic acid, a mixture of H ₂ O ₂ and performic acid, perbenzoic acid, H _2O2 mixture with chloroacetic acid, dichloroperacetic acid, _H2O2 mixture with water and dichloroperacetic acid, trichloroperacetic acid, mixture _{of H2O2} and _{trichloroacetic} acid, _{trifluoroperacetic} acid, H ₂ O ₂ and trifluoroacetic acid mixture, permethanesulfonic acid, H ₂ O ₂ and methanesulfonic acid mixture, hypochlorous acid, hypochlorite aqueous solution, etc.; (b) separation of oxidized Organic sulfur compounds, or adsorption to isolate them from oil. In this method, the recovered organosulfur compounds are mainly sulfoxides and/or sulfones.

JP04072387 (1992) discloses a fuel oil desulfurization process. The process uses an oxidant to treat fuel oil derived from petroleum, coal liquefied oil, gasoline, kerosene, light oil and heavy oil. The oxidant is oxygen, ozone and organic peroxides. Fuel oil can be directly oxidized or reoxidized in a mixture with an organic solvent such as acetone. Oxidized sulfur compounds can be easily removed by distillation due to the increase in boiling point, and can also be removed by using solvent extraction, deep freezing separation and chromatographic column separation techniques by taking advantage of the changed solubility and melting point of organic sulfur compounds.

US Patent No. 3,945,914 (1976) discloses a method for oxidative desulfurization of heavy oil. The method comprises the following steps: (a) mixing and reacting heavy oil with an oxidizing agent; (b) reacting the oxidized oil product with a metal or a compound containing the metal at high temperature to generate a compound containing metal and sulfur; (c) The sulfur-containing compounds are separated to obtain a desulfurized product oil. The above-mentioned peroxides are selected from organic peroxides, hydrogen peroxides, organic peroxyacids; the above-mentioned metals are cobalt, molybdenum, tungsten, nickel, titanium and the like.

US3719589 (1973) discloses a kind of technology of producing the hydrocarbon oil of low sulfur content, and this technology comprises: under the temperature about 23.9～93.3 ℃, oxidizes the hydrocarbon oil containing sulfur and asphalt with oxidizing agent, and oxidizing agent is selected from organic peroxide, Organic peracid, by heating the oxidized product to about 65.6-232.2°C, and maintaining the heated hydrocarbon oil at a fixed temperature range of about 148.9-260°C, removing the residual oxidant, and obtaining the upper layer as a hydrocarbon oil with reduced sulfur content , the lower layer contains a mixture of bitumen, separating the upper and lower layers.

US3668117 (1972) discloses the desulfurization method of sulfur-containing oil, the sulfur-containing oil is peroxidized with a kind of oxidizing agent earlier, then, the water of 1-20wt% is joined in the oil after peroxidation, makes above-mentioned water-containing oil The sulfur in the oil is removed through a desulfurization catalyst, the above desulfurization catalyst is selected from the group consisting of sodium oxide, potassium oxide or calcium oxide supported on alumina. The oxidizing agent is selected from organic oxides, organic peroxides, air or organic peracids.

After careful study, it can be found that in the prior art listed above, in order to improve the desulfurization rate, a lot of research has been done on the selection of reaction conditions and reagents (including catalysts). The operating conditions of the oil product design, or need to use a large number of oxidants and high-cost catalysts and special reagents (such as phase transfer agents), some oxidants or catalysts, especially the industrial regeneration of macromolecular catalysts, have high costs and large pollution, so it is not suitable industrial applications. Generally speaking, there are unsatisfactory places in desulfurization rate and production cost.

Therefore, finding and exploring a desulfurization method with wider application range, simple operation and higher comprehensive efficiency has obvious economic and social significance for the development of this technical field, especially for promoting the industrialization of desulfurization technology.

Contents of the invention

The purpose of the present invention is to provide a method for desulfurization of petroleum oils, which improves the oxidation efficiency of sulfides by introducing high-shear dispersion emulsification technology, so as to achieve the purposes of wide applicability, high desulfurization rate and low production cost.

The invention provides a method for oxidative desulfurization of petroleum oils, which includes oxidizing organic sulfides in petroleum oils (mainly generating sulfones or sulfoxides), and separating the generated oxidation products from the oils The process is characterized in that the oxidation reaction is completed under the action of a high-shear dispersion emulsification device, the oxidation reaction is completed under the action of a high-shear dispersion emulsification device, the reaction temperature is 30-110 °C, and the reaction pressure is normal pressure to 1Mpa, the reaction time is 1-180 minutes; the peripheral speed of the rotor of the high-shear dispersing and emulsifying device is 3m/s-50m/s.

The inventor of this case combined the research results of the prior art to explore the desulfurization technology and found that one of the keys to improving the desulfurization effect is to try to improve the efficiency of the oxidation reaction of sulfide in oil products. Therefore, a large number of prior art researches have focused on In the choice of oxidizing agent and catalyst. In the operation, it is also limited to make the raw material oil be oxidized under the condition of sufficient stirring. Due to the difference in the properties of various oil products and the high viscosity of petroleum oil products, the real full contact between the oil product and the oxidant in the oxidation reaction is It is more difficult, that is to say, making the oxidant fully dispersed in the oil is of great significance to the effect of the oxidation reaction.

Before the present invention, high-shear force dispersion emulsification technology was usually applied to the emulsification process of materials. The research results of the inventors of this case show that the oil product to be oxidized is subjected to high shear force to disperse and emulsify, so that the oil During the oxidation process, the product is always under the action of high shear force and keeps in full contact with the oxidant, or the oxidant is highly dispersed in the oil to be treated, and at the same time, under the action of high shear force, it is beneficial to the vulcanization in the oil oxidation of substances.

The research of the inventors shows that in order for the oil to meet the high-shear dispersion and emulsification effect required by the present invention in the oxidation reaction, the rotor of the high-shear dispersion and emulsification device used should have a relatively high peripheral speed. The high-shear emulsifying disperser consists of a stator and a rotor. For the device applicable to the present invention, the circumferential speed of the rotor is required to be 3m/s-50m/s. The emulsifiers that can realize the requirements of the peripheral line speed are generally suitable for the present invention. The specific high-shear dispersion emulsification device can have multiple options, and the stator diameter can be selected to be 6-50mm in operation. Correspondingly, the oxidation process can be The rotational speed of the rotor of the high-shear dispersing and emulsifying device is controlled to be 600-30000 rpm. In order to obtain a better oxidation effect, the rotation speed can be 8000-30000rpm, for example, the FA25/22Z high-shear dispersing and emulsifying machine produced by Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd. can be used. According to the different oil products to be processed, it can be adjusted and controlled at an appropriate speed, and the more suitable speed is 12000-25000rpm.

The petroleum oil products applicable to the present invention include various intermediate products and final products derived from petroleum, such as kerosene, diesel oil (including straight-run diesel oil and catalytic diesel oil), vacuum distillate oil (VGO), atmospheric residue, vacuum residual oil and crude oil.

According to the oil desulfurization method provided by the present invention, in the state of high-shear dispersion emulsification, the oxidizing agent and the catalyst mixture produce strong oxidation, and the organic sulfur compound in the oil can be oxidized into sulfone or sulfoxide. After the oxidation reaction is finished, the sulfone sulfides in the oil can be separated by extraction, adsorption or alkali treatment. The oxidizing agent for oil product oxidation reaction can be various oxidizing agents commonly used in the prior art, such as hydrogen peroxide and the like. In a specific application, the concentration of hydrogen peroxide may be 1-30m%, and a more suitable concentration is 15-30m%. The amount of oxidant used is related to the oil to be treated and the amount of sulfide contained therein, and can be determined by those skilled in the art. Usually, the volume ratio of oxidant to oil can be controlled to be 1:500-3:10.

The oil product desulfurization method of the present invention has no special requirements for the catalyst of the oxidation reaction, and conventional or known ones can be used. Considering the oxidation effect and the catalyst regeneration in the industrial process, it is preferred to use small molecule substances. For example, the applicable catalyst can be selected from From formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, m-chlorobenzoic acid, phosphotungstic acid and phosphomolybdic acid, etc. According to the method of the present invention, more suitable catalysts can be formic acid, trichloroacetic acid, trifluoroacetic acid and the like. The volume ratio of oxidant and catalyst in the oxidation process is 1:20-20:1, and the more suitable volume ratio is 1:5-5:1.

According to the method of the present invention, after the oxidation reaction is completed, any known method can be used to separate the oxidized sulfides (mainly sulfones or sulfoxides) from the oil. The preferred separation method of the present invention can use extraction, adsorption, alkali treatment or a combination of more than one of these steps to separate the sulfone from the oxidation product from the oil.

The extraction step is to mix the oxidized product with the extractant and then stand still at room temperature, then separate the oil product from the extractant layer, and collect the oil product, which can be the product after desulfurization. The extractant can be selected from acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), N-methylpyrrolidone, sulfolane, nitromethane, diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol (TETRA), diethylene glycol amine (DGA), N-formyl morpholine, methanol, ethanol, formaldehyde, acetaldehyde, formic acid or acetic acid, etc. A more suitable extractant is acetonitrile, dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), methanol, ethanol, formaldehyde, acetaldehyde, formic acid or acetic acid, etc.

The amount of extraction agent added and the number of extractions are not strictly limited, and can be determined according to the specific conditions of the oil product. In general, the volume ratio of the oil product to the extraction agent in each extraction operation can be 1:10 to 4:1, which is more suitable The volume ratio is 1:2 to 2:1.

The adsorption step is to contact the oxidation reaction product with a solid adsorbent, the space velocity of the process is 0.1-2.0h ^-1 , and the temperature is 20-90°C. The sulfide in the oil is adsorbed on the adsorbent to remove the sulfide in the oil. The adsorbent can be regenerated with methanol, ethanol, chloroform, carbon tetrachloride, benzene, toluene or their mixture. The solid adsorbent used can be selected from layered molecular sieves, MCM-41 molecular sieves, activated carbon, alumina, silica gel or titanium silicon oxide, etc., and the more suitable adsorbents are silica gel and titanium silicon oxide.

According to the method of the present invention, an alkali treatment method can also be used to remove sulfones in the oil: the oxidized oil is mixed with hydroxides of alkali metals or hydroxides of alkaline earth metals and heated at 70-350°C React for 30 to 180 minutes to break the C-S bond of the sulfone in the oil, and remove the sulfur in the form of inorganic salts such as sulfate, so as to achieve the purpose of desulfurization. The hydroxide of alkali metal or the hydroxide of alkaline earth metal used can comprise sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and their mixture, and above-mentioned hydroxide can be solid, also can be their of aqueous solution. Generally, sodium hydroxide or potassium hydroxide can be used. After the whole reaction is finished, the sulfates generated by the reaction are stored at the bottom of the reactor, and the petroleum oil is easily separated from the sulfates.

According to the needs of the use and properties of the oil, the above methods can be used repeatedly during the separation process, or more than one method can be used in combination.

According to the above description, it can be concluded that compared with the known technology, the key to the oxidative desulfurization method of petroleum oil provided by the present invention is to control the conditions and states of the oxidation reaction of the oil, so that the oil can achieve sufficient desulfurization under the action of high shear force. Dispersion and emulsification, in such an environment, the oxidation of the contained sulfide has a high selectivity, so it can be concluded that it has the following significant effects:

1. The oxidative desulfurization method for petroleum oil products of the present invention has a wide range of applications, especially for various high-sulfur oil products such as kerosene, diesel oil (including straight-run diesel oil and catalytic diesel oil), vacuum distillate oil (VGO), atmospheric residue , Desulfurization of vacuum residue and crude oil.

2. The petroleum oil oxidation desulfurization method provided by the present invention is simple and easy to operate. The requirements for oxidants and catalysts are low, and ordinary small molecules can meet the requirements, and the production cost is relatively low, which is more conducive to industrialization.

3. Low cost and high desulfurization rate. For example, the sulfur content of diesel oil can be reduced from 2742 μg/g to below 87 μg/g, and the desulfurization rate is as high as 96.8%; the sulfur content of vacuum distillate oil (VGO) can be reduced from 10087 μg/g down to 916μg/g, the desulfurization rate is as high as 90.9%.

4. The method of the present invention treats petroleum oil products, which not only achieves the purpose of desulfurization, but also does not cause environmental pollution. The catalyst and extractant can be recycled and used, and the adsorbent can be regenerated repeatedly. During alkali treatment, sulfur exists in the form of inorganic salts such as sulfate , is also easy to handle.

Detailed ways

The implementation of the present invention is further described below in conjunction with specific examples, in order to help readers better understand the technical features and beneficial effects of the present invention, but does not constitute any limitation to the applicable scope of the present invention.

In the following examples, the sulfur content in the oil was measured using an ANK7000 sulfur and nitrogen measuring instrument produced by ANK Company of the United States, and detected by ultraviolet fluorescence method.

Comparative example 1

Add 100ml of straight-run diesel oil and a mixture of 2ml of 30% hydrogen peroxide and 1ml of formic acid into the reactor, and carry out the oxidation reaction under the action of an ordinary electric mixer. for 30 minutes. After the reaction, the oxidized oil is separated. The oxidized oil and acetonitrile were mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized straight-run diesel oil. The sulfur content of the straight-run diesel oil decreased from 2742 μg/g to 864 μg/g, and the desulfurization rate was 68.5%.

Comparative example 2

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 2ml 30% hydrogen peroxide and 1ml formic acid, carry out oxidation reaction under the effect of JY92-IID type ultrasonic pulverizer (Ningbo Xinzhi Biotechnology Co., Ltd. produces), The power used is 1200W, the reaction temperature is 60° C., normal pressure, and the reaction time is 6 minutes. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile were mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized straight-run diesel oil. The sulfur content of the straight-run diesel oil decreased from 2742 μg/g to 503 μg/g, and the desulfurization rate was 81.7%.

Example 1

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 2ml 30% concentration hydrogen peroxide and 1ml formic acid, under the action of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, the rotation speed of the high-shear dispersing emulsifier is 22000 rpm, the reaction temperature is 60° C., different reaction pressures are controlled, and the reaction time is 30 minutes. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile are mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized straight-run diesel oil.

The desulfurization results of different oxidation pressures are shown in Table 1.

Table 1

Pressure, Mpa Raw material sulfur content, μg/g Sulfur content after desulfurization, μg/g Desulfurization rate, % Atmospheric pressure 2742 483 82.4 0.05 2742 427 84.4 0.1 2742 385 86.0 0.2 2742 361 86.8

Example 2

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 2ml 30% hydrogen peroxide and 1ml formic acid, carry out under the effect of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, different speeds are controlled, the reaction temperature is 60°C, the reaction time is 60 minutes, and the reaction pressure is 0.2Mpa. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile are mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized straight-run diesel oil. The desulfurization results of the high-shear dispersing emulsifier at different speeds are shown in Table 2.

Table 2

Speed, r/min Raw material sulfur content, μg/g Sulfur content after desulfurization, μg/g Desulfurization rate, % 10000 2742 391 85.7 16000 2742 352 87.2 22000 2742 328 88.0 25000 2742 323 88.2

Example 3

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 3ml 30% hydrogen peroxide and 3ml formic acid, carry out under the effect of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, the rotation speed of the high-shear dispersing emulsifier is 22000rpm, the reaction temperature is 80°C, and the reaction pressure is 0.2Mpa, and different oxidation reaction times are controlled. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile are mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized straight-run diesel oil.

The desulfurization results at different oxidation times are shown in Table 3.

table 3

Oxidation time, min Raw material sulfur content, μg/g Sulfur content after desulfurization, μg/g Desulfurization rate, % 15 2742 396 85.6 30 2742 247 91.0 45 2742 211 92.3 60 2742 187 93.2 90 2742 181 93.4 120 2742 181 93.4

Example 4

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 3ml 30% hydrogen peroxide and 3ml formic acid, carry out under the effect of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, the rotation speed of the high-shear dispersing emulsifier is 22000 rpm, the reaction time is 60 minutes, the reaction pressure is 0.2Mpa, and different reaction temperatures are controlled. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile are mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized straight-run diesel oil.

The desulfurization results at different oxidation temperatures are shown in Table 4.

Table 4

Oxidation temperature, °C Raw material sulfur content, μg/g Sulfur content after desulfurization, μg/g Desulfurization rate, % 50 2742 539 80.3 60 2742 328 88.0 70 2742 235 91.4 80 2742 187 93.2 90 2742 198 92.8 100 2742 254 90.7

Example 5

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 3ml 30% hydrogen peroxide and 3ml formic acid, carry out under the effect of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, the rotational speed of the high-shear dispersing emulsifier is 22000 rpm, the reaction temperature is 80°C, the reaction pressure is 0.2Mpa, and the reaction time is 60 minutes. After the reaction, the oxidized oil is separated.

The oxidized oil and extractant are mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized straight-run diesel oil. The desulfurization results of different extractants are shown in Table 5.

table 5

Extracting agent Raw material sulfur content, μg/g Sulfur content after desulfurization, μg/g Desulfurization rate, % Acetonitrile 2742 187 93.2 Dimethyl sulfoxide 2742 278 89.9 N,N-Dimethylformamide (DMF) 2742 121 95.6

Example 6

In the reactor, add the mixture of 100ml catalytic diesel oil and 4ml 30% hydrogen peroxide and 4ml formic acid, and oxidize under the action of a high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the reaction, the rotational speed of the high-shear dispersing emulsifier is 22000 rpm, the reaction temperature is 80°C, the reaction pressure is 0.2Mpa, and the reaction time is 60 minutes. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile are mixed and extracted twice at a volume ratio of 2:1 to obtain desulfurized catalytic diesel. The sulfur content of the catalytic diesel is reduced from 2435 μg/g to 437 μg/g, and the desulfurization rate is 82.1%.

Example 7

In the reactor, add the mixed solution of 100ml kerosene and 3ml 30% hydrogen peroxide and 3ml formic acid, carry out oxidation reaction under the effect of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) , the rotational speed of the high-shear dispersing emulsifier is 22000 rpm, the reaction temperature is 80°C, the reaction pressure is 0.2Mpa, and the reaction time is 60 minutes. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile are mixed and extracted twice at a volume ratio of 2:1, and the oil layer is collected to obtain desulfurized kerosene. The sulfur content of the kerosene decreased from 3780 μg/g to 489 μg/g, and the desulfurization rate was 87.1%.

Example 8

In the reactor, add 100ml of straight-run diesel oil, 2ml of 30% hydrogen peroxide and 1ml of trifluoroacetic acid mixture, in the action of a high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) The oxidation reaction was carried out at 22,000 rpm, the reaction temperature was 70° C., the reaction pressure was 0.2 Mpa, and the reaction time was 60 minutes. After the reaction, the oxidized oil is separated.

The oxidized oil and acetonitrile were mixed and extracted twice at a volume ratio of 2:1, and the sulfur content in straight-run diesel oil was reduced from 2742 μg/g to 246 μg/g, and the desulfurization rate was 91.0%.

Example 9

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 3ml 30% hydrogen peroxide and 3ml formic acid, carry out under the effect of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, the rotational speed of the high-shear dispersing emulsifier is 22000 rpm, the reaction temperature is 80°C, the reaction pressure is 0.2Mpa, and the reaction time is 60 minutes. After the reaction, the oxidized oil is separated.

The oxidized oil is contacted with silica gel adsorbent and adsorbed at a space velocity of 0.3h ^-1 and a temperature of 60°C. The sulfur content in the obtained straight-run diesel oil is reduced from 2742μg/g to 87μg/g, and the desulfurization rate is 96.8%. .

Example 10

In the reactor, add the mixed solution of 100ml straight-run diesel oil and 3ml 30% hydrogen peroxide and 3ml formic acid, carry out under the effect of high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, the rotational speed of the high-shear dispersing emulsifier is 22000 rpm, the reaction temperature is 80°C, the reaction pressure is 0.2Mpa, and the reaction time is 60 minutes. After the reaction, the oxidized oil is separated.

Then the separated oil and solid sodium hydroxide were mixed in the reactor, the weight ratio of oil and solid sodium hydroxide was 10:1, and the desulfurization reaction was carried out at a temperature of 330° C. and a stirring speed of 1000 r/min. The sulfur content of the obtained straight-run diesel oil decreased from 2742 μg/g to 469 μg/g, and the desulfurization rate was 82.9%.

Example 11

In the reactor, add vacuum distillate oil (VGO) 100ml and the mixed solution of 15ml 30% hydrogen peroxide and 15ml formic acid mixes, in high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/ Under the action of 22Z), the oxidation reaction is carried out, the reaction temperature is 90°C, the rotation speed of the high-shear dispersing emulsifier is 25000rpm, the reaction pressure is 0.2Mpa, and the reaction time is 60 minutes. After the reaction, the oxidized oil is separated.

The separated oil product is reacted with solid sodium hydroxide in an autoclave, the weight ratio of oil product and solid sodium hydroxide is 10:1, and the desulfurization reaction is carried out at a temperature of 330° C. and a stirring speed of 1000 r/min. The sulfur content of vacuum distillate oil (VGO) decreased from 10087μg/g to 916μg/g, and the desulfurization rate was 90.9%.

Example 12

In the reactor, add the mixed solution of atmospheric residue 100ml and 15ml 30% hydrogen peroxide and 15ml formic acid to mix, in the high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) The oxidation reaction is carried out under the action of the high-shear dispersing emulsifier with a rotational speed of 25,000 rpm, a reaction temperature of 90° C., a reaction pressure of 0.2 Mpa, and a reaction time of 60 minutes. After the reaction, the oxidized oil is separated.

Then the separated oil and solid sodium hydroxide were mixed in the reactor, the weight ratio of oil and solid sodium hydroxide was 10:1, and the desulfurization reaction was carried out at a temperature of 330° C. and a stirring speed of 1000 r/min. The sulfur content of atmospheric residual oil decreased from 31856μg/g to 13239μg/g, and the desulfurization rate was 58.4%.

Example 13

In the reactor, add 100 ml of crude oil and 10 ml of 30% hydrogen peroxide and 10 ml of formic acid to mix, and carry out under the action of a high-shear dispersing emulsifier (Shanghai Fluke Fluid Machinery Manufacturing Co., Ltd., FA25/22Z) For the oxidation reaction, the rotational speed of the high-shear dispersing emulsifier is 25,000 rpm, the reaction temperature is 90° C., the reaction pressure is 0.2 Mpa, and the reaction time is 60 minutes. After the reaction, the oxidized oil is separated.

Then the separated oil and solid sodium hydroxide were mixed in the reactor, the weight ratio of oil and solid sodium hydroxide was 10:1, and the desulfurization reaction was carried out at a temperature of 330° C. and a stirring speed of 1000 r/min. The sulfur content of crude oil decreased from 8745μg/g to 1683μg/g, and the desulfurization rate was 80.8%.

Claims (15)

1. The oxidative desulfurization method of petroleum oil products, including the oxidation reaction of organic sulfides in petroleum oil products, and the process of separating the oxidation products of sulfides from the oil products, characterized in that the oxidation reaction is to make organic sulfur compounds containing Petroleum oil products, oxidants and catalysts of sulfur compounds are completed under the action of a high-shear dispersing and emulsifying device, the reaction temperature is 30-110°C, the reaction pressure is normal pressure-1Mpa, and the reaction time is 1-180 minutes; the high-shear The circumferential speed of the rotor of the cutting, dispersing and emulsifying device is 3m/s-50m/s. 2. The oxidative desulfurization method according to claim 1, wherein the oxidation reaction process uses a high-shear dispersion emulsification device with a stator diameter of 6mm-500mm, and controls the rotor speed to be 600-30000rpm. 3. The oxidative desulfurization method as claimed in claim 1, wherein said oxidizing agent is hydrogen peroxide. 4. The oxidative desulfurization method according to claim 1 or 3, wherein the volume ratio of the oxidant to the oil is 1:500-3:10. 5. The oxidative desulfurization method according to claim 1, wherein the catalyst is selected from the group consisting of formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, benzoic acid, m-chlorobenzoic acid, phosphotungsten acid or phosphomolybdic acid. 6. The oxidative desulfurization method according to claim 1 or 5, wherein the volume ratio of the oxidant to the catalyst is 1:20-20:1. 7. The oxidative desulfurization method as claimed in claim 1, wherein after the oxidation reaction is completed, the oxidation product and the oil are separated by means of extraction, adsorption, alkali treatment or a combination of more than one of them. 8. The oxidative desulfurization method according to claim 7, wherein the extraction step is to mix the oxidized product with an extractant and then stand at room temperature, then separate the oil from the extractant, and the extractant is selected from acetonitrile, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, sulfolane, nitromethane, diethylene glycol, triethylene glycol, tetraethylene glycol, diethylene glycol amine, N-formyl morpholine, methanol, ethanol , formaldehyde, acetaldehyde, formic acid or acetic acid. 9. The oxidative desulfurization method according to claim 8, wherein during the extraction, the volume ratio of the oxidized oil product to the extractant is 1:10-4:1. 10. The oxidative desulfurization method according to claim 7, wherein the adsorption step is to contact the oxidation reaction product with a solid adsorbent, the space velocity of this process is 0.1-2.0h ^-1 , and the temperature is 20-90°C. 11. The oxidative desulfurization method according to claim 10, wherein the solid adsorbent used is selected from layered molecular sieves, MCM-41 molecular sieves, activated carbon, alumina, silica gel or titanium silicon oxide. 12. The oxidative desulfurization method according to claim 7, wherein the alkali treatment step is to add hydroxides of alkali metals or hydroxides of alkaline earth metals to the oxidation reaction product, and react at 70-350°C for 30-30°C. 180 minutes. 13. The oxidative desulfurization method according to claim 12, wherein the hydroxides of alkali metals or alkaline earth metals used are selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and mixtures thereof . 14. The oxidative desulfurization method according to claim 12 or 13, wherein a solid or an aqueous solution thereof is used for the hydroxide of the alkali metal or the hydroxide of the alkaline earth metal. 15. The oxidation desulfurization method according to claim 1, characterized in that said petroleum oil products include kerosene, diesel oil, vacuum distillate oil, atmospheric residue, vacuum residue and crude oil.