CN1253536C - Catalysis, oxidation sweetening method for distillate oil of petroleum - Google Patents

Abstract

The invention provides a method for catalytic oxidation desulfurization of petroleum distillate oil. The method uses carbonaceous material or/and transition metal-loaded carbonaceous material as a catalyst, reacts under the action of at least one peroxide and at least one acid, and produces peroxyacid and hydroxyl free radicals in the reaction for synergistic oxidation Organosulfur compounds in petroleum distillates. Compared with the prior art, the biggest advantage of the present invention is that after the petroleum distillate oil is oxidized, low-sulfur products can be obtained without subsequent adsorption or extraction, and ultra-low-sulfur products can be obtained if further adsorption or extraction is carried out . The present invention has wide applicability and can be adapted to various distillate oils (such as: straight-run gasoline, catalytically cracked gasoline, coking gasoline, hydrogenated gasoline, commercial gasoline, straight-run diesel oil, catalytic cracked diesel oil, coking diesel oil, hydrogenated refined diesel oil) Or commercial diesel oil, straight-run wax oil, coker wax oil) deep desulfurization.

Description

Petroleum distillate oil catalytic oxidation desulfurization method

technical field

The invention relates to a method for desulfurizing petroleum distillate oil, in particular to a method for catalytic oxidation desulfurization of petroleum distillate oil.

Background technique

The increasingly stringent environmental protection requirements have made the world's oil refining industry face the severe challenge of producing cleaner gasoline and diesel fuel. The production of clean gasoline and diesel has become the main theme of today's refineries, and the reduction of sulfur content is the top priority in the production of clean gasoline and diesel. The United States requires gasoline sulfur content to be reduced to 30-50ppm. The European Community has proposed a more stringent new standard for clean gasoline from 2000 to 2005, reducing the current sulfur content from 100ppm to 15ppm. Europe and the United States have also put forward strict restrictions on the sulfur content of diesel oil. The sulfur content of diesel oil in Europe will be reduced from 350ppm to 50ppm in 2005, and it is still under discussion recently to further reduce it to 10ppm; the sulfur content of diesel oil in the United States will also be greatly reduced from the current 500ppm to 15ppm in 2006. In order to meet the new opportunities and new challenges of clean fuel production in the new century, various new technologies for producing clean fuel are being developed, especially the technology for producing low-sulfur and ultra-low-sulfur diesel. Among them, new catalysts and processes for selective hydrotreating, new technologies such as gasoline and diesel adsorption desulfurization, diesel biodesulfurization, and selective oxidation desulfurization are particularly eye-catching. my country is also accelerating the development and research of new technologies for clean fuel production to provide technical reserves for the production of cleaner diesel fuel.

The traditional oil desulfurization technology is hydrodesulfurization. For deep desulfurization, hydrodesulfurization must use very high pressure and increase the reaction temperature, thus increasing the difficulty and cost of deep desulfurization. The American Petroleum Institute pointed out in a study in 2000 that in order to produce diesel with a sulfur content of less than 30 ppm, a new high-pressure hydrogenation unit must be installed and operated at a pressure of 1100-1200 psig. Pressure exceeding 1000 psig requires a very thick reactor wall, which can only be produced by a few manufacturers, and the production time is very long; at the same time, there are many places to be improved in the existing hydrogenation equipment, such as reactors, hydrogen compressors, Circulating scrubber, interstage stripper and other related hardware; the amount of hydrogen required for deep desulfurization will also increase relatively. The consumption of hydrogen and the investment in hydrogen production equipment are one of the main costs of deep desulfurization. In deep desulfurization of diesel, hydrogen consumption is the largest operating cost. How to reduce the usage of hydrogen is a key goal of hydrodesulfurization. In most cases, 10ppm sulfur diesel consumes 25-45% more hydrogen than 500ppm sulfur diesel. In addition, the deep hydrodesulfurization catalyst must be replaced with a new type of hydrodesulfurization catalyst with higher selectivity. The lower the sulfur content of the product, the non-linear increase in hydrogen consumption will undoubtedly greatly increase the cost of hydrodesulfurization. With the further development of industry and agriculture, the demand for petroleum products in my country will increase year by year. If hydrogenation deep desulfurization is adopted, the cost of diesel oil will be greatly increased. Although gasoline hydrogenation can achieve deep desulfurization, it will cause the quality of gasoline to decline, because gasoline contains a large amount of olefins, which will saturate part of the olefins during hydrogenation, thus affecting the octane number of gasoline. Therefore, developing a high-efficiency and low-cost desulfurization technology is of great significance for protecting the environment and accelerating the development of my country's national economy.

The use of peroxide oxidation is a very promising processing route in petroleum refining. It can be used to remove organic sulfur compounds in petroleum distillate oil, and can produce ultra-clean oil products to meet the increasingly stringent sulfur requirements of refined oil products in the world. content regulations. Oxidative desulfurization (ODS), as a new deep desulfurization technology for transportation fuel oil, has received more and more attention. Many studies have been done on oxidation desulfurization process at home and abroad, but there is no report on industrialization.

U.S. Patent Nos. 6,160,193 and 6,274,785 disclose a method for oxidation-extraction desulfurization of petroleum distillates: "Use hydrogen peroxide and acetic acid to oxidize organic sulfur in petroleum distillates to corresponding sulfoxides or sulfones, and then use dimethyl sulfoxide to The oxidized oil is extracted, and finally activated alumina is used for adsorption to achieve the purpose of deep removal of sulfur compounds." Among them, the use of acid is large, the process route is long, and the oil loss is also large.

UniPure has applied for a number of patents, such as world patent WO 02/18518, U.S. patent application 2002/0029997, U.S. patent 6,406,166 and U.S. patent 6,402,940, which disclose a method using 30% H ₂ O ₂ -HCOOH oxidation-extraction (or adsorption ) method for processing deep desulfurization of petroleum distillate oil. The amount of formic acid is relatively large, and its concentration is high. After oxidation treatment, the amount of adsorbent activated alumina is also large, regeneration is difficult, and the consumption and loss of formic acid are also large; if solvent extraction is used, the oil loss will be increased. Large, resulting in an increase in the cost of oxidative desulfurization; as the amount of formic acid increases, the oil recovery rate decreases.

BP has applied for a series of patents, such as world patents WO 02/097006, WO 02/062926, WO 02/062927 and U.S. patent application 2002/0148756, which disclose the method of petroleum distillate oxidation-extraction desulfurization: "Firstly, the petroleum distillate Medium and low pressure hydrogenation treatment, the high sulfur content of the distillation is oxidized with hydrogen peroxide under the action of heteropolyacid and phase transfer agent, and then extracted with polar solvent to achieve the purpose of removing organic sulfur compounds.” Heteropoly The oxidation performance of acid-catalyzed hydrogen peroxide to organic sulfur is poor, and a phase transfer agent needs to be added, which brings difficulties to the separation after the reaction.

Contents of the invention

The object of the present invention is to provide a catalytic oxidation desulfurization method of petroleum distillate oil using carbonaceous materials and inorganic oxyacids or/and organic acids as catalysts, so as to overcome the deficiencies in the prior art.

Design of the present invention is such:

Commercial carbonaceous materials contain a small amount of iron, and the surface of carbonaceous materials has oxygen-containing groups, so the action of carbonaceous materials and hydrogen peroxide can generate hydroxyl radicals with strong oxidizing ability. There are carboxyl, carbonyl, phenolic, lactone, and quinone groups on its surface. From the perspective of electron transfer, the electron transfer between species participating in the redox reaction causes the electron donor to be oxidized while the electron acceptor is reduced. In organic chemistry, it is not straightforward which species are oxidized and which are reduced, but usually oxidation reactions involve the gain of oxygen or the loss of hydrogen. Carbonaceous materials are conducive to the electron transfer process due to their special surface chemical structure.

The present invention uses carbonaceous materials or carbonaceous materials loaded with transition metal ions as catalysts in the oxidative desulfurization process, which has dual functions in the oxidation reaction process, being both catalysts and adsorbents, and has the function of coupling reaction and separation together. The final separated oil phase has a low residual sulfur concentration. The carbonaceous material catalyst has a large specific surface area and strong lipophilicity, and can be dispersed in the oil phase when added to the reaction system, providing a large reaction contact area. On the other hand, carbonaceous material catalysts together with hydrogen peroxide can generate hydroxyl radicals with very strong oxidizing ability under acidic conditions, which can strengthen the oxidative desulfurization effect. The surface of the carbonaceous material catalyst has a large number of oxygen-containing groups and its microporous structure. During the oxidation reaction, it can absorb the sulfone generated in the reaction, so that the sulfur content of the oxidized petroleum distillate is low; at the same time, the carbonaceous material catalyst is in the Surface modification under the action of peroxide enhances its adsorption capacity for organic sulfur.

Technical solutions:

The method for catalytic oxidation desulfurization of petroleum distillate oil in the present invention, its main steps are: the catalytic oxidation of petroleum distillate oil and the oil-water separation to obtain low-sulfur oil, it is characterized in that, said petroleum distillate oil catalytic oxidation process is: Activated carbon or/and transition metal-loaded activated carbon is used as a catalyst, phosphoric acid or/and monobasic organic carboxylic acid is used as a cocatalyst, and the reaction is carried out in the presence of hydrogen peroxide and pH=1~6, and the reaction temperature is 60~95°C. The reaction time is not less than 15 minutes;

Wherein: said transition metal is iron, cobalt or/and nickel, and its load is 5%～25% of active carbon weight; Said monobasic organic carboxylic acid is formic acid, acetic acid or X _n CH _3-n COOH wherein: n=1～3, X=F, Cl, Br; the consumption of catalyst is 0.1%～0.9% of the weight of the oxidized petroleum distillate; the molar ratio of hydrogen peroxide to sulfur in the oxidized petroleum distillate is at least 4 .

According to the method proposed by the present invention, the reaction temperature in the heterogeneous catalytic oxidation desulfurization reaction is preferably 70°C to 95°C; pH=1.0 to 3.5 is good; the transition metal of the load is preferably ferrous ion or iron ion; the activated carbon can be Surface treatment, or direct use without pretreatment.

Detailed ways

The method for catalytic oxidation desulfurization of petroleum distillate oil of the present invention, it comprises the steps:

(A) mixing sulfur-containing petroleum distillate oil with hydrogen peroxide, the molar ratio of added hydrogen peroxide to sulfur-containing petroleum distillate oil being at least 4;

(B) Add phosphoric acid, formic acid, acetic acid or/and X _n CH _3-n COOH to the above mixture, wherein: n=1~3, X=F, Cl, Br, so that the pH value is 1.0~3.5;

(C) add catalyzer in the mixture by step (B) gained: gac or/and the gac of loaded iron, cobalt or/and nickel, the consumption of catalyzer is 0.1%～0.9% of oxidized petroleum distillate weight, at temperature Under the condition of 70 ~ 95 ℃, after reacting for at least 15 minutes, use filtration method to separate liquid and solid;

(D) separating the oil phase and the water phase from the liquid phase obtained in step (C), the separated oil phase is a desulfurization product, and then washing, absorbing or extracting to obtain an ultra-low sulfur oil product;

Wherein: the adsorbent is preferably activated alumina, silica gel or activated carbon, and the extractant is preferably 90% to 95% DMF aqueous solution, 90% to 95% acetonitrile aqueous solution or furfural.

The invention provides a method for catalytic oxidation desulfurization of petroleum distillate oil. The method uses carbonaceous materials or/and carbonaceous materials loaded with transition metals as catalysts, reacts under the action of peroxides and acids, and generates peroxyacids and hydroxyl radicals in the reaction to synergistically oxidize organic sulfur in petroleum distillates compound. Carbonaceous materials have specific surface physical and chemical properties and good lipophilicity. They not only have very strong catalytic oxidation performance for organic sulfur compounds, but also can adsorb organic sulfur oxides. Compared with the prior art, the greatest advantage of the present invention is that after the petroleum distillate is oxidized, its sulfur content can reach a very low level without adsorption or extraction, and ultra-low sulfur content can be obtained if further adsorption or extraction is carried out. sulfur products. The present invention has wide applicability, and it can be adapted to various distillate oils (such as: straight-run gasoline, catalytically cracked gasoline, coker gasoline, hydrogenated gasoline, commercial gasoline, straight-run diesel oil, catalytic cracked diesel oil, coking diesel oil, hydrogenated refined gasoline, etc.) Deep desulfurization of diesel oil, commercial diesel oil, straight-run gas oil or coker gas oil).

The present invention is described further below by embodiment, and its purpose is for better understanding content of the present invention. Therefore, the examples given do not limit the protection scope of the present invention:

Example 1

Dissolve thiophene in n-octane to form a model oil with a sulfur content of 1447ppm. Add 36ml of model oil to a 250ml batch reactor, then add 0.10g of activated carbon and stir at room temperature for 5min. The batch reactor is heated to 60°C, and then 2g of H ₂ O ₂ with a concentration of 30% was added to the reactor, adjusted to pH 2 with formic acid, and reacted at 60°C for 120 minutes. After the reaction, the oil phase was taken for GC-FPD analysis, and 31.29% of thiophene was converted.

Comparative ratio

Dissolve thiophene in n-octane to form a model oil with a sulfur content of 1447ppm. Add 36ml of model oil to a 250ml batch reactor, heat the batch reactor to 60°C, and then add 2g of 30% H ₂ O ₂ Add it into the reactor, adjust the pH value to 2 with formic acid, and react at 60°C for 120 minutes. After the reaction, the oil phase is taken for GC-FPD analysis, and the conversion of thiophene is 6.41%.

Example 2

Dissolve thiophene in n-octane to form a model oil with a sulfur content of 1447ppm. Add 36ml of model oil to a 250ml batch reactor, then add 0.40g of activated carbon and stir at room temperature for 5min, heat the batch reactor to 60°C, and then 2g of H ₂ O ₂ with a concentration of 30% was added to the reactor and the pH value was adjusted to 2 with formic acid to react at 60°C for 120 min. After the reaction, the oil phase was taken for GC-FPD analysis, and 83.21% of thiophene was converted.

Example 3

50g catalytically cracked gasoline (FCC gasoline, mercaptans have been removed) (gasoline sulfur content 998ppm) and 0.4g activated carbon are added to a 500ml batch reactor, start stirring and be warmed up to a specified temperature; then, pour 1.6g30% hydrogen peroxide aqueous solution Put it into the flask, adjust the pH value to 2 with formic acid, and keep stirring at a high speed; react at 60°C for 120 minutes, and take the oil phase after the reaction to measure the sulfur content to 297ppm.

Example 4

Dissolve DBT in n-octane to form a model oil with a sulfur content of 2037ppm. Add 36ml of model oil to a 250ml batch reactor, then add 0.10g of activated carbon and stir at room temperature for 5min, heat the batch reactor to 60°C, and then Add 1.82g of 30% H ₂ O ₂ into the reactor, adjust the pH value to 2 with formic acid, and react at 60°C for 60 minutes. After the reaction, take the oil phase for GC-FPD analysis, and the DBT is 86.70% converted.

Comparative ratio

Dissolve DBT in n-octane to form a model oil with a sulfur content of 2037ppm. Add 36ml of model oil to a 250ml batch reactor, heat the batch reactor to 60°C, and then add 1.82g of 30% H ₂ O ₂ was added to the reactor, formic acid was used to adjust the pH value to 1, and the reaction was carried out at 60°C for 60 minutes. After the reaction, the oil phase was taken for GC-FPD analysis, and the DBT was 57.88% converted.

Example 5-18

The model oil oxidative desulfurization experiment was carried out in a method similar to that described in Example 4, and the catalyst dosage, pH value and experimental results are listed in Table 1.

Table 1 Example pH Amount of activated carbon (g) 30% H ₂ O ₂ Amount (g) Reaction temperature (°C) Response time (min) Conversion rate(%) 5 2.5 0 1.82 60 60 57.88 6 2.5 0.1 1.82 60 60 86.70 7 2.5 0.2 1.82 60 60 100 8 2.5 0.3 1.82 60 60 100 9 2.5 0.4 1.82 60 60 100 10 2.5 0.5 1.82 60 60 95.09 11 2.5 0.6 1.82 60 60 84.63 12 6 0.3 1.82 60 60 63.33 13 5 0.3 1.82 60 60 100 14 4 0.3 1.82 60 60 100 15 3 0.3 1.82 60 60 100 16 2 0.3 1.82 60 60 100 17 1 0.3 1.82 60 60 100 18 0 0.3 1.82 60 60 94.50

Example 19

Dissolve DBT in n-octane to form a model oil with a sulfur content of 2037ppm. Add 36ml of model oil to a 250ml batch reactor, then add 0.10g of activated carbon and stir at room temperature for 5min, heat the batch reactor to 60°C, and then Add 1.82g of 30% H ₂ O ₂ into the reactor, adjust the pH value to 2 with trifluoroacetic acid, and react at 60°C for 60 minutes. After the reaction, take the oil phase for GC-FPD analysis, and the DBT is 100% converted.

Example 20

Dissolve DBT in n-octane to form a model oil with a sulfur content of 2037ppm. Add 36ml of model oil to a 250ml batch reactor, then add 0.10g of activated carbon and stir at room temperature for 5min, heat the batch reactor to 60°C, and then Add 1.82g of 30% H ₂ O ₂ into the reactor, add 2ml of 20% phosphoric acid, adjust the pH value to 1.5 with formic acid, and react at 60°C for 60 minutes. After the reaction, take the oil phase for GC-FPD analysis, DBT 100% conversion.

Example 21

Dissolve DBT in n-octane to form a model oil with a sulfur content of 2037ppm. Add 36ml of model oil to a 250ml batch reactor, then add 0.10g of activated carbon and stir at room temperature for 5min, heat the batch reactor to 60°C, and then Add 1.82g of 30% _H2O2 into the reactor, add 2ml of 20% phosphoric acid, adjust the pH value to 1.0 with trifluoroacetic acid, react at 60°C for 60min, and take the oil phase after the reaction for GC- _FPD analysis , DBT 100% conversion.

Example 22

Take a certain amount of FeSO ₄ ·7H ₂ O and dissolve it in water, then add the solution of ferrous ions to the activated carbon, and use the same amount of impregnation method to attach the ferrous ions, so that the content of iron on the activated carbon is 5% of the mass of the activated carbon.

Add 36ml of model oil (with a sulfur content of 2037ppm) into a 250ml batch reactor, then add 0.1g of catalyst and stir at room temperature for 5min, heat the batch reactor _to 60°C, then add 1.82g of 30% _H2O2 In the reactor, adjust the pH value to 2 with formic acid, and react at 60°C for 60 minutes. After the reaction, the oil phase is taken for GC-FPD analysis, and the DBT is 100% converted.

Example 23

Take a certain amount of FeSO ₄ ·7H ₂ O and dissolve it in water, then add the solution of ferrous ions to the activated carbon, and use the equal impregnation method to attach the ferrous ions, so that the content of iron on the activated carbon is 10% of the mass of the activated carbon (catalyst).

Add 36ml of model oil (with a sulfur content of 2037ppm) into a 250ml batch reactor, then add 0.1g of catalyst and stir at room temperature for 5min, heat the batch reactor _to 60°C, then add 1.82g of 30% _H2O2 In the reactor, adjust the pH value to 2 with formic acid, and react at 60°C for 60 minutes. After the reaction, the oil phase is taken for GC-FPD analysis, and the DBT is 100% converted.

Example 24

Dissolve a certain amount of FeSO ₄ ·7H ₂ O in water, then add the solution of ferrous ions to activated carbon, and use equal impregnation method to attach ferrous ions, so that the content of iron on the activated carbon is 15% of the mass of activated carbon (catalyst).

Add 36ml of model oil (with a sulfur content of 2037ppm) into a 250ml batch reactor, then add 0.1g of catalyst and stir at room temperature for 5min, heat the batch reactor _to 60°C, then add 1.82g of 30% _H2O2 In the reactor, adjust the pH value to 2 with formic acid, and react at 60°C for 60 minutes. After the reaction, the oil phase is taken for GC-FPD analysis, and the DBT is 100% converted.

Example 25

Take a certain amount of FeSO ₄ ·7H ₂ O and dissolve it in water, then add the solution of ferrous ions to the activated carbon, and use the same amount of impregnation method to attach the ferrous ions, so that the content of iron on the activated carbon is 20% of the mass of the activated carbon.

Add 36ml of model oil (with a sulfur content of 2037ppm) into a 250ml batch reactor, then add 0.1g of catalyst and stir at room temperature for 5min, heat the batch reactor _to 60°C, then add 1.82g of 30% _H2O2 In the reactor, adjust the pH value to 2 with formic acid, and react at 60°C for 60 minutes. After the reaction, the oil phase is taken for GC-FPD analysis, and the DBT is 100% converted.

Example 26

Take a certain amount of FeSO ₄ ·7H ₂ O and dissolve it in water, then add the solution of ferrous ions to the activated carbon, and use the same amount of impregnation method to attach the ferrous ions, so that the content of iron on the activated carbon is 25% of the mass of the activated carbon.

Add 36ml of model oil (with a sulfur content of 2037ppm) into a 250ml batch reactor, then add 0.1g of catalyst and stir at room temperature for 5min, heat the batch reactor _to 60°C, then add 1.82g of 30% _H2O2 In the reactor, adjust the pH value to 2 with formic acid, and react at 60°C for 60 minutes. After the reaction, the oil phase is taken for GC-FPD analysis, and the DBT is 100% converted.

Comparative ratio

Published European patent EP0565324 once reported the use of hydrogen peroxide and formic acid (without solid catalyst) to oxidize organic sulfur compounds in petroleum, and then use extraction and adsorption methods to reduce the sulfur content in oil. Below according to the oxidative treatment method of patent EP0565324, provide comparative examples 1～7 and contrast with the embodiment 12～18 of this clearly adding solid catalyst (illustrate that said solid catalyst can catalyze peroxide fast oxidation organosulfur compound under mild condition , and comparable or better conversion of sulfur in petroleum distillates without extraction and adsorption). The experimental results are shown in Table 4.

Table 4 comparative example pH value catalyst 30% H ₂ O ₂ Amount (g) Reaction temperature (°C) Response time (min) Conversion rate(%) 1 6 0 1.82 60 60 25.82 2 5 0 1.82 60 60 34.51 3 4 0 1.82 60 60 42.17 4 3 0 1.82 60 60 48.50 5 2 0 1.82 60 60 57.88 6 1 0 1.82 60 60 90.82 7 0 0 1.82 60 60 100

Example 27

Add 100g of hydrotreated diesel oil (diesel sulfur content 800ppm, diesel density 0.8219g/cm ³ (15°C)) and 0.1g activated carbon into a 500ml batch reactor, start stirring and heat up to a specified temperature; then, 1.6g of 30% over Pour the aqueous hydrogen oxide solution into the flask, and keep stirring at high speed, adjust the pH value to 2.5 with formic acid, react at 90°C for 15 minutes, then separate the oil from water, take the oil phase and measure the sulfur content to be 248ppm.

Example 28-39

The oxidative desulfurization experiment of hydrotreated diesel oil (diesel sulfur content 800ppm, diesel density 0.8219g/cm ³ (15°C)) was carried out in a method similar to that described in Example 27. The composition of the catalyst and the experimental results are listed in Table 5.

table 5 Example pH value Amount of activated carbon (g) 30% H ₂ O ₂ Amount (g) Reaction temperature (°C) Response time (min) Residual sulfur (ppm) 28 3 0.1 1.6 70 30 248 29 3 0.2 1.6 70 30 113 30 3 0.3 1.6 70 30 104 31 3 0.4 1.6 70 30 100 32 3 0.5 1.6 70 30 206 33 3 0.6 1.6 70 30 239 34 1 0.2 1.6 70 30 157 35 2 0.2 1.6 70 30 134 36 2.5 0.2 1.6 70 30 107 37 2.7 0.2 1.6 70 30 102 38 3.3 0.2 1.6 70 30 118 39 4 0.2 1.6 70 30 144

Example 40

100g FCC diesel oil (diesel oil sulfur content 7268ppm, diesel oil density 0.8580g/cm ³ (15 ℃)) and 0.8g active carbon are added 500ml batch reactor, start stirring and be warming up to specified temperature; Then, the hydrogen peroxide of 15.3g30% The aqueous solution was poured into the flask, and kept stirring at high speed, adjusted the pH value to 2.5 with formic acid, reacted at 90°C for 15 minutes, then separated the oil from water, and took the oil phase to measure the sulfur content as 294ppm.

Example 41

Add 100g FCC diesel oil (diesel oil sulfur content 7268ppm, diesel oil density 0.8580g/cm ³ (15 ℃)) and 1.0g gac into 500ml batch reactor, start stirring and be warming up to specified temperature; Then, the hydrogen peroxide of 15.3g30% The aqueous solution was poured into the flask, and kept stirring at high speed, adjusted the pH value to 2 with formic acid, reacted at 90°C for 15 minutes, then separated the oil from water, and took the oil phase to measure the sulfur content as 271ppm.

Example 42

Add 100g FCC diesel oil (diesel oil sulfur content 7268ppm, diesel oil density 0.8580g/cm ³ (15 ℃)) and 1.2g gac into 500ml batch reactor, start stirring and be warming up to specified temperature; Then, the hydrogen peroxide of 15.3g30% Pour the aqueous solution into a flask and keep stirring at high speed, adjust the pH value to 2 with formic acid, react at 90°C for 15 minutes, then separate the oil from water, take the oil phase and measure the sulfur content to be 268ppm.

Example 43

100g straight-run diesel oil (1520ppm diesel fuel sulfur content, diesel oil density 0.824g/cm ³ (15°C)) and 0.8g activated carbon are added to a 500ml batch reactor, start stirring and be warmed up to the specified temperature; then, 3.3g30% peroxidized Pour the aqueous hydrogen solution into the flask, and keep stirring at high speed, adjust the pH value to 1.5 with formic acid, react at 90°C for 15 minutes, then separate the oil from water, take the oil phase and measure the sulfur content to be 147ppm.

Example 44

100g straight-run diesel oil (1520ppm diesel oil sulfur content, diesel oil density 0.8219g/cm ³ (15°C)) and 1.0g activated carbon are added to a 500ml batch reactor, start stirring and be warmed up to the specified temperature; then, 3.3g30% peroxidized Pour the aqueous hydrogen solution into the flask and keep stirring at a high speed, adjust the pH value to 1.5 with formic acid, react at 90°C for 15 minutes, then separate the oil from water, take the oil phase and measure the sulfur content to be 134ppm.

Example 45

100g straight-run wax oil (wax oil sulfur content 1734ppm, diesel oil density 0.9216g/cm ³ (15 ℃)) and 1.0g active carbon are added 500ml batch reactor, start stirring and be warming up to specified temperature; Then, 4.5g30% Pour hydrogen peroxide aqueous solution into the flask, add 4ml of phosphoric acid with a concentration of 20%, and keep stirring at high speed, adjust the pH value to 1.5 with formic acid, react at 90°C for 15min, then separate oil from water, take the oil phase and measure the sulfur content to be 187ppm.

Example 46

According to Example 35, the diesel oil after oxidation treatment was washed with water, then dried with anhydrous MgSO ₄ , and then statically adsorbed at room temperature using activated alumina to obtain 24ppm clean diesel oil.

Example 47

According to Example 37, the oxidized diesel oil was washed with water, then dried with anhydrous MgSO ₄ , and then statically adsorbed at room temperature using activated alumina to obtain 16 ppm clean diesel oil.

Claims (4)

1, a kind of method of fraction oil of petroleum catalytic oxidation desulfurization, its key step is: the catalyzed oxidation of fraction oil of petroleum and obtain low sulfur oil after oily water separation, it is characterized in that, said fraction oil of petroleum catalytic oxidation process is: with gac or/and the gac of carrying transition metal is a catalyzer, with phosphoric acid or/and the unary organic carboxylic acid is a promotor, have hydrogen peroxide to exist and pH=1～6 conditions under react, temperature of reaction is 60～95 ℃, the reaction times is for being no less than 15 minutes;

Wherein: said transition metal is iron, cobalt or/and nickel, and its charge capacity is 5%～25% of a gac weight; Said unary organic carboxylic acid is formic acid, acetate or X _nCH _3-nCOOH is wherein: n=1～3, X=F, Cl, Br; Catalyst consumption is 0.1%～0.9% of an oxidized petroleum fractions weight of oil; The molar ratio of sulphur is at least 4 in hydrogen peroxide and the oxidized fraction oil of petroleum.

2, the method for claim 1, it is characterized in that wherein said fraction oil of petroleum is straight-run spirit, catalytically cracked gasoline, coker gasoline, hydrofined gasoline, commercial gasoline, straight-run diesel oil, catalytic cracking diesel oil, coker gas oil, hydrofining diesel oil, commercial diesel oil, straight-run gas oil or wax tailings.

3, method as claimed in claim 1 or 2 is characterized in that, said catalytic oxidation desulfurization method comprises the steps:

(A) the sulfur-bearing oil distillate is mixed with hydrogen peroxide, the molar ratio of sulphur is at least 4 in hydrogen peroxide that is added and the sulfur-bearing oil distillate;

(B) in said mixture, add phosphoric acid, formic acid, acetate or/and X _nCH _3-nCOOH is wherein: n=1～3, and X=F, Cl, Br makes the pH value 1.0～3.5;

(C) in mixture, add catalyzer by step (B) gained: gac or/and load iron, cobalt or/and the gac of nickel, catalyst consumption is 0.1%～0.9% of an oxidized petroleum fractions weight of oil, in temperature is under 70～95 ℃ of conditions, reacts and adopts filter method to carry out liquid-solid separation at least after 15 minutes;

(D) to carrying out oil phase and aqueous phase separation by the liquid phase of step (C) gained, separated oil phase is a desulfurization product, obtains the super low sulfur oil product again after washing, absorption or extraction.

4, method as claimed in claim 3, it is characterized in that, the sorbent material that said absorption is adopted in the step (D) is activated alumina, silica gel or gac, and the extraction agent that said extraction is adopted is 90%～95% the DMF aqueous solution, 90%～95% acetonitrile solution or furfural.