Preparation method and use method of desulfurization and denitrification catalyst

Abstract

The present invention discloses a desulfurization and denitrification catalyst preparation method and a use method thereof, and relates to the field of catalyst preparation, the method comprises the following steps: S1, placing a three-neck flask in a constant temperature water bath kettle, adding absolute ethyl alcohol, starting a digital display electric stirrer, and adjusting the rotation speed for stirring; adding butyl titanate into the three-neck flask, and continuously stirring to obtain a mixed solution A; s2, putting a lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask to be mixed with the mixed solution A, then pouring a citric acid solution into the three-necked flask, continuously stirring, stopping stirring, and aging at room temperature to obtain a solid B; s4, drying the solid B in a drying oven; and S5, dropwise adding a certain amount of a complexing agent into the solid B dried in the step S4, and standing at room temperature to obtain the desulfurization and denitrification catalyst. The catalyst provided by the invention has a relatively good removal effect in both desulfurization and denitrification processes.

Description

Technical Field

[0001] The present invention relates to the field of catalyst preparation, and in particular to a method for preparing a desulfurization and denitrification catalyst and a method for using the same. Background Art

[0002] Photocatalytic oxidation desulfurization (PODS) is a new type of oxidation desulfurization method with broad application research prospects. Usually, the photocatalytic oxidation desulfurization method is combined with the liquid-liquid extraction method. The advantages of the photocatalytic oxidation desulfurization reaction are safe reaction conditions, low operating costs, easy separation of products, and no production of three wastes. The research difficulties are that the system has a small response range to light and a slow desulfurization rate.

[0003] The heterocyclic nitrogen compounds contained in petroleum not only have a strong corrosive effect on equipment, but also in the process of oil refining, a large amount of nitrides are deposited on the surface of the catalyst, which leads to a decrease in the performance of the catalyst, thereby increasing the economic cost. In addition, when burning fuel containing sulfur and nitrogen, toxic and harmful gases will be generated, which are very easy to change under certain conditions, thus causing the destruction of ozone in the troposphere. In the long run, these toxic gases will pollute the air and reduce air quality. There are many measures to reduce exhaust gas emissions, but the most important thing is to improve it from the source, that is, to use clean fuel. Using clean fuel can not only improve the combustion performance of fuel, but also significantly reduce air pollution. Existing catalysts are generally used to remove sulfides or nitrides alone, and are unique. However, nitrides and sulfides generally exist at the same time in petroleum. If the catalyst can remove both sulfides and nitrides well, it will save a certain amount of cost. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the above-mentioned shortcomings and deficiencies of the prior art, the present application provides a method for preparing a desulfurization and denitrification catalyst and a method for using the same, by which not only the nitrogen compounds in the oil products can be removed, but also the sulfides can be removed.

[0006] (II) Technical solution

[0007] To achieve the above objectives, the embodiments of the present application adopt the following technical solutions:

[0008] The present invention provides a method for preparing a desulfurization and denitrification catalyst, comprising the following steps:

[0009] S1, placing a three-necked flask in a constant temperature water bath, adding anhydrous ethanol, turning on a digital electric stirrer, adjusting the speed for stirring; pipetting butyl titanate into the three-necked flask, and continuously stirring to obtain a mixed solution A;

[0010] S2, putting the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask and mixing them with the mixed solution A, then pouring the citric acid solution into the three-necked flask and continuing to stir, then stopping, and placing it at room temperature for aging to obtain a solid B;

[0011] S4, placing solid B in an oven to dry;

[0012] S5, adding a certain amount of complexing agent to the solid B obtained by drying in S4, and allowing the mixture to stand at room temperature to obtain a desulfurization and denitrification catalyst.

[0013] Further, ammonium metavanadate is dissolved in deionized water, heated while stirring to obtain a yellow solution, the pH is adjusted to obtain a mixed solution B, the mixed solution B is transferred to a polytetrafluoroethylene high-pressure reactor for heating, and after natural cooling at room temperature, the mixed solution B is repeatedly washed with deionized water and anhydrous ethanol solution to obtain a solid C after precipitation. The solid C is dried and dissolved in deionized water to obtain a vanadium-containing precipitate.

[0014] Furthermore, the pH of the mixed solution B is 1-5.

[0015] Furthermore, ammonium metavanadate is directly sintered to obtain vanadium pentoxide, which is then dissolved in deionized water to obtain a vanadium-containing precipitate.

[0016] Furthermore, the complexing agent is a hydrogen peroxide solution.

[0017] On the other hand, an embodiment of the present application also provides a method for using a desulfurization and denitrification catalyst, which is characterized in that the above-mentioned desulfurization and denitrification catalyst is used, and the method of use includes the following steps: placing simulated oil, methanol, a drop of hydrogen peroxide solution, a desulfurization and denitrification catalyst, and a rotor into a beaker, stirring the reaction at a uniform speed on a magnetic stirrer, taking the upper clear liquid, and measuring the removal result after centrifugation.

[0018] Furthermore, when measuring the desulfurization rate, the simulated oil includes dibenzothiophene and n-dodecane.

[0019] Furthermore, when measuring the denitrification rate, the simulated oil includes quinoline and n-dodecane.

[0020] Furthermore, the simulated oil includes dibenzothiophene, quinoline and n-dodecane, wherein the mass ratio of dibenzothiophene to quinoline is 4-7:3-6.

[0021] (III) Beneficial effects

[0022] The beneficial effects of the present invention are:

[0023] The present invention complexes two metal ions, vanadium and lanthanum, so that the catalyst can have a good removal effect in the process of desulfurization and denitrification.

[0024] When making the catalyst, citric acid or sodium citrate solution can complex vanadium ions and lanthanum together. Complexing agents, such as hydrogen peroxide solution, can convert vanadium ions that have not formed vanadium pentoxide after the reaction in the high-pressure reactor into vanadium pentoxide, thereby further improving the removal effect.

[0025] When using the catalyst, adding hydrogen peroxide can make peroxotitanic acid, so that the desulfurization and denitrification catalyst can play an effective role in the desulfurization or denitrification process. By removing nitrides and sulfides in different ways according to the ratio of nitrides and sulfides in the simulated oil, the catalyst cost can be saved.

[0026] Under ultraviolet light, the vanadium, lanthanum and peroxytitanic acid in the present invention generate photogenerated electron-hole pairs, combined with the redox cycle of vanadium and the electronic modification of lanthanum, to generate highly oxidizing active oxygen species (such as ·OH, ·O2-). These active species oxidize sulfur-containing compounds into sulfoxides or sulfones, and oxidize nitrogen-containing compounds into nitro compounds or inorganic nitrogen, ultimately achieving efficient desulfurization and denitrification. Peroxytitanic acid further improves the oxidation efficiency by providing additional oxidation capacity and synergizing with the photocatalytic process. DETAILED DESCRIPTION

[0027] The embodiments of the present invention are described in detail below.

[0028] Example 1

[0029] 1.08 g of lanthanum acetate was dissolved in 30 ml of deionized water to obtain a lanthanum acetate solution, and 0.057 g of citric acid was dissolved in 20 ml of deionized water to obtain a citric acid solution;

[0030] Place a 100ml three-necked flask in a constant temperature water bath at 30°C, add 20g of anhydrous ethanol, turn on the digital electric stirrer, adjust the speed to above 500rpm and maintain the intensity; use a pipette to accurately transfer 20g of butyl titanate to the system, and stir continuously for 1h until the system reacts evenly;

[0031] Vanadium-containing precipitate: Method 1, take 0.293g of ammonium metavanadate and dissolve it in 30ml deionized water, heat while stirring to obtain a yellow solution, adjust the pH to 4 with dilute hydrochloric acid solution, transfer the mixed solution to a 100ml polytetrafluoroethylene high-pressure reactor, keep heating at 160°C for 2h, cool naturally to room temperature, collect the precipitate, wash and centrifuge repeatedly, and dry it in a 110°C constant temperature drying oven for 12h to obtain a vanadium-containing precipitate. Method 2, directly sinter ammonium metavanadate to obtain vanadium pentoxide and then dissolve it in deionized water to obtain the vanadium-containing precipitate. This application uses method 1 as an example for illustration, and will not be repeated later.

[0032] Then pour the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask, then pour the citric acid solution into the three-necked flask and continue stirring for 3 hours until the system is evenly mixed, and age at room temperature for 10 hours; place the obtained solid in an oven and age at 70°C for 12 hours;

[0033] Three drops of hydrogen peroxide solution were added to the obtained solid, and the solid was allowed to stand at room temperature for 12 hours to obtain a vanadium-lanthanum co-doped peroxytitanic acid photocatalytic oxidation desulfurization and denitrification catalyst.

[0034] Example 2

[0035] 1.3 g of lanthanum acetate was dissolved in 30 ml of deionized water to obtain a lanthanum acetate solution, and 0.019 g of citric acid was dissolved in 15 ml of deionized water to obtain a citric acid solution;

[0036] Place a 100ml three-necked flask in a constant temperature water bath at 30°C, add 20g of anhydrous ethanol, turn on the digital electric stirrer, adjust the speed to above 500rpm and maintain the intensity; use a pipette to accurately transfer 3.4g of butyl titanate to the system, and stir continuously for 0.5h until the system reacts evenly;

[0037] Take 0.351 g of ammonium metavanadate and dissolve it in 30 ml of deionized water, heat it while stirring to obtain a yellow solution, adjust the pH to 5 with a dilute hydrochloric acid solution, transfer the mixed solution to a 100 ml polytetrafluoroethylene autoclave, keep heating at 160°C for 2 hours, cool it naturally to room temperature, collect the precipitate, wash it repeatedly, centrifuge it, and dry it in a constant temperature drying oven at 110°C for 12 hours to obtain a vanadium-containing precipitate;

[0038] Then pour the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask, then pour the citric acid solution into the three-necked flask and continue stirring for 2 hours until the system is evenly mixed, and age at room temperature for 8 hours; place the obtained solid in an oven and age at 70°C for 12 hours;

[0039] One drop of hydrogen peroxide solution was dripped onto the obtained solid, and the solid was allowed to stand at room temperature for 8 hours to obtain a vanadium-lanthanum co-doped peroxytitanic acid photocatalytic oxidation desulfurization and denitrification catalyst.

[0040] Example 3

[0041] 0.650 g of lanthanum acetate was dissolved in 30 ml of deionized water to obtain a lanthanum acetate solution, and 0.019 g of citric acid was dissolved in 15 ml of deionized water to obtain a citric acid solution;

[0042] Place a 100ml three-necked flask in a constant temperature water bath at 30°C, add 14.7g of anhydrous ethanol, turn on the digital electric stirrer, adjust the speed to above 500rpm and maintain the intensity; use a pipette to accurately transfer 4.7g of butyl titanate to the system, and stir continuously for 1h until the system reacts evenly;

[0043] Take 0.234 g of ammonium metavanadate and dissolve it in 30 ml of deionized water, stir and heat to obtain a yellow solution, adjust the pH to 3 with dilute hydrochloric acid solution, transfer the mixed solution to a 100 ml polytetrafluoroethylene autoclave, keep heating at 160°C for 2 hours, cool naturally to room temperature, collect the precipitate, repeatedly wash and centrifuge, and dry it in a constant temperature drying oven at 110°C for 12 hours to obtain a vanadium-containing precipitate;

[0044] Then pour the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask, then pour the citric acid solution into the three-necked flask and continue stirring for 2.5 hours until the system is evenly mixed, and place it at room temperature for 10 hours; place the obtained solid in an oven and age it at 70°C for 12 hours;

[0045] Two drops of hydrogen peroxide solution were added to the obtained solid, and the solid was allowed to stand at room temperature for 8 hours to obtain a vanadium-lanthanum co-doped peroxytitanic acid photocatalytic oxidation desulfurization and denitrification catalyst.

[0046] Example 4

[0047] 0.866 g of lanthanum acetate was dissolved in 30 ml of deionized water to obtain a lanthanum acetate solution, and 0.038 g of citric acid was dissolved in 20 ml of deionized water to obtain a citric acid solution;

[0048] Place a 100ml three-necked flask in a constant temperature water bath at 30°C, add 14.7g of anhydrous ethanol, turn on the digital electric stirrer, adjust the speed to above 500rpm and maintain the intensity; use a pipette to accurately transfer 4.7g of butyl titanate to the system, and stir continuously for 1h until the system reacts evenly;

[0049] Take 0.205g of ammonium metavanadate and dissolve it in 30ml of deionized water, heat it while stirring to obtain a yellow solution, adjust the pH to 2 with a dilute hydrochloric acid solution, transfer the mixed solution to a 100ml polytetrafluoroethylene autoclave, keep heating at 160°C for 2h, cool it naturally to room temperature, collect the precipitate, wash it repeatedly, centrifuge it, and dry it in a constant temperature drying oven at 110°C for 12h to obtain a vanadium-containing precipitate;

[0050] Then pour the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask, then pour the citric acid solution into the three-necked flask and continue stirring for 2.5 hours until the system is evenly mixed, and place it at room temperature for 10 hours; place the obtained solid in an oven and age it at 70°C for 12 hours;

[0051] Three drops of hydrogen peroxide solution were added to the obtained solid, and the solid was allowed to stand at room temperature for 8 hours to obtain a vanadium-lanthanum co-doped peroxytitanic acid photocatalytic oxidation desulfurization and denitrification catalyst.

[0052] Example 5

[0053] 0.433 g of lanthanum acetate was dissolved in 30 ml of deionized water to obtain a lanthanum acetate solution, and 0.019 g of citric acid was dissolved in 15 ml of deionized water to obtain a citric acid solution;

[0054] Place a 100ml three-necked flask in a constant temperature water bath at 30°C, add 14.7g of anhydrous ethanol, turn on the digital electric stirrer, adjust the speed to above 500rpm and maintain the intensity; use a pipette to accurately transfer 4.7g of butyl titanate to the system, and stir continuously for 1h until the system reacts evenly;

[0055] Take 0.175g of ammonium metavanadate and dissolve it in 30ml of deionized water, heat it while stirring to obtain a yellow solution, adjust the pH to 2 with a dilute hydrochloric acid solution, transfer the mixed solution to a 100ml polytetrafluoroethylene autoclave, keep heating at 160°C for 2h, cool it naturally to room temperature, collect the precipitate, wash it repeatedly, centrifuge it, and dry it in a constant temperature drying oven at 110°C for 12h to obtain a vanadium-containing precipitate;

[0056] Then pour the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask, then pour the citric acid solution into the three-necked flask and continue stirring for 2.5 hours until the system is evenly mixed, and place it at room temperature for 10 hours; place the obtained solid in an oven and age it at 70°C for 12 hours;

[0057] Four drops of hydrogen peroxide solution were dripped onto the obtained solid, and the solid was allowed to stand at room temperature for 12 hours to obtain a vanadium-lanthanum co-doped peroxytitanic acid photocatalytic oxidation desulfurization and denitrification catalyst.

[0058] Example 6

[0059] 0.758 g of lanthanum acetate was dissolved in 30 ml of deionized water to obtain a lanthanum acetate solution, and 0.019 g of citric acid was dissolved in 15 ml of deionized water to obtain a citric acid solution;

[0060] Place a 100ml three-necked flask in a constant temperature water bath at 40°C, add 14.7g of anhydrous ethanol, turn on the digital electric stirrer, adjust the speed to above 500rpm and maintain the intensity; use a pipette to accurately transfer 4.7g of butyl titanate to the system, and stir continuously for 1h until the system reacts evenly;

[0061] Take 0.117 g of ammonium metavanadate and dissolve it in 30 ml of deionized water, stir and heat to obtain a yellow solution, adjust the pH to 2 with a dilute hydrochloric acid solution, transfer the mixed solution to a 100 ml polytetrafluoroethylene autoclave, keep heating at 160° C. for 2 h, cool naturally at room temperature, wash the precipitate repeatedly with a mixed solution of deionized water and anhydrous ethanol for at least 3 times, transfer it to a 110° C. constant temperature drying oven and keep it for 12 h to obtain a vanadium-containing precipitate;

[0062] Then pour the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask, then pour the citric acid solution into the three-necked flask and continue stirring for 2.5 hours until the system is evenly mixed, and age at room temperature for 10 hours;

[0063] The obtained solid was placed in an oven and aged at 70°C for 12 h;

[0064] Two drops of hydrogen peroxide solution were added to the obtained solid, and the solid was allowed to stand at room temperature for 8 hours to obtain a vanadium-lanthanum co-doped peroxytitanic acid photocatalytic oxidation desulfurization and denitrification catalyst.

[0065] Example 7

[0066] 0.758 g of lanthanum acetate was dissolved in 30 ml of deionized water to obtain a lanthanum acetate solution, and 0.019 g of citric acid was dissolved in 15 ml of deionized water to obtain a citric acid solution;

[0067] Place a 100ml three-necked flask in a constant temperature water bath at 40°C, add 14.7g of anhydrous ethanol, turn on the digital electric stirrer, adjust the speed to above 500rpm and maintain the intensity; use a pipette to accurately transfer 4.7g of butyl titanate to the system, and stir continuously for 1h until the system reacts evenly;

[0068] Take 0.1 g of ammonium metavanadate and dissolve it in 30 ml of deionized water, heat it while stirring to obtain a yellow solution, adjust the pH to 2 with a dilute hydrochloric acid solution, transfer the mixed solution to a 100 ml polytetrafluoroethylene autoclave, keep heating at 160° C. for 2 h, cool it naturally at room temperature, wash the precipitate repeatedly with a mixed solution of deionized water and anhydrous ethanol for at least 3 times, transfer it to a 110° C. constant temperature drying oven and keep it for 12 h to obtain a vanadium-containing precipitate;

[0069] Then pour the lanthanum acetate solution and the vanadium-containing precipitate into a three-necked flask, then pour the citric acid solution into the three-necked flask and continue stirring for 2.5 hours until the system is evenly mixed, and age at room temperature for 10 hours;

[0070] The obtained solid was placed in an oven and aged at 70°C for 12 h;

[0071] Two drops of hydrogen peroxide solution were added to the obtained solid, and the solid was allowed to stand at room temperature for 8 hours to obtain a vanadium-lanthanum co-doped peroxytitanic acid photocatalytic oxidation desulfurization and denitrification catalyst.

[0072] The desulfurization method is as follows:

[0073] Simulated oil: dibenzothiophene + n-dodecane, ultrasonic dissolution;

[0074] 1. Put simulated oil + methanol + drop of hydrogen peroxide solution + (using the catalyst in the above Examples 1 to 7) + rotor into a beaker (sealed with plastic wrap);

[0075] 2. Place the beaker on a magnetic stirrer and stir at a constant speed;

[0076] 3. Total reaction time 4h (0.5h dark light, 3.5h UV light irradiation);

[0077] 4. Take an appropriate amount of supernatant, centrifuge, and measure the desulfurization rate.

[0078] The denitrification method is as follows:

[0079] Simulated oil: quinoline + n-dodecane, ultrasonic dissolution;

[0080] 1. Put simulated oil + methanol + drop of hydrogen peroxide solution + (using the catalyst in the above Examples 1 to 7) + rotor into a beaker (sealed with plastic wrap);

[0081] 2. Place the beaker on a magnetic stirrer and stir at a constant speed;

[0082] 3. Total reaction time 4h (0.5h dark light, 3.5h UV light irradiation);

[0083] 4. Take an appropriate amount of the supernatant, centrifuge, and measure the denitrification rate.

[0084] The data and removal rates of Examples 1 to 7 are as follows:

[0085]

[0086]

[0087] As shown in the table above, the catalyst in Example 6 has the highest desulfurization or denitrification rates, which are 98.6% and 70.2% respectively.

[0088] Furthermore, the catalyst prepared in Example 6 was used, and the simulated oil was a mixture of dibenzothiophene, quinoline and n-dodecane, and the removal steps were as follows:

[0089] 1. Simulated oil: dibenzothiophene, quinoline, n-dodecane, ultrasonic dissolution;

[0090] 2. Put simulated oil + methanol + drop of hydrogen peroxide solution + catalyst in Example 6 + rotor into a beaker (seal with plastic wrap);

[0091] 3. Place the beaker on a magnetic stirrer and stir at a constant speed;

[0092] 4. Total reaction time 4h (0.5h dark light, 3.5h UV light irradiation);

[0093] 5. Take an appropriate amount of the supernatant, centrifuge, and measure the desulfurization rate and denitrification rate.

[0094] The specific mixing ratio of dibenzothiophene and quinoline and the removal rate after mixing are shown in the following table.

[0095]

[0096] It can be concluded from the above table that when the ratio of dibenzothiophene and quinoline in the simulated oil is in Example 9, the desulfurization rate and denitrification rate are the highest. However, the desulfurization rate and denitrification rate of Example 9 are still less than the removal rate in Example 6, because the removal rate in Example 6 is the desulfurization rate measured by dibenzothiophene alone mixed with n-dodecane as the simulated oil, and the denitrification rate measured by quinoline alone mixed with n-dodecane as the simulated oil. When Example 9 is measuring the desulfurization rate, quinoline is also present in the simulated oil, which has a certain impact on desulfurization, and when measuring denitrification, dibenzothiophene is also present in the simulated oil, which has a certain impact on denitrification. Thereby causing the removal rate of Example 9 to be slightly less than the removal rate in Example 6.

[0097] It can be seen from Example 6 and Example 9 that Example 9 is closer to actual petroleum, which contains not only nitrides but also a certain amount of sulfides. The catalyst of the present application can be used for desulfurization and denitrification at the same time, with a desulfurization rate of 90.3% and a denitrification rate of 60.7%. At this time, the removal ratio (desulfurization rate 90.3%: denitrification rate 60.7%) is about 1.49. The removal ratio is the ratio of the desulfurization rate to the denitrification rate.

[0098] Example 11: The catalyst prepared in Example 6 is used again. Dibenzothiophene is first removed from the catalyst and the mixture is mixed with n-dodecane as a simulated oil. The measured desulfurization rate is 98.6%. The desulfurized catalyst is then recovered. The recovered catalyst is then used to remove quinoline and the mixture is mixed with n-dodecane as a simulated oil. The measured denitrification rate is 50.2%. The removal ratio (desulfurization rate 98.6%: denitrification rate 50.2%) is about 1.95.

[0099] Example 12: The catalyst prepared in Example 6 was used again. First, quinoline was removed from the catalyst and the mixture was mixed with n-dodecane as a simulated oil. The measured denitrification rate was 70.2%. Then, the catalyst after denitrification was recovered. Then, the recovered catalyst was used to remove dibenzothiophene and the mixture was mixed with n-dodecane as a simulated oil. The measured desulfurization rate was 81.6%. The removal ratio (desulfurization rate 81.6%: denitrification rate 70.2%) was about 1.16.

[0100] In this case, it can be concluded that when the catalyst is directly mixed with simulated oil containing sulfides and nitrides for desulfurization and denitrification, the average removal rate measured is 75.5% (the desulfurization rate reaches 90.3%, and the denitrification rate reaches 60.7%). The average removal rate measured in Example 11 is 74.4% (the desulfurization rate is 98.6%, and the denitrification rate is 50.2%). The average removal rate measured in Example 12 is 75.9% (the denitrification rate is 70.2%, and the desulfurization rate is 81.6%). It can be seen that the average removal rate is stable at around 74% to 76%. The removal ratio is 1.16 to 1.95.

[0101] In this way, users can choose different removal methods according to the sulfur content and nitrogen content in the oil. For example, when the removal ratio in the simulated oil is greater than 1.16-1.95, users can use the catalyst of this application to desulfurize first, and then recover the catalyst for denitrification. When the removal ratio in the simulated oil is less than 1.16-1.95, users can use the catalyst of this application to denitrify first, and then recover the catalyst for desulfurization. When the removal ratio in the simulated oil is equal to 1.16-1.95, in order to save steps, the catalyst of this application can be directly used to desulfurize and denitrify the oil at the same time.

[0102] The beneficial effects of the present invention are:

[0103] The present invention complexes two metal ions, vanadium and lanthanum, so that the catalyst can have a good removal effect in the process of desulfurization and denitrification.

[0104] When making the catalyst, citric acid or sodium citrate solution can complex vanadium ions and lanthanum together. Complexing agents, such as hydrogen peroxide solution, can convert vanadium ions that have not formed vanadium pentoxide after the reaction in the high-pressure reactor into vanadium pentoxide, thereby further improving the removal effect.

[0105] When using the catalyst, adding hydrogen peroxide can make peroxotitanic acid, so that the desulfurization and denitrification catalyst can play an effective role in the desulfurization or denitrification process. According to the ratio of nitrides and sulfides in petroleum, nitrides and sulfides can be removed in different ways, thus saving catalyst costs.

[0106] In the description of this specification, specific features, structures, materials or characteristics may be combined in an appropriate manner in any one or more embodiments or examples.

[0107] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a desulfurization and denitrification catalyst, characterized in that: The following steps are involved: S1, placing a three-necked flask in a constant temperature water bath, adding anhydrous ethanol, turning on a digital electric stirrer, adjusting the speed for stirring; pipetting butyl titanate into the three-necked flask, and continuously stirring to obtain a mixed solution A; S2, placing the lanthanum acetate solution and the vanadium-containing precipitate in a three-necked flask and mixing them with the mixed solution A, then pouring the citric acid solution into the three-necked flask and continuing to stir, then stopping, and placing it at room temperature for aging to obtain a solid B; S4, placing solid B in an oven to dry; S5, adding a certain amount of complexing agent to the solid B dried in S4, and leaving it to stand at room temperature to obtain the desulfurization and denitrification catalyst.

2. The method for preparing a desulfurization and denitrification catalyst according to claim 1, characterized in that: Dissolve ammonium metavanadate in deionized water, heat while stirring to obtain a yellow solution, adjust the pH to obtain a mixed solution B, transfer the mixed solution B to a polytetrafluoroethylene high-pressure reactor for heating, cool naturally at room temperature, repeatedly wash the mixed solution B with deionized water and anhydrous ethanol solution, obtain solid C after precipitation, dry the solid C and dissolve it in deionized water to obtain the vanadium-containing precipitate.

3. The method for preparing a desulfurization and denitrification catalyst according to claim 2, characterized in that: The pH of the mixed solution B is 1-5.

4. The method for preparing a desulfurization and denitrification catalyst according to claim 1, characterized in that: The ammonium metavanadate is directly sintered to obtain vanadium pentoxide, which is then dissolved in deionized water to obtain the vanadium-containing precipitate.

5. The method for preparing a desulfurization and denitrification catalyst according to claim 1, characterized in that: The complexing agent is a hydrogen peroxide solution.

6. A method for using a desulfurization and denitrification catalyst, characterized in that: The desulfurization and denitrification catalyst according to any one of claims 1 to 5 is used, and the method of use comprises the following steps: placing the simulated oil, methanol, a drop of hydrogen peroxide solution, the desulfurization and denitrification catalyst, and a rotor into a beaker, stirring the reaction at a uniform speed on a magnetic stirrer, taking the upper clear liquid, and measuring the removal result after centrifugation.

7. The method for using the desulfurization and denitrification catalyst according to claim 6, characterized in that: When measuring the desulfurization rate, the simulated oil includes dibenzothiophene and n-dodecane.

8. The method for using the desulfurization and denitrification catalyst according to claim 6, characterized in that: When measuring the denitrification rate, the simulated oil includes quinoline and n-dodecane.

9. The method for using the desulfurization and denitrification catalyst according to claim 6, characterized in that: The simulated oil comprises dibenzothiophene, quinoline and n-dodecane, wherein the mass ratio of dibenzothiophene to quinoline is 4-7:3-6.

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