CN113617397B - Preparation of porous carbon-supported NHPI catalyst and application of catalyst in fuel oil oxidative desulfurization - Google Patents
Preparation of porous carbon-supported NHPI catalyst and application of catalyst in fuel oil oxidative desulfurization Download PDFInfo
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Abstract
The invention relates to a preparation method of a porous carbon supported NHPI catalyst and application thereof in fuel oil oxidative desulfurization, N-hydroxyphthalimide NHPI is supported on porous carbon PC dispersed in absolute ethanol solution by a dipping and supporting method, and is dried to prepare the supported catalyst NHPI/PC, the preparation process is simple, cobalt salts including but not limited to cobalt acetate, cobalt chloride and cobalt acetylacetonate are used as cocatalysts, the activity of the supported catalyst NHPI/PC taking NHPI as an active center for oxidative desulfurization is obviously improved, various sulfides, particularly aromatic sulfides, in oil phases of fuel oil and the like can be effectively removed by stirring at relatively low temperature and normal pressure, the catalyst is easy to separate, the problems of complicated separation and difficult recovery of homogeneous catalysts are solved, the circulating performance is excellent, compared with the traditional desulfurization process, the desulfurization efficiency is extremely high, the reaction condition is mild, the air is used as an oxidant, the desulfurization cost and the operation difficulty are obviously reduced, the deep desulfurization standard is met, and the development concept of green chemical industry is met.
Description
Technical Field
The invention relates to preparation of a porous carbon-supported NHPI catalyst and application thereof in fuel oil oxidative desulfurization, and belongs to the field of fuel oil desulfurization.
Background
In recent years, with the rapid development of industrialization, the demand of human beings for fuel is increasing ≡! However, since the fuel contains sulfur-containing compounds, such as Benzothiophene (BT) and Dibenzothiophene (DBT), sulfur oxide is generated during combustion to form an environment damaged by acid rain, fuel standards are introduced in various countries, and sulfur content of the fuel is controlled, so that desulfurization is particularly important to solve the problem.
At present, the industrially used desulfurization process mainly comprises Hydrodesulfurization (HDS), the hydrodesulfurization process is mature, the removal of mercaptan, sulfide and disulfide is very effective, the removal of thiophene compounds with steric hindrance is difficult, the reaction conditions are harsh, high temperature (320-380 ℃) and high pressure (30-70 atm) are needed, the desulfurization cost is high, and the waste of energy sources and the improvement of fuel price are directly caused. Therefore, it is imperative to develop a non-hydrodesulfurization mode which is efficient, low in cost and mild in reaction conditions.
N-hydroxyphthalimide (NHPI) is a cheap, easily available and nontoxic catalyst, is a precursor of phthalimide-N-oxyl (PINO) free radical, but when NHPI is simply used as a homogeneous catalyst, the catalyst has the advantages of high activity and mild reaction conditions, but has complicated separation from products, the catalyst is difficult to recover and regenerate, and the activity of removing various sulfides in fuel oil is required to be improved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a porous carbon-supported NHPI catalyst and application thereof in fuel oil oxidative desulfurization.
The invention aims to prepare the supported heterogeneous catalyst with excellent performance by loading NHPI on the surface of porous carbon, solve the defects of a homogeneous catalyst, can be recycled, has good performance in the application of oxidizing and desulfurizing fuel oil, and meets the standard of deep desulfurization;
the invention is realized by the following technical scheme:
a preparation method of a porous carbon-supported NHPI catalyst comprises the following steps: n-hydroxyphthalimide NHPI is loaded on porous carbon PC dispersed in absolute ethanol solution by an impregnation loading method, and dried to prepare a loaded catalyst NHPI/PC.
The preparation method of the porous carbon-supported NHPI catalyst comprises the following specific steps:
(1) Preparation of porous carbon PC: mixing petroleum coke, urea and zirconia particles into a stainless steel ball milling tank according to a mass ratio of 1:1-1:20, ball milling in a planetary ball mill at a rotating speed of 100-600rpm, calcining the mixture obtained by ball milling at a calcining temperature of 500-1000 ℃, wherein the calcining atmosphere is argon and nitrogen, the heating rate is 2 ℃/min-10 ℃/min, and the calcining time is 1h-5h, so as to obtain porous carbon PC;
(2) Dispersing 0.05g-1g of porous carbon PC in 10ml-100ml of absolute ethanol solution by ultrasonic treatment for 10-60 min;
(3) Grinding commercial grade 0.01g-0.3g N-hydroxyphthalimide NHPI, adding the ground commercial grade into the mixed solution of the porous carbon PC and the absolute ethyl alcohol in the step (2), stirring for 6-24 hours at the reaction temperature of 25-75 ℃ and the stirring rotation speed of 100-800rpm, and carrying out impregnation loading;
(4) And (3) taking the mixture subjected to the impregnation and loading, drying for 4-12 hours at the vacuum drying temperature of 30-70 ℃ in a vacuum drying oven, taking out, grinding to obtain a supported catalyst NHPI/PC, and preserving.
The invention also aims to remarkably improve the activity of the supported catalyst NHPI/PC taking NHPI as an active center for oxidative desulfurization by taking cobalt salt as a cocatalyst, has simple process, can be carried out at relatively low temperature, normal pressure and air atmosphere, remarkably reduces desulfurization cost and operation difficulty, remarkably improves the desulfurization rate of various sulfides in an oil phase, particularly aromatic sulfides, and accords with the development of green chemical industry.
The invention is realized by the following technical scheme:
the application of the porous carbon supported NHPI catalyst in fuel oil oxidative desulfurization comprises the steps of preparing a desulfurized oil product by using the supported catalyst NHPI/PC prepared in the above way, carrying out oxidative desulfurization on an oil phase containing sulfides including but not limited to fuel oil under activated oxygen, adding cobalt salts including but not limited to cobalt acetate, cobalt chloride and cobalt acetylacetonate as a catalytic auxiliary agent during oxidative desulfurization, separating and recycling the supported catalyst NHPI/PC, wherein the supported catalyst NHPI/PC can be recycled;
catalytic oxidation to remove aliphatic and aromatic sulfides in the oil phase, including, but not limited to, dibenzothiophene (DBT), 4-methyldibenzothiophene (4-DMDBT), 4, 6-dimethyldibenzothiophene (4, 6-DMDBT);
the application of the porous carbon-supported NHPI catalyst in combustion comprises the following specific steps:
respectively dissolving Dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT) or 4, 6-dimethyldibenzothiophene (4, 6-DMDBT) in dodecane, and preparing simulated oil with 50-800ppm of sulfur content by taking hexadecane as an internal standard;
adding 5ml-50ml of model oil, 0.01g-1g of supported catalyst NHPI/PC and 0.001g-0.01g of cocatalyst cobalt salt into a three-neck flask provided with a condenser tube in sequence, placing the three-neck flask into an oil bath, blowing air into a reaction device in a bubble form by using an air pump, fully stirring by using a magnetic rotation heating stirrer, taking upper clean oil as a desulfurization oil product under the conditions that the temperature of the oil bath is 80-140 ℃, the air flow is 50-200ml/min and the stirring speed is 100-1000rmp, standing or centrifugally separating to recover the supported catalyst NHPI/PC, and measuring the sulfur content by gas chromatography, wherein the calculated desulfurization rate can preferably reach 100%.
The beneficial effects of the invention are as follows:
(1) According to the invention, amorphous carbon petroleum coke is treated into a porous carbon PC carrier with low cost and excellent performance, and N-hydroxyphthalimide NHPI is loaded on the porous carbon PC by a simple impregnation loading method to prepare the supported heterogeneous catalyst NHPI/PC with excellent performance, and the supported heterogeneous catalyst NHPI/PC has the advantages of proper preparation conditions and parameters, simple preparation process, high NHPI desulfurization activity, mild reaction conditions and the like, so that the heterogeneous catalyst is easy to separate and recycle.
(2) According to the invention, the prepared supported catalyst NHPI/PC can effectively remove various sulfides, particularly aromatic sulfides, in oil phases such as fuel oil at relatively low temperature and normal pressure under the synergistic effect of cobalt salt serving as a cocatalyst, the catalyst takes air as an oxidant, the desulfurization cost is greatly reduced, the catalyst is a heterogeneous catalyst, the catalyst is easy to separate from desulfurized oil products, the cycle performance is excellent, and compared with the traditional desulfurization process, the catalyst has the advantages of extremely high desulfurization efficiency, mild reaction conditions, easiness in operation and accordance with the development concept of green chemical industry.
Drawings
FIG. 1 shows XRD and FT-IR spectra of PC, NHPI, and NHPI/PC prepared in example 1 of the invention.
FIG. 2 is a schematic diagram of the catalytic oxidation reaction mechanism of the present invention.
FIG. 3 is a graph of the cyclic performance of the supported catalyst NHPI/PC of the present invention.
FIG. 4 is a GC-MS analysis chart of the invention.
Detailed Description
The following description of the embodiments of the invention will be given with reference to the accompanying drawings and examples.
The material reagents used in the present invention are commercially available without any particular explanation.
When the sulfur content is measured by a gas chromatograph, the desulfurization rate is calculated as follows:
example 1:
(1) A preparation method of a porous carbon supported NHPI catalyst comprises the following steps:
preparation of porous carbon PC-1: mixing petroleum coke and urea into a stainless steel ball milling tank according to a mass ratio of 1:10 and zirconia particles, ball milling in a planetary ball mill at a rotating speed of 450rpm, calcining the mixture obtained by ball milling at a calcining temperature of 1000 ℃, calcining the mixture in nitrogen at a heating rate of 5 ℃/min for 2 hours to obtain porous carbon PC-1;
weighing 0.08g of porous carbon PC-1, adding 20ml of absolute ethyl alcohol into a beaker, then carrying out ultrasonic dispersion for half an hour, taking out 0.02g of commercial grade N-hydroxyphthalimide NHPI added with grinding treatment, stirring for 24 hours at the reaction temperature of 25 ℃ and the stirring rotation speed of 800rpm, carrying out impregnation loading until the NHPI is completely and fully dispersed in the PC-1, taking out the mixture after impregnation loading, placing the mixture into a vacuum drying oven, drying for 12 hours at the vacuum drying temperature of 60 ℃, taking out and grinding to obtain a supported catalyst NHPI/PC-1, and storing;
referring to fig. 1, the supported catalyst NHPI/PC-1 was successfully prepared;
(2) The application of the porous carbon-supported NHPI catalyst in fuel oil oxidative desulfurization comprises the following steps:
20ml of model oil containing DBT (sulfur content 200 ppm), 0.05g of supported catalyst NHPI/PC-1 and 0.0024g of cocatalyst cobalt acetate are sequentially added into a three-neck flask provided with a condenser tube, the three-neck flask is placed in an oil bath with 120 ℃, air is blown into a reaction device in a bubble mode by an air pump, the mixture is fully stirred by a magnetic rotary heating stirrer, the mixture is reacted at the air flow rate of 150ml/min and the stirring speed of 800rmp, the upper clean oil is taken every one hour, the sulfur content is measured by a gas chromatograph, the desulfurization rate is calculated, and the desulfurization rate can reach 100% after the reaction for 3 hours.
Example 2:
(1) A preparation method of a porous carbon supported NHPI catalyst comprises the following steps:
preparation of porous carbon PC-2: mixing petroleum coke and urea into a stainless steel ball milling tank according to a mass ratio of 1:1 and zirconia particles, ball milling in a planetary ball mill at a rotating speed of 100rpm, calcining the mixture obtained by ball milling at a calcining temperature of 500 ℃, calcining the mixture in nitrogen at a heating rate of 2 ℃/min for 1h, and obtaining porous carbon PC-2;
weighing 0.05g of porous carbon PC-2, adding 10ml of absolute ethyl alcohol into a beaker, then carrying out ultrasonic dispersion for half an hour, taking out 0.01g of commercial grade N-hydroxyphthalimide NHPI added with grinding treatment, stirring for 18 hours at the reaction temperature of 30 ℃ and the stirring rotation speed of 600rpm, carrying out impregnation loading until the NHPI is completely and fully dispersed in the PC-2, taking out the mixture after impregnation loading, placing the mixture into a vacuum drying oven, drying for 10 hours at the vacuum drying temperature of 50 ℃, taking out and grinding to obtain a supported catalyst NHPI/PC-2, and storing;
(2) The application of the porous carbon-supported NHPI catalyst in fuel oil oxidative desulfurization comprises the following steps:
5ml of model oil containing 4-MDBT (sulfur content 50 ppm), 0.01g of supported catalyst NHPI/PC-2 and 0.0014g of catalyst promoter cobalt acetylacetonate are sequentially added into a three-neck flask provided with a condenser tube, the three-neck flask is placed in an oil bath with a temperature of 80 ℃, air is blown into a reaction device in a bubble form by an air pump, the mixture is fully stirred by a magnetic cyclone heating stirrer, the mixture is reacted at a stirring speed of 100rmp at an air flow rate of 20ml/min, the upper clean oil is taken every one hour, the sulfur content is measured by a gas chromatograph, the desulfurization rate is calculated, and the desulfurization rate can reach 100% after 8 hours of reaction.
Example 3:
(1) A preparation method of a porous carbon supported NHPI catalyst comprises the following steps:
preparation of porous carbon PC-3: mixing petroleum coke and urea into a stainless steel ball milling tank according to a mass ratio of 1:20 and zirconia particles, ball milling in a planetary ball mill at a rotating speed of 600rpm, calcining the mixture obtained by ball milling at a calcining temperature of 1000 ℃, calcining the mixture in argon at a heating rate of 10 ℃/min for 5 hours to obtain porous carbon PC-3;
1g of porous carbon PC-3 is weighed and added into a beaker, then 100ml of absolute ethyl alcohol is measured and put into the beaker, then ultrasonic dispersion is carried out for half an hour, 0.3g of commercial grade N-hydroxyphthalimide NHPI added into the grinding treatment is taken out, stirring is carried out for 7 hours at the reaction temperature of 75 ℃ and the stirring rotation speed of 800rpm, impregnation loading is carried out until the NHPI is completely and fully dispersed into PC-3, the mixture after impregnation loading is taken out and put into a vacuum drying oven, drying is carried out for 12 hours at the vacuum drying temperature of 50 ℃, and the mixture is taken out and ground to obtain a supported catalyst NHPI/PC-3 for preservation;
(2) The application of the porous carbon-supported NHPI catalyst in fuel oil oxidative desulfurization comprises the following steps:
50ml of model oil containing DBT (sulfur content 800 ppm), 1g of supported catalyst NHPI/PC-3 and 0.0024g of cocatalyst cobalt chloride are sequentially added into a three-neck flask provided with a condenser tube, the three-neck flask is placed in an oil bath at 140 ℃, air is blown into a reaction device in a bubble mode by an air pump, the mixture is fully stirred by a magnetic rotation heating stirrer, the mixture is reacted at the stirring speed of 800rmp with the air flow rate of 200ml/min, the upper clean oil is taken every one hour, the sulfur content is measured by a gas chromatograph, and the desulfurization rate is calculated, so that the desulfurization rate can reach 95% after the reaction for 3 hours.
Example 4:
(1) A preparation method of a porous carbon supported NHPI catalyst comprises the following steps:
preparation of porous carbon PC-4: mixing petroleum coke and urea into a stainless steel ball milling tank according to a mass ratio of 1:5 and zirconia particles, ball milling in a planetary ball mill at a rotating speed of 500rpm, calcining the mixture obtained by ball milling at a calcining temperature of 900 ℃, calcining the mixture in nitrogen at a heating rate of 4 ℃/min for 4 hours, and obtaining porous carbon PC-4;
weighing 0.075g of porous carbon PC-4, adding 20ml of absolute ethyl alcohol into a beaker, then carrying out ultrasonic dispersion for half an hour, taking out 0.02g of commercial grade N-hydroxyphthalimide NHPI added with grinding treatment, stirring for 12 hours at the reaction temperature of 35 ℃ and the stirring rotation speed of 50rpm, carrying out impregnation loading until the NHPI is completely and fully dispersed in the PC-4, taking out the mixture after impregnation loading, placing the mixture into a vacuum drying oven, drying for 12 hours at the vacuum drying temperature of 50 ℃, taking out and grinding to obtain a supported catalyst NHPI/PC-4, and storing;
(2) The application of the porous carbon-supported NHPI catalyst in fuel oil oxidative desulfurization comprises the following steps:
20ml of model oil containing 4,6-DMDBT (sulfur content: 500 ppm), 0.05g of supported catalyst NHPI/PC-4 and 0.0024g of cocatalyst cobalt acetate are sequentially added into a three-neck flask provided with a condenser tube, the three-neck flask is placed into an oil bath at 120 ℃, air is blown into a reaction device in a bubble mode by an air pump, the mixture is fully stirred by a magnetic rotation heating stirrer, the mixture is reacted at a blowing air flow rate of 100ml/min and a stirring speed of 8000rmp, upper clear oil is taken every other hour, the sulfur content is measured by a gas chromatograph, the desulfurization rate is calculated, and the desulfurization rate can reach 97% after 4 hours of reaction.
Example 5:
(1) A preparation method of a porous carbon supported NHPI catalyst comprises the following steps:
preparation of porous carbon PC-5: mixing petroleum coke and urea into a stainless steel ball milling tank according to a mass ratio of 1:8 and zirconia particles, ball milling in a planetary ball mill at a rotating speed of 550rpm, calcining the mixture obtained by ball milling at a calcining temperature of 700 ℃, calcining the mixture in nitrogen at a heating rate of 3 ℃/min for 3 hours to obtain porous carbon PC-5;
weighing 0.085g of porous carbon PC-5, adding 40ml of absolute ethyl alcohol into a beaker, then carrying out ultrasonic dispersion for half an hour, taking out 0.015g of commercial grade N-hydroxyphthalimide NHPI added with grinding treatment, stirring for 12 hours at the reaction temperature of 25 ℃ and the stirring rotation speed of 500rpm, carrying out impregnation loading until the NHPI is completely and fully dispersed in PC-5, taking out the mixture after impregnation loading, placing the mixture into a vacuum drying oven, drying for 12 hours at the vacuum drying temperature of 50 ℃, taking out and grinding to obtain a supported catalyst NHPI/PC-5, and storing;
(2) The application of the porous carbon-supported NHPI catalyst in fuel oil oxidative desulfurization comprises the following steps:
20ml of model oil containing DBT (sulfur content 800 ppm), 0.05g of supported catalyst NHPI/PC-5 and 0.0014g of cocatalyst cobalt acetate are sequentially added into a three-neck flask provided with a condenser tube, the three-neck flask is placed in an oil bath at 110 ℃, air is blown into a reaction device in a bubble mode by an air pump, the mixture is fully stirred by a magnetic rotary heating stirrer, the mixture is reacted at the air flow rate of 150ml/min and the stirring speed of 800rmp, the upper clean oil is taken every one hour, the sulfur content is measured by a gas chromatograph, the desulfurization rate is calculated, and the desulfurization rate can reach 79% after 4 hours of reaction.
Comparative example:
the activity of oxidation desulfurization is carried out by taking independent N-hydroxyphthalimide NHPI, porous carbon PC and cobalt acetate as catalysts;
20ml of model oil (sulfur content 100 ppm) containing DBT (sulfur content) is added into a three-neck flask with a condenser pipe, the three-neck flask is placed in an oil bath at 120 ℃, then air is blown into a reaction device in the form of bubbles by an air pump, the mixture is fully stirred by a magnetic rotation heating stirrer, the mixture is reacted at the stirring speed of 800rmp at the air flow rate of 150ml/min, the upper clear oil is taken every one hour, the sulfur content is measured by a gas chromatograph, after 4 hours of reaction, the desulfurization rate by taking N-hydroxyphthalimide NHPI as a catalyst is 49%, the desulfurization rate by taking porous carbon PC-1 as a catalyst is 20%, and the desulfurization rate by taking cobalt acetate as a catalyst is 25%.
Referring to FIG. 2, the desulfurization mechanism of the catalytic oxidation reaction of examples 1-5 of the present invention can be seen.
As can be seen from fig. 3, the catalyst has good cycle performance;
referring to FIG. 4, it can be seen that DBT in the model oil is oxidized to DBTO 2 。
The embodiment and the comparative example show that the invention solves the problems of complicated separation and difficult recovery of homogeneous catalyst by loading NHPI on the surface of porous carbon, has good cycle performance, and the catalyst NHPI/PC prepared by the invention has excellent performance in the aspect of oil phase desulfurization containing various sulfides, especially aromatic sulfides including but not limited to fuel oil under the synergistic effect of cobalt salt as a cocatalyst.
The present invention is not limited to the above-mentioned embodiments, and any person skilled in the art should, within the scope of the present invention, use the equivalent structures or equivalent processes disclosed in the present invention, or use the equivalent structures or equivalent processes directly or indirectly in other related technical fields, so that the present invention is easily contemplated to be modified or replaced. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (9)
1. The preparation method of the porous carbon-supported NHPI oxidation desulfurization catalyst is characterized by comprising the following steps of: loading N-hydroxyphthalimide NHPI on porous carbon PC dispersed in an absolute ethanol solution by an impregnation loading method, and drying to prepare a supported catalyst NHPI/PC;
the specific preparation steps of the porous carbon PC are as follows: mixing petroleum coke, urea and zirconia particles into a stainless steel ball milling tank according to the mass ratio of 1:1-1:20, ball milling the mixture in a planetary ball mill at the rotating speed of 100-600rpm, calcining the mixture obtained by ball milling at the calcining temperature of 500-1000 ℃, wherein the calcining atmosphere is argon and nitrogen, the heating rate is 2 ℃/min-10 ℃/min, and the calcining time is 1h-5h, thereby obtaining the porous carbon PC.
2. The method for preparing the porous carbon-supported NHPI oxidation desulfurization catalyst according to claim 1, wherein the dosage ratio of porous carbon PC to absolute ethanol solution is (0.05-1) g: (10-100) mL, porous carbon PC was dispersed in absolute ethanol solution by sonication.
3. The preparation method of the porous carbon-supported NHPI oxidation desulfurization catalyst according to claim 1, wherein the mass ratio of porous carbon PC to N-hydroxyphthalimide NHPI is (0.05-1): 0.01-0.3.
4. The method for preparing a porous carbon supported NHPI oxidation desulfurization catalyst according to claim 1, wherein N-hydroxyphthalimide NHPI is added into a mixed solution of porous carbon PC and absolute ethanol solution during impregnation and supporting, and stirring is carried out for 6-24 hours at a reaction temperature of 25-75 ℃ and a stirring rotation speed of 100-800 rpm.
5. The method for preparing the porous carbon supported NHPI oxidation desulfurization catalyst according to claim 1, wherein a vacuum drying oven is used in drying, and the drying time is 4-12h at 30-70 ℃.
6. The application of the porous carbon-supported NHPI oxidation desulfurization catalyst in fuel oil oxidation desulfurization is characterized in that the supported catalyst NHPI/PC prepared according to any one of claims 1-5 is used for carrying out oxidation desulfurization on an oil phase containing sulfide under activated oxygen to prepare a desulfurized oil product, and the supported catalyst NHPI/PC is separated and recycled.
7. The application of the porous carbon-supported NHPI oxidation desulfurization catalyst in fuel oil oxidation desulfurization according to claim 6, wherein cobalt salt is further added as a catalyst aid during the oxidation desulfurization, and the cobalt salt comprises cobalt acetate, cobalt chloride and cobalt acetylacetonate.
8. The use of a porous carbon-supported NHPI oxidation desulfurization catalyst according to claim 7 in fuel oxidation desulfurization, wherein the sulfur content ratio of the supported catalyst NHPI/PC, cobalt salt, oil phase, and oil phase is: (0.01-1) g: (0.001-0.01) g: (5-50) mL: (50-800) ppm.
9. The application of the porous carbon-supported NHPI oxidation desulfurization catalyst in fuel oil oxidation desulfurization according to claim 8, wherein the temperature is 80-140 ℃, the air flow is 50-200mL/min, and the stirring speed is 100-1000rpm.
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