A butylphosphonic acid modified magnesium-based hydrodesulfurization material and a method of making the same

Abstract

The application belongs to the technical field of hydrodesulfurization and particularly relates to a butyl phosphonic acid modified magnesium-based hydrodesulfurization material and a preparation method thereof. The magnesium-based hydrodesulfurization material uses raw materials including magnesium, carbon black and butyl phosphonic acid, and the preparation method includes the following steps: adding magnesium into carbon black for ball milling; performing hydrogenation treatment on the obtained solid product; adding the hydrogenation treated solid product into butyl phosphonic acid for ball milling; and performing heat treatment on the solid product obtained in the last step to obtain the butyl phosphonic acid modified magnesium-based hydrodesulfurization material. In the application, magnesium hydride in the magnesium-based hydrodesulfurization material is used as a high-activity hydrogen source for the hydrodesulfurization of dibenzothiophene in anthracene oil liquid phase, and in the hydrodesulfurization process, high temperature and high pressure are not needed; the surface of the magnesium hydride is modified by butyl phosphonic acid, so that dibenzothiophene molecules stand and adsorb on the surface of the magnesium hydride, direct hydrogenolysis desulfurization reaction occurs, and the benzene ring will not be saturated by hydrogenation, so that the selectivity of the hydrodesulfurization reaction can be improved.

Description

Technical Field

[0001] This invention belongs to the field of hydrodesulfurization technology, specifically relating to a butylphosphonic acid-modified magnesium-based hydrodesulfurization material and its preparation method. Background Technology

[0002] Anthracene oil is the distillate from coal tar at atmospheric distillation at 280–360℃ (accounting for 20 wt%–28 wt% of coal tar). Currently, anthracene oil is mainly used as fuel, preservative, and in the production of carbon black. After refining, anthracene oil has important applications in high-end materials, pharmaceuticals, and dye production. However, the presence of sulfur-containing compounds can seriously affect product quality. The main sulfur-containing compound is dibenzothiophene, which has a similar molecular structure and boiling point to anthracene (anthracene has a boiling point of 340℃, while dibenzothiophene has a boiling point of 333℃). It is difficult to remove by recrystallization or distillation. Catalytic hydrogenation can convert the sulfur in dibenzothiophene into hydrogen sulfide, making it easier to remove. However, the hydrogenation process is a gas-liquid-solid three-phase coupled reaction system. In the liquid phase, the mass transfer of hydrogen molecules is slow, resulting in a low amount of hydrogen on the surface of the catalyst material, which is not conducive to the hydrodesulfurization reaction. In order to improve the mass transfer rate of hydrogen molecules in the liquid phase and the activity of the catalyst material, the hydrodesulfurization reaction is generally carried out under high temperature and high pressure (280-420℃, 2-15MPa), and the liquid circulation volume is large, which seriously restricts the process efficiency.

[0003] Furthermore, hydrodesulfurization catalysts are generally cobalt-molybdenum or nickel-tungsten sulfides. Dibenzothiophene molecules exhibit two adsorption structures on the catalyst surface: one is upright adsorption (also known as vertical adsorption, S-terminal adsorption, or single-point adsorption), where the S-terminus undergoes chemisorption on the catalyst surface, while the benzene ring remains unadsorbed. This is a direct hydrodesulfurization pathway, where the CS bond of the thiophene ring breaks and hydrogen is added, but the benzene ring is not saturated with hydrogen, producing biphenyl and hydrogen sulfide. The other is horizontal adsorption (also known as parallel adsorption, benzene ring adsorption, or multi-site adsorption), where both the benzene and thiophene rings undergo chemisorption on the material surface. This is a hydrogenation pathway, where the benzene ring becomes hydrogen-saturated, and then the CS bond of the thiophene ring breaks and hydrogen is added, producing bicyclohexane and hydrogen sulfide. This reaction pathway undoubtedly increases hydrogen consumption. The coexistence of these two adsorption structures on the catalyst surface results in low selectivity for the direct hydrodesulfurization reaction, with the benzene ring being hydrogenated to the less valuable bicyclohexane, and further increasing hydrogen consumption.

[0004] Therefore, there is an urgent need for a hydrodesulfurization reaction process that can effectively supply hydrogen to dibenzothiophene molecules on the surface of the catalyst material, as well as a catalyst material that enables direct hydrodesulfurization of dibenzothiophene, in order to overcome the problem of slow mass transfer of hydrogen molecules in the liquid phase during the hydrogenation process, and to solve the problem of dibenzothiophene molecules lying flat on the surface of the catalyst material, which leads to hydrogenation saturation of the benzene ring and high hydrogen consumption, thereby achieving efficient hydrodesulfurization of dibenzothiophene. Summary of the Invention

[0005] The technical problem to be solved by this invention is to provide a butylphosphonic acid-modified magnesium-based hydrodesulfurization material and its preparation method, so as to effectively solve the problems of high temperature and high pressure required in the catalytic hydrodesulfurization process and poor selectivity of the hydrogenation reaction. The technical solution adopted is as follows:

[0006] A magnesium-based hydrodesulfurization material modified with butylphosphonic acid, the raw materials used include magnesium, carbon black and butylphosphonic acid, and the mass ratio of magnesium, carbon black and butylphosphonic acid is 1:0.053~0.176:0.007~0.023.

[0007] A method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material includes the following steps:

[0008] S1. Add magnesium to carbon black and ball mill;

[0009] S2. The solid product obtained by ball milling in step S1 is subjected to hydrogenation treatment;

[0010] S3. Add butylphosphonic acid to the solid product that has undergone hydrogenation treatment in step S2 and ball mill it.

[0011] S4. The solid product obtained by ball milling in step S3 is subjected to heat treatment to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0012] Preferably, in step S1, the mass ratio of magnesium to carbon black is 1:0.053 to 0.176, the ball milling speed is 420 to 600 r / min, and the ball milling time is 2 to 4 h.

[0013] As a further preferred option, the mass ratio of magnesium to carbon black is 1:0.111, the ball milling speed is 540 r / min, and the ball milling time is 3 h.

[0014] Preferably, in step S2, the hydrogenation treatment temperature is 280–420°C, and the hydrogenation treatment duration is 1–3 hours.

[0015] As a further preferred option, the hydrogenation treatment temperature is 320℃ and the hydrogenation treatment time is 2h.

[0016] Preferably, in step S3, the mass ratio of magnesium to butylphosphonic acid is 1:0.007 to 0.023, the ball milling speed is 300 to 480 r / min, and the ball milling time is 1 to 3 h.

[0017] As a further preferred option, the mass ratio of magnesium to butylphosphonic acid is 1:0.012, the ball milling speed is 420 r / min, and the ball milling time is 2 h.

[0018] Preferably, in step S4, the heat treatment temperature is 260–280°C and the heat treatment duration is 1–3 hours.

[0019] As a further preferred option, the heat treatment temperature is 270℃ and the heat treatment time is 2h.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0021] (1) Using magnesium hydride as a highly active hydrogen source for the hydrodesulfurization of dibenzothiophene in the liquid phase of anthracene oil overcomes the problem of slow mass transfer of hydrogen molecules in the liquid phase during the hydrodesulfurization process. No high temperature and high pressure are required during the hydrodesulfurization process, which can reduce the material requirements of the hydrogenation reaction equipment and reduce energy consumption.

[0022] (2) The surface of magnesium hydride is modified with butylphosphonic acid, so that dibenzothiophene molecules stand and adsorb on the surface of magnesium hydride, and a direct hydrodesulfurization reaction occurs, while the benzene ring will not be hydrogenated to saturation. This can improve the selectivity of the hydrodesulfurization reaction, reduce the hydrogen consumption in the hydrodesulfurization process, and lower the energy barrier of the hydrodesulfurization reaction, thus making the reaction conditions milder.

[0023] (3) Butylphosphonic acid has a limited domain effect on magnesium hydride particles, which can prevent magnesium hydride particles from merging and growing during high-temperature reaction, thus maintaining the hydrodesulfurization reactivity of the material.

[0024] (4) Using carbon black as a grinding aid for magnesium reduces the particle size of magnesium, which is beneficial for magnesium to hydrogenate into magnesium hydride. In addition, carbon black has an auxiliary effect on the upright adsorption of dibenzothiophene molecules on the surface of magnesium hydride and direct hydrogen desulfurization during the hydrodesulfurization process. Attached Figure Description

[0025] Figure 1 This is an adsorption structure diagram of dibenzothiophene molecules on the surface of the magnesium-based hydrodesulfurization material prepared in this invention.

[0026] Figure 2 This is an X-ray diffraction pattern of the magnesium raw material used in Example 1.

[0027] Figure 3 This is the infrared spectrum of the magnesium-based hydrodesulfurization material modified with butylphosphonic acid in Example 1.

[0028] Figure 4 This is a transmission electron microscope image of the butylphosphonic acid-modified magnesium-based hydrodesulfurization material of Example 1.

[0029] Figure 5 This is the X-ray diffraction pattern of the butylphosphonic acid-modified magnesium-based hydrodesulfurization material of Example 1.

[0030] The accompanying drawings are for illustrative purposes only; certain well-known structures and their descriptions may be omitted from the drawings by those skilled in the art, and therefore should not be construed as limiting the invention. Detailed Implementation

[0031] Unless otherwise specified, the chemical substances and instruments used in this invention are available through conventional commercial channels.

[0032] This invention provides a method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material, comprising the following steps:

[0033] S1. Add magnesium to carbon black and ball mill; wherein the mass ratio of magnesium to carbon black is 1:0.053 to 1:0.176, the ball milling speed is 420 to 600 r / min, and the ball milling time is 2 to 4 h.

[0034] S2. The solid product obtained by ball milling in step S1 is subjected to hydrogenation treatment; the hydrogenation treatment temperature is 280-420℃ and the hydrogenation treatment time is 1-3h.

[0035] S3. The solid product treated by hydrogenation in step S2 is added to butylphosphonic acid and ball-milled; the mass ratio of magnesium to butylphosphonic acid is 1:0.007 to 0.023, the ball milling speed is 300 to 480 r / min, and the ball milling time is 1 to 3 h.

[0036] S4. The solid product obtained by ball milling in step S3 is subjected to heat treatment to obtain butylphosphonic acid-modified magnesium-based hydrodesulfurization material. The heat treatment temperature is 260-280℃, and the heat treatment time is 1-3h.

[0037] The hydrodesulfurization performance test method for the butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared by this invention is as follows: In a 100 mL batch reactor, 0.5 g of the butylphosphonic acid-modified magnesium-based hydrodesulfurization material and 30 g of anthracene oil (3 wt% dibenzothiophene content) are added. Hydrogen gas (99.999% purity) is then introduced until the pressure reaches 0.6 MPa. The reactor is then heated to 250 °C and reacted for 10 min. Samples of the liquid at the bottom and the gas in the upper space are taken and analyzed using a mass spectrometer (Bruker MALDI-TOF type). The dibenzothiophene content in liquid samples and the biphenyl content in gaseous samples were determined by mass spectrometry. The hydrogen sulfide content in gaseous samples was determined by micro-sulfur spectroscopy (Wuhan Huashuo HC-5 GC-FPD sulfur spectrometer). The dibenzothiophene hydrodesulfurization conversion rate (calculated as: (1 - dibenzothiophene content in the liquid phase after reaction ÷ dibenzothiophene content in the liquid phase before reaction) × 100%) and the selectivity of direct hydrodesulfurization reaction (biphenyl content in the gas phase after reaction ÷ hydrogen sulfide content in the gas phase after reaction × 100%) were then calculated.

[0038] Technical principle of the invention:

[0039] Magnesium hydride, formed by the hydrogenation of magnesium, is used as a hydrogen source to supply highly active hydrogen for the hydrodesulfurization of dibenzothiophene. During the hydrodesulfurization process, a hydrogen pressure of <0.8 MPa is sufficient to maintain magnesium in its hydride state, ensuring a steady-state reaction. Even without gaseous hydrogen, the hydrodesulfurization reaction can be maintained for a considerable period (consuming hydrogen within the magnesium hydride lattice). Therefore, the hydrogenation reaction does not require the high temperature and pressure (280–420℃, 2–15 MPa) of conventional hydrogenation processes, thus reducing the material requirements of the hydrogenation reaction equipment and lowering energy consumption. Furthermore, a mechanochemical reaction—mechanical chemistry—is used to anchor butylphosphonic acid on the surface of magnesium hydride. Under the steric hindrance of butylphosphonic acid molecules, dibenzothiophene molecules adsorb upright on the magnesium hydride surface (e.g., ...). Figure 1 As shown, butylphosphonic acid selectively activates the CS bond, resulting in a direct hydrodesulfurization reaction, while the benzene ring does not undergo hydrogenation saturation, thus reducing hydrogen consumption in the hydrodesulfurization process. Furthermore, butylphosphonic acid can regulate the electronic structure of the adsorption sites, stabilizing the transition state of the dibenzothiophene molecule hydrogenation reaction, lowering the reaction energy barrier, and mildening the reaction conditions (temperature and pressure). In addition, butylphosphonic acid has a limited-domain effect on magnesium hydride particles, preventing particle agglomeration and growth during high-temperature reactions, thus maintaining the material's hydrodesulfurization reactivity. Before magnesium is hydrogenated to magnesium hydride, carbon black is added as a grinding aid, and high-energy ball milling is used to reduce the particle size of magnesium, which is beneficial for hydrogenation to form magnesium hydride. During the hydrodesulfurization process, carbon black assists in the upright adsorption of dibenzothiophene molecules on the magnesium hydride surface and in the direct hydrodesulfurization.

[0040] The present invention will be further described in detail below with reference to specific embodiments.

[0041] Example 1

[0042] A method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material includes the following steps:

[0043] (1) 1.500g of magnesium (particle size <74μm, purity 98.5%) and 0.167g of carbon black (graphitized carbon black, CB No. 012282931) were loaded into a ball mill jar and filled with argon gas (purity 99.999%) to 2atm. The ball mill was then carried out in a planetary ball mill (ND8-1L type, Nanjing Nanda Tianzun Electronics Co., Ltd., ball mill jar volume 100mL, grinding ball material is sintered zirconium dioxide, the ratio of the number of grinding balls with diameters of 9mm, 5mm and 3mm is 20:40:40, the ratio of the rotation speed to the revolution speed is 2:1, and the machine is stopped and cooled for 5min after every 5min of forward revolution and 5min of reverse revolution). The ball mill speed was 540r / min and the ball milling time was 3h. X-ray diffraction of the magnesium raw material used (Rigaku Smartlab X-ray diffractometer, Cu target, Kα rays, scanning step size 0.01°, scanning speed 2° / min) as follows: Figure 2 As shown in the figure, there are only diffraction peaks of crystalline magnesium, and no obvious diffraction peaks of other impurities.

[0044] (2) Take 1.000g of the solid product from step (1) ball milling in a glove box (Lab2000 type, ITEX Inert Gas Systems Ltd., oxygen content <0.1ppm, water content <0.1ppm) protected by argon gas (purity 99.999%), put it into the sample cell of a high pressure gas adsorption instrument (PCT-Pro type, CETRAM Instruments Ltd., France), and treat it with hydrogen at 320℃ for 2h.

[0045] (3) In an argon-protected glove box, the solid product from the hydrogenation treatment in step (2) was loaded into a ball mill jar and 0.009 g of butylphosphonic acid (BPA, CAS No. 3321-64-0, P(O)(OH)2(CH2)3CH3, purity 99%) was added. The ball milling was carried out at a speed of 420 r / min for 2 h.

[0046] (4) In an argon-protected glove box, the solid product obtained in step (3) is placed into the sample cell of a high-pressure gas adsorption instrument, evacuated to <0.001 atm, then filled with hydrogen to 2.5 MPa, heated to 270℃ for 2 hours, evacuated every 20 minutes and filled with hydrogen to 2.5 MPa, and then cooled to room temperature to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0047] The infrared spectrum of the butylphosphonic acid-modified magnesium-based hydrodesulfurization material (measured by a Thermo Fisher Scientific iS10 infrared spectrometer) is as follows: Figure 3 As shown in the figure, absorption peaks of the methyl and methylene groups in butylphosphonic acid are present, indicating that butylphosphonic acid is anchored to magnesium hydride; transmission electron microscope (TEM) images of the material (JEOL JEM-2100 TEM) are shown below. Figure 4As shown in the figure, the larger magnesium hydride particles are approximately 100 nm in size; the X-ray diffraction of the material is as follows. Figure 5 As shown in the figure, the magnesium hydride is crystalline with a grain size of 84 nm (calculated using the Scherrer formula based on the 27.90° diffraction peak of the (110) crystal plane of magnesium hydride). There are also a very small amount of elemental magnesium (due to incomplete hydrogenation of magnesium) and magnesium hydroxide (due to the reaction of the sample with water in the air during the operation). There are no diffraction peaks related to butylphosphonic acid (butylphosphonic acid molecules are dispersed on the surface of magnesium hydride, rather than aggregated into crystals).

[0048] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was tested in an intermittent batch reactor and found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.7% and a direct hydrodesulfurization (to produce bicyclohexane) selectivity of 99.5%.

[0049] Example 2

[0050] The difference between this embodiment and embodiment 1 is that the amount of grinding aid carbon black used in step (1) of ball milling magnesium is reduced, and the amount of carbon black added is 0.079g, so as to obtain magnesium-based hydrodesulfurization material modified with butylphosphonic acid.

[0051] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 97.4% and a direct hydrodesulfurization selectivity of 94.2%.

[0052] Example 3

[0053] The difference between this embodiment and embodiment 1 is that the amount of grinding aid carbon black is increased in step (1) when ball milling magnesium. The amount of carbon black added is 0.265g, and butylphosphonic acid modified magnesium-based hydrodesulfurization material is obtained.

[0054] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 98.3% and a direct hydrodesulfurization selectivity of 97.4%.

[0055] Example 4

[0056] The difference between this embodiment and embodiment 1 is that the ball milling intensity during step (1) of ball milling magnesium and carbon black is reduced, the ball milling speed is 420 r / min, and the ball milling time is 2 h, so as to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0057] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 96.5% and a direct hydrodesulfurization selectivity of 95.3%.

[0058] Example 5

[0059] The difference between this embodiment and embodiment 1 is that the ball milling intensity is increased in step (1) when ball milling magnesium and carbon black, the ball milling speed is 600 r / min, and the ball milling time is 4 h, so as to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0060] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.8% and a direct hydrodesulfurization selectivity of 98.1%.

[0061] Example 6

[0062] The difference between this embodiment and embodiment 1 is that the reaction intensity during the hydrogenation treatment in step (2) is reduced, the hydrogenation treatment temperature is 280°C, and the hydrogenation treatment time is 1 hour, so as to obtain the magnesium-based hydrogenation desulfurization material modified with butylphosphonic acid.

[0063] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 90.4% and a direct hydrodesulfurization selectivity of 99.0%.

[0064] Example 7

[0065] The difference between this embodiment and embodiment 1 is that the reaction intensity during the hydrogenation treatment in step (2) is increased, the hydrogenation treatment temperature is 340℃, and the hydrogenation treatment time is 3h, so as to obtain a magnesium-based hydrogenation desulfurization material modified with butylphosphonic acid.

[0066] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.7% and a direct hydrodesulfurization selectivity of 99.2%.

[0067] Example 8

[0068] The difference between this embodiment and embodiment 1 is that the amount of butylphosphonic acid used in step (3) is reduced, and the amount of butylphosphonic acid added is 0.006g, so as to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0069] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.2% and a direct hydrodesulfurization selectivity of 91.6%.

[0070] Example 9

[0071] The difference between this embodiment and embodiment 1 is that the amount of butylphosphonic acid in step (3) is increased to 0.019g, and butylphosphonic acid modified magnesium-based hydrodesulfurization material is obtained.

[0072] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.5% and a direct hydrodesulfurization selectivity of 99.6%.

[0073] Example 10

[0074] The difference between this embodiment and embodiment 1 is that the ball milling intensity in step (3) is reduced, the ball milling speed is 300 r / min, and the ball milling time is 1 h, so as to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0075] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 98.0% and a direct hydrodesulfurization selectivity of 86.2%.

[0076] Example 11

[0077] The difference between this embodiment and embodiment 1 is that the ball milling intensity in step (3) is increased, the ball milling speed is 480 r / min, and the ball milling time is 3 h, so as to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0078] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.9% and a direct hydrodesulfurization selectivity of 98.4%.

[0079] Example 12

[0080] The difference between this embodiment and embodiment 1 is that the heat treatment intensity in step (4) is reduced, the heat treatment temperature is 260℃, and the heat treatment time is 1h, so as to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0081] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 97.5% and a direct hydrodesulfurization selectivity of 93.3%.

[0082] Example 13

[0083] The difference between this embodiment and embodiment 1 is that the heat treatment intensity in step (4) is increased, the heat treatment temperature is 280℃, and the heat treatment time is 3h, so as to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

[0084] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.3% and a direct hydrodesulfurization selectivity of 95.1%.

[0085] Comparative Example

[0086] The difference between this embodiment and embodiment 1 is that butylphosphonic acid is not added in step (3), but the other operations are the same, and magnesium-based hydrodesulfurization material is obtained.

[0087] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this embodiment was found to have a dibenzothiophene hydrodesulfurization conversion rate of 99.0% and a direct hydrodesulfurization selectivity of 47.1%.

[0088] As can be seen from Examples 1-13 and the comparative examples, butylphosphonic acid can be modified onto the surface of magnesium hydride by ball milling. The resulting butylphosphonic acid-modified magnesium-based hydrodesulfurization material is used for the hydrodesulfurization of dibenzothiophene in anthracene oil. The reaction conversion rate is high and the direct hydrodesulfurization selectivity is high. Butylphosphonic acid is crucial for improving the direct hydrodesulfurization selectivity.

[0089] The preferred process conditions for preparing butylphosphonic acid-modified magnesium-based hydrodesulfurization materials are as follows: the mass ratio of magnesium to carbon black is 1:0.111, the ball milling speed is 540 r / min, and the ball milling time is 3 h; the hydrogenation treatment temperature after ball milling of magnesium and carbon black is 320℃, and the hydrogenation treatment time is 2 h; when adding butylphosphonic acid for ball milling, the mass ratio of magnesium to butylphosphonic acid is 1:0.012, the ball milling speed is 420 r / min, and the ball milling time is 2 h; the final heat treatment temperature is 270℃, and the heat treatment time is 2 h.

[0090] Of course, the above description is not intended to limit the present invention, and the present invention is not limited to the examples given above. Any changes, modifications, additions or substitutions made by those skilled in the art within the scope of the present invention should also fall within the protection scope of the present invention.

Claims

1. A butylphosphonic acid-modified magnesium-based hydrodesulfurization material, characterized in that, The raw materials used include magnesium, carbon black, and butylphosphonic acid, and the mass ratio of magnesium, carbon black, and butylphosphonic acid used is 1:0.053~0.176:0.007~0.

023.

2. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material as described in claim 1, characterized in that, Includes the following steps: S1. Add magnesium to carbon black and ball mill; S2. The solid product obtained by ball milling in step S1 is subjected to hydrogenation treatment; S3. Add butylphosphonic acid to the solid product that has undergone hydrogenation treatment in step S2 and ball mill it. S4. The solid product obtained by ball milling in step S3 is subjected to heat treatment to obtain butylphosphonic acid modified magnesium-based hydrodesulfurization material.

3. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 2, characterized in that, In step S1, the mass ratio of magnesium to carbon black is 1:0.053 to 0.176, the ball milling speed is 420 to 600 r / min, and the ball milling time is 2 to 4 h.

4. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 3, characterized in that, The mass ratio of magnesium to carbon black was 1:0.111, the ball milling speed was 540 r / min, and the ball milling time was 3 h.

5. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 2, characterized in that, In step S2, the hydrogenation treatment temperature is 280–420°C, and the hydrogenation treatment time is 1–3 hours.

6. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 5, characterized in that, The hydrogenation treatment temperature was 320℃, and the hydrogenation treatment time was 2 hours.

7. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 2, characterized in that, In step S3, the mass ratio of magnesium to butylphosphonic acid is 1:0.007 to 0.023, the ball milling speed is 300 to 480 r / min, and the ball milling time is 1 to 3 h.

8. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 7, characterized in that, The mass ratio of magnesium to butylphosphonic acid was 1:0.012, the ball milling speed was 420 r / min, and the ball milling time was 2 h.

9. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 2, characterized in that, In step S4, the heat treatment temperature is 260–280°C, and the heat treatment time is 1–3 hours.

10. The method for preparing a butylphosphonic acid-modified magnesium-based hydrodesulfurization material according to claim 9, characterized in that, The heat treatment temperature is 270℃ and the heat treatment time is 2h.

Images