Magnesium-based hydrodesulfurization material modified by butyl phosphonic acid and preparation method of magnesium-based hydrodesulfurization material

Abstract

The invention 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 is prepared from the following raw materials: magnesium, carbon black and butyl phosphonic acid, and the preparation method comprises the following steps: adding the magnesium into the carbon black for ball milling; carrying out hydrotreating on a solid product obtained by ball milling; adding the hydrotreated solid product into butyl phosphonic acid for ball milling; and carrying out heat treatment on a solid product obtained by ball milling in the previous step to prepare the butyl phosphonic acid modified magnesium-based hydrodesulfurization material. Magnesium hydride in the magnesium-based hydrodesulfurization material is used as a high-activity hydrogen source for hydrodesulfurization of dibenzothiophene in an anthracene oil liquid phase, and high temperature and high pressure are not needed in the hydrodesulfurization process; the surface of magnesium hydride is modified by butyl phosphonic acid, so that dibenzothiophene molecules stand and are adsorbed on the surface of magnesium hydride, a direct hydrogenolysis desulfurization reaction is carried out, and a benzene ring is not subjected to hydrogenation saturation, so that the selectivity of the hydrodesulfurization reaction can be improved.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrodesulfurization, and particularly relates to a butylphosphonic acid-modified magnesium-based hydrodesulfurization material and a preparation method thereof. Background Art

[0002] Anthracene oil fraction is the distillate at 280-360°C during atmospheric distillation of coal tar (accounting for 20wt%-28wt% of coal tar). At present, anthracene oil is mainly used as fuel, preservative, and production of carbon black. After refining, anthracene oil has important applications in high-end materials, medicine, and dye production, but the presence of sulfur-containing compounds in it will seriously affect product quality. The main sulfur-containing compound is dibenzothiophene, which has a similar molecular structure and boiling point to anthracene (the boiling point of anthracene is 340°C and the boiling point of dibenzothiophene is 333°C). It is difficult to remove it by recrystallization or distillation. Catalytic hydrogenation can convert the sulfur in dibenzothiophene into hydrogen sulfide, which is easy 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 catalytic material, which is not conducive to the hydrodesulfurization reaction. In order to increase the mass transfer rate of hydrogen molecules in the liquid phase and the activity of the catalytic material, the hydrodesulfurization reaction is generally carried out under high temperature and high pressure (280-420°C, 2-15MPa), and the liquid circulation volume is large, which seriously restricts the process efficiency.

[0003] Furthermore, the hydrodesulfurization catalytic material is generally a sulfide of cobalt-molybdenum or nickel-tungsten. There are two adsorption structures of dibenzothiophene molecules on the surface of the catalytic material. One is standing adsorption (also known as vertical adsorption, S atom end adsorption, and single-point adsorption). The S atom end is chemically adsorbed on the surface of the catalytic material, while the benzene ring is not adsorbed. The reaction is a direct hydrogenation desulfurization path. The CS bond of the thiophene ring is broken and hydrogenated, while the benzene ring is not saturated by hydrogenation. The products are biphenyl and hydrogen sulfide. The second is lying adsorption (also known as parallel adsorption, benzene ring adsorption, and multi-site adsorption). Both the benzene ring and the thiophene ring are chemically adsorbed on the surface of the material. The reaction is a hydrogenation path. The benzene ring is saturated by hydrogenation, and then the CS bond of the thiophene ring is broken and hydrogenated. The products are bicyclohexane and hydrogen sulfide. This reaction path will undoubtedly increase the consumption of hydrogen. The coexistence of two adsorption structures of dibenzothiophene molecules on the surface of the catalytic material results in low selectivity of the direct hydrogenation desulfurization reaction. The benzene ring is hydrogenated and saturated to bicyclohexane of low value, and the hydrogen consumption is increased.

[0004] Therefore, there is an urgent need for a hydrodesulfurization reaction process that can effectively supply hydrogen to the dibenzothiophene molecules on the surface of the catalytic material, as well as a catalytic material that can directly desulfurize dibenzothiophene by hydrogenation, so as to overcome the problem of slow mass transfer of hydrogen molecules in the liquid phase during the hydrogenation process, and solve the problem of flat adsorption of dibenzothiophene molecules on the surface of the catalytic material, resulting in 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 the present invention is to provide a magnesium-based hydrodesulfurization material modified with butylphosphonic acid and a preparation method thereof, so as to effectively solve the problem that the catalytic hydrodesulfurization process requires high temperature and high pressure and the hydrogenation reaction has poor selectivity. The technical solution adopted is:

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

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

[0008] S1, adding magnesium to carbon black for ball milling;

[0009] S2, subjecting the solid product obtained by ball milling in step S1 to hydrogenation treatment;

[0010] S3, adding butylphosphonic acid to the solid product subjected to the hydrogenation treatment in step S2 for ball milling;

[0011] S4, heat-treating the solid product obtained by ball milling in step S3 to obtain a magnesium-based hydrodesulfurization material modified with butylphosphonic acid.

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

[0013] As a further preference, 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 hydrotreatment temperature is 280-420° C., and the hydrotreatment time is 1-3 hours.

[0015] As a further preference, the hydrotreatment temperature is 320° C. and the hydrotreatment time is 2 h.

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

[0017] As a further preference, 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 time is 1-3 hours.

[0019] As a further preference, the heat treatment temperature is 270° C. and the heat treatment time is 2 h.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) Using magnesium hydride as a highly active hydrogen source for the hydrodesulfurization of dibenzothiophene in the anthracene oil liquid phase overcomes the problem of slow mass transfer of hydrogen molecules in the liquid phase during the hydrogenation process. During the hydrodesulfurization process, high temperature and high pressure are not required, thereby reducing the material requirements of the hydrogenation reaction equipment and reducing 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 hydrogenation desulfurization reaction occurs, while the benzene ring will not be hydrogenated and saturated, thereby improving the selectivity of the hydrodesulfurization reaction, reducing the hydrogen consumption in the hydrodesulfurization process, and lowering the energy barrier of the hydrodesulfurization reaction, making the reaction conditions milder.

[0023] (3) The limited domain effect of butylphosphonic acid on magnesium hydride particles can prevent the magnesium hydride particles from merging and growing during the high-temperature reaction, thereby maintaining the hydrodesulfurization reaction activity of the material.

[0024] (4) Using carbon black as a grinding aid for magnesium can reduce the particle size of magnesium, which is beneficial to the hydrogenation of magnesium to form magnesium hydride. In addition, during the hydrodesulfurization process, carbon black has an auxiliary effect on the standing adsorption of dibenzothiophene molecules on the surface of magnesium hydride and direct hydrogenation desulfurization. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0026] Figure 2 is the 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 photograph of the magnesium-based hydrodesulfurization material modified with butylphosphonic acid in Example 1.

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

[0030] The drawings are only used for illustrative purposes; for those skilled in the art, some well-known structures and their descriptions in the drawings may be omitted, and therefore, they should not be understood as limitations on the present invention. DETAILED DESCRIPTION

[0031] Unless otherwise specified, the chemical substances and instruments used in the present invention can be obtained through conventional commercial channels.

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

[0033] S1. Add magnesium to carbon black for ball milling; 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° C., and the hydrogenation treatment time is 1-3 hours.

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

[0036] S4, heat-treating the solid product obtained by ball milling in step S3 to obtain a magnesium-based hydrodesulfurization material modified with butylphosphonic acid at a temperature of 260 to 280° C. for 1 to 3 hours.

[0037] The hydrodesulfurization performance test method of the magnesium-based hydrodesulfurization material modified with butylphosphonic acid prepared by the present invention is as follows: 0.5 g of the magnesium-based hydrodesulfurization material modified with butylphosphonic acid and 30 g of anthracene oil (dibenzothiophene content 3 wt%) are loaded into a 100 mL batch reactor, and then hydrogen (purity 99.999%) is introduced to a pressure of 0.6 MPa, and then heated to 250° C., reacted for 10 min, and then the bottom liquid and the upper space gas of the reactor were sampled and the mass spectrometry (MALDI-TOF type, Bruker, Germany) was used to analyze the results. The content of dibenzothiophene in the liquid sample and the content of biphenyl in the gas sample were determined by a mass spectrometer, and the content of hydrogen sulfide in the gas sample was determined by a trace sulfur spectrum (Wuhan Huashuo HC-5 GC-FPD sulfur spectrometer), and the conversion rate of dibenzothiophene hydrodesulfurization (the calculation formula is: (1-the content of dibenzothiophene in the liquid phase after the reaction ÷ the content of dibenzothiophene in the liquid phase before the reaction) × 100%) and the selectivity of direct hydrogenolysis desulfurization reaction (the content of biphenyl in the gas phase after the reaction ÷ the content of hydrogen sulfide in the gas phase after the reaction × 100%) were calculated.

[0038] Technical principle of the present invention:

[0039] The magnesium hydride generated after the hydrogenation of magnesium is used as a hydrogen source to supply highly active hydrogen to the hydrodesulfurization of dibenzothiophene. During the hydrodesulfurization process, only a hydrogen pressure of <0.8MPa is required to maintain the magnesium in a hydrogenated state (magnesium hydride) and keep the reaction system in a steady state; even if there is no gaseous hydrogen in the reaction system, the hydrodesulfurization reaction can be maintained for a considerable period of time (consuming the hydrogen in the magnesium hydride lattice). Therefore, the hydrogenation reaction does not require high temperature and high pressure (280-420°C, 2-15MPa) like the conventional hydrogenation process, thereby reducing the material requirements of the hydrogenation reaction equipment and reducing energy consumption. Furthermore, by using mechanical force to induce chemical reactions - mechano-chemistry, butylphosphonic acid is anchored on the surface of magnesium hydride. Under the steric hindrance of the butylphosphonic acid molecules, the dibenzothiophene molecules stand and adsorb on the surface of magnesium hydride (such as Figure 1 As shown in the figure, the CS bond is selectively activated to cause a direct hydrogenation desulfurization reaction, while the benzene ring will not be saturated with hydrogenation, thereby reducing the hydrogen consumption in the hydrodesulfurization process; furthermore, butylphosphonic acid can also regulate the electronic structure of the adsorption site, stabilize the transition state of the hydrogenation reaction of dibenzothiophene molecules, reduce the reaction energy barrier, and moderate the reaction conditions (temperature and pressure); in addition, the limited domain effect of butylphosphonic acid on magnesium hydride particles can prevent the magnesium hydride particles from merging and growing during the high-temperature reaction, so that the hydrodesulfurization reaction activity of the material can be maintained. Before magnesium is hydrogenated to magnesium hydride, carbon black is first added as a grinding aid, and the particle size of magnesium is reduced by high-energy ball milling to facilitate hydrogenation to generate magnesium hydride; in the hydrodesulfurization process, carbon black has an auxiliary effect on the standing adsorption and direct hydrogenation desulfurization of dibenzothiophene molecules on the surface of magnesium hydride.

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

[0041] Example 1

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

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

[0044] (2) In a glove box (Lab2000, Itex Inert Gas Systems Co., Ltd., oxygen content <0.1 ppm, water content <0.1 ppm) protected by argon (purity 99.999%), 1.000 g of the solid product obtained by ball milling in step (1) was placed in the sample cell of a high-pressure gas adsorption instrument (PCT-Pro, Setram Instruments, France), and hydrogenated at 320° C. for 2 h.

[0045] (3) In an argon-filled glove box, the solid product of the hydrogenation treatment in step (2) is placed in a ball mill, and 0.009 g of butylphosphonic acid (BPA, CAS No. 3321-64-0, P(O)(OH)2(CH2)3CH3, purity 99%) is added, and ball milling is performed at a ball milling 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 in a sample cell of a high-pressure gas adsorption instrument, evacuated to <0.001 atm, and then filled with hydrogen to 2.5 MPa, heated to 270° C. for heat treatment for 2 h, during which the vacuum is evacuated every 20 min, and hydrogen is filled to 2.5 MPa, and then cooled to room temperature to obtain a magnesium-based hydrodesulfurization material modified with butylphosphonic acid.

[0047] The infrared spectrum of the prepared magnesium-based hydrodesulfurization material modified with butylphosphonic acid (tested by the Thermo Fisher Scientific iS10 infrared spectrometer) is as follows: Figure 3 As shown in the figure, it can be seen that there are absorption peaks of methyl and methylene in butylphosphonic acid, indicating that butylphosphonic acid is anchored on magnesium hydride; the transmission electron microscope (Japanese JEOL JEM-2100 transmission electron microscope) photo of the material is shown in Figure 4As shown in the figure, it can be seen that the larger magnesium hydride particles are about 100nm; the X-ray diffraction of the material is as follows Figure 5 As shown in the figure, it can be seen that the magnesium hydride is crystalline with a grain size of 84 nm (calculated using the Scherrer formula based on the diffraction peak at 27.90° on the (110) crystal plane of the magnesium hydride crystal). In addition, there is a very small amount of elemental magnesium (due to incomplete hydrogenation of magnesium) and magnesium hydroxide (due to the reaction with water in the air during sample operation), and there is no diffraction peak 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 example was measured in a batch reactor to have a dibenzothiophene hydrodesulfurization conversion rate of 99.7% and a direct hydrogenolysis desulfurization (to generate dicyclohexane) selectivity of 99.5%.

[0049] Example 2

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

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

[0052] Example 3

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

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

[0055] Example 4

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

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

[0058] Example 5

[0059] The difference between this embodiment and embodiment 1 is that the ball milling intensity during the ball milling of magnesium and carbon black in step (1) is increased, the ball milling speed is 600 r / min, and the ball milling time is 4 h, thereby obtaining a magnesium-based hydrodesulfurization material modified with butylphosphonic acid.

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

[0061] Example 6

[0062] The difference between this embodiment and embodiment 1 is that the reaction intensity during the hydrotreatment in step (2) is reduced, the hydrotreatment temperature is 280° C., the hydrotreatment time is 1 h, and a butylphosphonic acid-modified magnesium-based hydrodesulfurization material is obtained.

[0063] The butylphosphonic acid-modified magnesium-based hydrodesulfurization material prepared in this example was measured to have a dibenzothiophene hydrodesulfurization conversion rate of 90.4% and a direct hydrogenolysis desulfurization 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° C., the hydrogenation treatment time is 3 h, and a butylphosphonic acid-modified magnesium-based hydrodesulfurization material is obtained.

[0066] The butylphosphonic acid modified magnesium-based hydrodesulfurization material prepared in this example was measured to have a dibenzothiophene hydrodesulfurization conversion rate of 99.7% and a direct hydrogenolysis desulfurization 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 to 0.006 g, and a magnesium-based hydrodesulfurization material modified with butylphosphonic acid is obtained.

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

[0070] Example 9

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

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

[0073] Example 10

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

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

[0076] Embodiment 11

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

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

[0079] Example 12

[0080] The difference between this embodiment and embodiment 1 is that the heat treatment intensity of step (4) is reduced, the heat treatment temperature is 260° C., the heat treatment time is 1 h, and a magnesium-based hydrodesulfurization material modified with butylphosphonic acid is obtained.

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

[0082] Example 13

[0083] The difference between this embodiment and embodiment 1 is that: the heat treatment intensity of step (4) is increased, the heat treatment temperature is 280° C., the heat treatment time is 3 h, and a butylphosphonic acid-modified magnesium-based hydrodesulfurization material is obtained.

[0084] The butylphosphonic acid modified magnesium-based hydrodesulfurization material prepared in this example was measured to have a dibenzothiophene hydrodesulfurization conversion rate of 99.3% and a direct hydrogenolysis desulfurization 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), and other operations are the same to obtain a magnesium-based hydrodesulfurization material.

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

[0088] It can be seen from Examples 1 to 13 and the comparative example that butylphosphonic acid can be modified on the surface of magnesium hydride by ball milling. The obtained 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 hydrogenolysis desulfurization selectivity is high. Butylphosphonic acid is crucial to improving the direct hydrogenolysis desulfurization selectivity.

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

[0090] Of course, the above description is not a limitation of the present invention, and the present invention is not limited to the above examples. Changes, modifications, additions or substitutions made by technicians in this technical field within the essential scope of the present invention should also fall within the protection scope of the present invention.

Claims

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

023.

2. The method for preparing a magnesium-based hydrodesulfurization material modified with butylphosphonic acid according to claim 1, characterized in that: The steps include: S1, adding magnesium to carbon black for ball milling; S2, subjecting the solid product obtained by ball milling in step S1 to hydrogenation treatment; S3, adding butylphosphonic acid to the solid product subjected to the hydrogenation treatment in step S2 for ball milling; S4, heat-treating the solid product obtained by ball milling in step S3 to obtain a magnesium-based hydrodesulfurization material modified with butylphosphonic acid.

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

4. The method for preparing a magnesium-based hydrodesulfurization material modified with butylphosphonic acid according to claim 3, characterized in that: 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.

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

6. The method for preparing a magnesium-based hydrodesulfurization material modified with butylphosphonic acid according to claim 5, characterized in that: The hydrotreatment temperature is 320°C and the hydrotreatment time is 2 h.

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

8. The method for preparing a magnesium-based hydrodesulfurization material modified with butylphosphonic acid according to claim 7, characterized in that: 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.

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

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