A method for preparing a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst
The method for preparing Pt-doped Ni2P/Al2O3 catalysts solves the problems of complex and high cost in the preparation of existing fuel desulfurization catalysts, achieves efficient hydrodesulfurization, reduces preparation costs, and improves catalytic activity.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- JIANGSU UNIV
- Filing Date
- 2024-01-08
- Publication Date
- 2026-07-03
AI Technical Summary
Existing fuel desulfurization catalysts have complex preparation processes, harsh reaction conditions, high processing costs, and are susceptible to sulfide poisoning, leading to increased production costs for enterprises and making it difficult to achieve ultra-deep desulfurization.
The Pt-doped Ni2P/Al2O3 hydrodesulfurization catalyst was prepared by mixing aluminum isopropoxide, ethanol and concentrated HNO3 under magnetic stirring, adding P123 and drying and calcining to form support A, then impregnating it with Ni(NO3)2 and (NH4)2HPO4, and finally adding platinum acetylacetone and calcining to form Pt-Ni2P/Al2O3 catalyst.
It significantly reduced the preparation cost, improved the catalytic activity, and Pt's hydrogenation capacity was far higher than that of existing catalysts. It optimized the interaction between the support and the active component, and achieved a highly efficient hydrodesulfurization effect.
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Figure CN117943071B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of petrochemicals, specifically relating to a method for preparing a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst. Background Technology
[0002] In recent years, with the rapid development of my country's economy and the automotive industry, fuel consumption has increased year by year, and the demand for various oil products in my country is growing daily. Improving the quality and efficiency of the coal tar industry chain is an urgent issue. However, the increasingly deteriorating quality of crude oil and the increasing imports of sulfur-containing and high-sulfur crude oil have led to a shortage of high-quality oil products. Diesel, with its higher combustion efficiency and stronger power compared to gasoline, is widely used. However, the sulfur oxides emitted by diesel engines cause significant environmental damage. Government legislation is becoming increasingly stringent on exhaust emission standards, with China VI and Euro VI standards being more comprehensive, and the quality standards for petroleum products are becoming increasingly stringent, allowing for lower sulfur content. Sawant et al. disclosed a desulfurization catalyst, belonging to the molybdenum-based catalyst family, which has advantages including high activity and selectivity, and can achieve desulfurization reactions under relatively low temperature and pressure. However, it also has some disadvantages. First, its preparation process is relatively complex, requiring high temperature and high pressure conditions. Second, the catalyst's activity is easily poisoned by sulfides, reducing its efficiency. In addition, the lifespan of a catalyst is affected by catalyst deactivation and particle formation, requiring periodic regeneration or replacement.
[0003] Therefore, how to prepare catalysts with ultra-deep desulfurization performance to remove sulfides from diesel fuel until it becomes "sulfur-free" has always been one of the research hotspots and challenges in the petrochemical field. Summary of the Invention
[0004] In view of the problems of complex catalyst preparation process, harsh reaction conditions, high processing cost, and environmental pollution that lead to a significant increase in enterprise production costs in existing fuel desulfurization technologies, this invention aims to provide a catalyst for oil desulfurization that has low processing cost, mild conditions, and can achieve energy conservation and emission reduction.
[0005] To achieve the above technical objectives, the present invention adopts the following technical solution;
[0006] A method for preparing a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst includes the following steps:
[0007] (1) Under magnetic stirring, aluminum isopropoxide (Al[OCH(CH3)2]3) was added to ethanol (EtOH). After stirring for a period of time, concentrated HNO3 was added dropwise (dropwise to avoid condensation). After the temperature dropped to room temperature, a mixture of P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) and EtOH was added. Finally, the product was dried and calcined, and the resulting product was denoted as carrier A.
[0008] (2) Using the carrier A obtained in step (1), an impregnation experiment was conducted. The liquid reagent used was deionized water. The amount of deionized water required to achieve the same volume of impregnation was recorded as V1. Then, nickel nitrate (Ni(NO3)2) and diammonium hydrogen phosphate ((NH4)2HPO4) were dissolved in V1 of the deionized water. The resulting mixture was dried at room temperature. After drying, it was dried and calcined to obtain the solid product, which is Ni2P / Al2O3.
[0009] (3) Based on the Ni2P / Al2O3 obtained in step (2), an impregnation experiment was conducted. The liquid reagent used was dichloromethane (CH2Cl2). The amount of dichloromethane (CH2Cl2) required to achieve an equal volume impregnation state was obtained and denoted as M1. Then, platinum acetylacetone (C 10 H 14 O4Pt) is dissolved in CH2Cl2 with a mass of M1. After complete dissolution, the resulting mixed solution is dried at room temperature and then calcined in a muffle furnace. The calcined solution yields the Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst, denoted as Pt-Ni2P / Al2O3.
[0010] Furthermore, in step (1), the dosage relationship of Al[OCH(CH3)2]3, EtOH, concentrated HNO3, and P123 is 8.16g: 60.0mL: 3.2mL: 4.00g; the concentrated HNO3 is added dropwise and completed within 10-15min; the mixture of P123 and ethanol is added dropwise and completed within 5-10min.
[0011] Furthermore, in step (1), the stirring time is 4 hours and the stirring speed is 800 rpm; the drying temperature is 120-140℃ and the time is 48 hours.
[0012] Furthermore, in step (1), the calcination temperature is 550-560℃, the time is 4h, and the heating rate is 1℃ / min.
[0013] Furthermore, in step (2), V1 ≥ 30 mL, and the ratio of the amounts of Ni(NO3)3, (NH4)2HPO4 to deionized water is 0.257 g: 0.234 g: V1 mL.
[0014] More preferably, the ratio of Ni(NO3)3, (NH4)2HPO4 to deionized water is 0.257g:0.234g:30mL.
[0015] Furthermore, in step (2), the drying time at room temperature is 12 hours, the drying temperature is 120°C, and the time is 12 hours; the calcination temperature is 550°C, the time is 4 hours, and the heating rate is 1°C / min.
[0016] Furthermore, in step (3), the C 10 H 14 The ratio of O4Pt to CH2Cl2 is 0.0304g-0.671g:3g; the loading of Pt in the Pt-Ni2P / Al2O3 is 0.5wt.%-10wt.%.
[0017] Furthermore, in step (3), the drying time at room temperature is 12 hours, the calcination temperature is 250°C, the calcination time is 2 hours, and the heating rate is 1°C / min.
[0018] The advantages and significant effects of this invention are as follows:
[0019] (1) The active phase Pt is introduced for the first time to adjust the particle size of the active phase and the amount of L acid and B acid on the surface of the support. While achieving significant results, the preparation cost is greatly reduced. There has been no related report of this method in previous studies on hydrodesulfurization. This invention is original.
[0020] (2) The active component used in the hydrodesulfurization reaction of this invention is Pt. The noble metal Pt has a strong hydrogenation ability and its catalytic activity (TOF value) is much higher than that of the hydrodesulfurization catalysts currently reported. This result has not been seen in previous hydrodesulfurization studies.
[0021] (3) Pt-doped Ni2P / Al2O3 catalysts affect the interaction between the support and the active component, thereby improving hydrogenation activity; the present invention further optimizes and limits the loading of Pt, and achieves significant technical effects within the limited range. Attached Figure Description
[0022] Figure 1The XRD patterns of the Pt-Ni2P / Al2O3 catalysts are shown below; (a) is the Ni2P / Al2O3 obtained in Example 2, (b) is Pt-Ni2P / Al2O3 with a Pt loading of 0.5 wt.%, (c) is Pt-Ni2P / Al2O3 with a Pt loading of 2 wt.%, (d) is Pt-Ni2P / Al2O3 with a Pt loading of 5 wt.%, and (e) is Pt-Ni2P / Al2O3 with a Pt loading of 10 wt.%.
[0023] Figure 2 HRTEM image of a Pt-Ni2P / Al2O3 catalyst with a Pt loading of 5 wt.% at 100 nm.
[0024] Figure 3 The values represent the 4,6-DMDBT HDS conversion of the Pt-Ni2P / Al2O3 catalyst, where (a) represents Ni2P / Al2O3, (b) represents Pt-Ni2P / Al2O3 with a Pt loading of 0.5 wt.%, (c) represents Pt-Ni2P / Al2O3 with a Pt loading of 2 wt.%, (d) represents Pt-Ni2P / Al2O3 with a Pt loading of 5 wt.%, and (e) represents Pt-Ni2P / Al2O3 with a Pt loading of 10 wt.%. Detailed Implementation
[0025] The following detailed description of various exemplary embodiments of the present invention should not be construed as limiting the present invention, but rather as a more detailed description of certain aspects, features, and implementations of the present invention.
[0026] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0027] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art.
[0028] Note: The impregnation experiment used in this invention is as follows: referring to the impregnation method, the pores inside the solid to be impregnated are filled with liquid reagent until saturation is achieved, and the amount of liquid reagent used at this time is determined.
[0029] Example 1:
[0030] (1) Under magnetic stirring, 8.16 g of Al[OCH(CH3)2]3 was dissolved in a three-necked flask containing 40.0 mL of EtOH. The stirring time was 4 h (800 rpm), and then 3.2 mL of concentrated HNO3 was added dropwise over 10 min (to avoid condensation). After the temperature dropped to room temperature, 4.0 g of P123 was dissolved in 20 mL of EtOH and added dropwise to the flask over 5 min. The mixture was dried at 120 °C for 48 h. Calcination was carried out at 550 °C for 4 h (heating rate of 1 °C / min) to completely remove the structure-directing agent. The resulting product was denoted as support A.
[0031] (2) Take 0.5g of the obtained carrier A, put it in a tube and label it, indicating that it is a carrier and its content and mass, for use as a pre-impregnation sample; put the sample (0.5g) for pre-impregnation into the sample tube, add deionized water drop by drop, and accurately record how many milliliters of water are added to achieve the same volume impregnation state. The result shows that the amount of deionized water used is 30mL; the 30mL of water obtained is the amount of water used to achieve the same volume impregnation state of carrier A.
[0032] Based on carrier A for subsequent experiments; calculate the mass of Ni(NO3)2 and (NH4)2HPO4 required to be added to carrier A (3g) to load 6wt.% of the active component Ni2P: the specific operation is as follows: first, clarify that the effective substances of Ni(NO3)2 and (NH4)2HPO4 are NiO and P2O5, respectively. The sum of the masses of NiO and P2O5 is 6 wt.% compared to the sum of the masses of NiO, P2O5 and the impregnation amount. Meanwhile, the ratio of the mass of NiO divided by its relative molecular mass is 1:2 compared to the ratio of twice the mass of P2O5 divided by its relative molecular mass. By combining these ratios, we can calculate the masses of NiO and P2O5. Since n(NiO) = n(Ni(NO3)2) and 2n(P2O5) = n((NH4)2HPO4), based on the relative molecular masses of Ni(NO3)2 and (NH4)2HPO4, the masses of Ni(NO3)2 and (NH4)2HPO4 are calculated to be 0.257 and 0.234 g, respectively.
[0033] 0.257 g of Ni(NO3)2 and 0.234 g of (NH4)2HPO4 were dissolved in 30 mL of deionized water and dried at room temperature for 12 h. The sample was then dried in an oven at 120 °C for 12 h and calcined in a muffle furnace at 550 °C for 4 h (heating rate of 1 °C / min) to obtain Ni2P / Al2O3.
[0034] Take 3g of calcined Ni2P / Al2O3 and divide it into four equal parts. Place each part into a crucible and conduct an impregnation experiment. The liquid reagent used is CH2Cl2. Pre-impregnate according to the relative molecular mass and molar ratio of CH2Cl2. Calculate the amount of CH2Cl2 required to achieve the same volume impregnation state. The calculated amount of CH2Cl2 is 3g.
[0035] (3) Prepare Pt-Ni2P / Al2O3, wherein the loading of Pt is 0.5 wt.%;
[0036] Calculations show that adding C to Ni2P / Al2O3 with a 0.5 wt.% loading of the active component Pt results in the following requirements: 10 H 14 The quality of O4Pt;
[0037] Calculation method: The loading is 0.5 wt.%, and the ratio of (the mass of Pt) to (the sum of the mass of Pt and the mass of 3g Ni2P / Al2O3) is 0.5 wt.%, so the mass of Pt is first calculated to be 0.0151g. Then, based on the equality of the amounts of substance and the fact that Pt and C... 10 H 14 The molecular weight of O4Pt was obtained, and C was calculated. 10 H 14 The mass of O4Pt is 0.0304g;
[0038] 0.0304g of C 10 H 14 O4Pt was dissolved in 3g of CH2Cl2, dried at room temperature for 12h, and then calcined in a muffle furnace at 250℃ for 2h with a heating rate of 1℃ / min. After calcination, Pt-Ni2P / Al2O3 with a Pt loading of 0.5wt.% was obtained.
[0039] Example 2:
[0040] (1) Under magnetic stirring, 8.16 g of Al[OCH(CH3)2]3 was dissolved in a three-necked flask containing 40.0 mL of EtOH. The stirring time was 4 h (800 rpm), and then 3.2 mL of concentrated HNO3 was added dropwise over 10 min (to avoid condensation). After the temperature dropped to room temperature, 4.0 g of P123 was dissolved in 20 mL of EtOH and added dropwise to the flask over 5 min. The mixture was dried at 120 °C for 48 h. Calcination was carried out at 550 °C for 4 h (heating rate of 1 °C / min) to completely remove the structure-directing agent. The resulting product was denoted as support A.
[0041] (2) Take 0.5g of the obtained carrier A, put it in a tube and label it, indicating that it is a carrier and its content and mass, for use as a pre-impregnation sample; put the sample (0.5g) for pre-impregnation into the sample tube, add deionized water drop by drop, and accurately record how many milliliters of water are added to achieve the same volume impregnation state. The result is calculated that the amount of deionized water used is 30mL; the 30mL of water obtained is the amount of water used to achieve the same volume impregnation state of carrier A.
[0042] Based on carrier A for subsequent experiments; calculate the mass of Ni(NO3)2 and (NH4)2HPO4 required to be added to carrier A (3g) to load 6wt.% of the active component Ni2P: the specific operation is as follows: first, clarify that the effective substances of Ni(NO3)2 and (NH4)2HPO4 are NiO and P2O5, respectively. The sum of the masses of NiO and P2O5 is 6 wt.% compared to the sum of the masses of NiO, P2O5 and the impregnation amount. Meanwhile, the ratio of the mass of NiO divided by its relative molecular mass is 1:2 compared to the ratio of twice the mass of P2O5 divided by its relative molecular mass. Combining these ratios, we obtain the masses of NiO and P2O5. Since n(NiO) = n(Ni(NO3)2) and 2n(P2O5) = n((NH4)2HPO4), based on the relative molecular masses of Ni(NO3)2 and (NH4)2HPO4, the masses of Ni(NO3)2 and (NH4)2HPO4 are calculated to be 0.257 and 0.234 g, respectively.
[0043] 0.257 g of Ni(NO3)2 and 0.234 g of (NH4)2HPO4 were dissolved in 30 mL of deionized water and dried at room temperature for 12 h. The sample was then dried in an oven at 120 °C for 12 h and calcined in a muffle furnace at 550 °C for 4 h (heating rate of 1 °C / min) to obtain Ni2P / Al2O3.
[0044] Take 3g of calcined Ni2P / Al2O3 and divide it into four equal parts. Place each part into a crucible and conduct an impregnation experiment. The liquid reagent used is CH2Cl2. Pre-impregnate according to the relative molecular mass and molar ratio of CH2Cl2. Calculate the amount of CH2Cl2 required to achieve the same volume impregnation state. The calculated amount of CH2Cl2 is 3g.
[0045] (3) Prepare Pt-Ni2P / Al2O3, wherein the loading of Pt is 5 wt.%;
[0046] The calculation shows that C needs to be added to load 5 wt.% of the active component Pt onto Ni2P / Al2O3. 10 H 14 The quality of O4Pt;
[0047] Calculation method: The loading is 5 wt.%, and the mass ratio of Pt (the sum of the mass of Pt and the mass of 3g Ni2P / Al2O3) is 5 wt.%, so the mass of Pt is first calculated to be 0.158g. Then, based on the equality of the amounts of substance and the fact that Pt and C... 10 H 14 The molecular weight of O4Pt was obtained, and C was calculated. 10 H 14 The mass of O4Pt is 0.318g;
[0048] 0.318g of C 10 H 14 O4Pt was dissolved in 3g of CH2Cl2, dried at room temperature for 12h, and then calcined in a muffle furnace at 250℃ for 2h with a heating rate of 1℃ / min. After calcination, Pt-Ni2P / Al2O3 with a Pt loading of 5wt.% was obtained.
[0049] Example 3:
[0050] (1) Under magnetic stirring, 8.16 g of Al[OCH(CH3)2]3 was dissolved in a three-necked flask containing 40.0 mL of EtOH. The stirring time was 4 h (800 rpm), and then 3.2 mL of concentrated HNO3 was added dropwise over 10 min (to avoid condensation). After the temperature dropped to room temperature, 4.0 g of P123 was dissolved in 20 mL of EtOH and added dropwise to the flask over 5 min. The mixture was dried at 120 °C for 48 h. Calcination was carried out at 550 °C for 4 h (heating rate of 1 °C / min) to completely remove the structure-directing agent. The resulting product was denoted as support A.
[0051] (2) Take 0.5g of the obtained carrier A, put it in a tube and label it, indicating that it is a carrier and its content and mass, for use as a pre-impregnation sample; put the sample (0.5g) for pre-impregnation into the sample tube, add deionized water drop by drop, and accurately record how many milliliters of water are added to achieve the same volume impregnation state. The result is calculated that the amount of deionized water used is 30mL; the 30mL of water obtained is the amount of water used to achieve the same volume impregnation state of carrier A.
[0052] Based on carrier A for subsequent experiments; calculate the mass of Ni(NO3)2 and (NH4)2HPO4 required to be added to carrier A (3g) to load 6wt.% of the active component Ni2P: the specific operation is as follows: first, clarify that the effective substances of Ni(NO3)2 and (NH4)2HPO4 are NiO and P2O5, respectively. The sum of the masses of NiO and P2O5 is 6 wt.% of the sum of the masses of NiO and P2O5 and the total mass of the impregnation. Simultaneously, the ratio of the mass of NiO divided by its relative molecular mass to the mass of P2O5 is 1:2. Solving this equation, we obtain the masses of NiO and P2O5. Since n(NiO) = n(Ni(NO3)2) and 2n(P2O5) = n((NH4)2HPO4), based on the relative molecular masses of Ni(NO3)2 and (NH4)2HPO4, the masses of Ni(NO3)2 and (NH4)2HPO4 are calculated to be 0.257 and 0.234 g, respectively.
[0053] 0.257 g of Ni(NO3)2 and 0.234 g of (NH4)2HPO4 were dissolved in 30 mL of deionized water and dried at room temperature for 12 h. The sample was then dried in an oven at 120 °C for 12 h and calcined in a muffle furnace at 550 °C for 4 h (heating rate of 1 °C / min) to obtain Ni2P / Al2O3.
[0054] 3g of calcined Ni2P / Al2O3 was divided into four equal portions and placed in four crucibles for impregnation experiments. The liquid reagent used was CH2Cl2. Pre-impregnation was performed according to the relative molecular mass and molar ratio of CH2Cl2. The amount of CH2Cl2 required to achieve the same volume impregnation state was calculated, and the result showed that the amount of CH2Cl2 used was 3g.
[0055] (3) Prepare Pt-Ni2P / Al2O3, wherein the loading of Pt is 5 wt.%;
[0056] The calculation shows that C needs to be added to load 2 wt.% of the active component Pt onto Ni2P / Al2O3. 10 H 14 The quality of O4Pt;
[0057] Calculation method: The loading is 2 wt.%, and the mass ratio of Pt (the sum of the mass of Pt and the mass of 3g Ni2P / Al2O3) is 2 wt.%, so the mass of Pt is first calculated to be 0.061g. Then, based on the equality of the amounts of substance and the fact that Pt and C... 10 H 14 The molecular weight of O4Pt was obtained, and C was calculated. 10 H 14 The mass of O4Pt is 0.123g;
[0058] 0.123g of C 10 H 14 O4Pt was dissolved in 3g of CH2Cl2, dried at room temperature for 12h, and then calcined in a muffle furnace at 250℃ for 2h with a heating rate of 1℃ / min. After calcination, Pt-Ni2P / Al2O3 with a Pt loading of 2wt.% was obtained.
[0059] Example 4:
[0060] (1) Under magnetic stirring, 8.16 g of Al[OCH(CH3)2]3 was dissolved in a three-necked flask containing 40.0 mL of EtOH. The stirring time was 4 h (800 rpm), and then 3.2 mL of concentrated HNO3 was added dropwise over 10 min (to avoid condensation). After the temperature dropped to room temperature, 4.0 g of P123 was dissolved in 20 mL of EtOH and added dropwise to the flask over 5 min. The mixture was dried at 120 °C for 48 h. Calcination was carried out at 550 °C for 4 h (heating rate of 1 °C / min) to completely remove the structure-directing agent. The resulting product was denoted as support A.
[0061] (2) Take 0.5g of the obtained carrier A, put it in a tube and label it, indicating that it is a carrier and its content and mass, for use as a pre-impregnation sample; put the sample (0.5g) for pre-impregnation into the sample tube, add deionized water drop by drop, and accurately record how many milliliters of water are added to achieve the same volume impregnation state. The result is calculated that the amount of deionized water used is 30mL; the 30mL of water obtained is the amount of water used to achieve the same volume impregnation state of carrier A.
[0062] Based on carrier A for subsequent experiments; calculate the mass of Ni(NO3)2 and (NH4)2HPO4 required to be added to carrier A (3g) to load 6wt.% of the active component Ni2P: the specific operation is as follows: first, clarify that the effective substances of Ni(NO3)2 and (NH4)2HPO4 are NiO and P2O5, respectively. The sum of the masses of NiO and P2O5 is 6 wt.% compared to the sum of the masses of NiO, P2O5 and the impregnation amount. Meanwhile, the ratio of the mass of NiO divided by its relative molecular mass is 1:2 compared to the ratio of twice the mass of P2O5 divided by its relative molecular mass. Combining these ratios, we obtain the masses of NiO and P2O5. Since n(NiO) = n(Ni(NO3)2) and 2n(P2O5) = n((NH4)2HPO4), based on the relative molecular masses of Ni(NO3)2 and (NH4)2HPO4, the masses of Ni(NO3)2 and (NH4)2HPO4 are calculated to be 0.257 and 0.234 g, respectively.
[0063] 0.257 g of Ni(NO3)2 and 0.234 g of (NH4)2HPO4 were dissolved in 30 mL of deionized water and dried at room temperature for 12 h. The sample was then dried in an oven at 120 °C for 12 h and calcined in a muffle furnace at 550 °C for 4 h (heating rate of 1 °C / min) to obtain Ni2P / Al2O3.
[0064] Take 3g of calcined Ni2P / Al2O3 and divide it into four equal parts. Place each part into a crucible and conduct an impregnation experiment. The liquid reagent used is CH2Cl2. Pre-impregnate according to the relative molecular mass and molar ratio of CH2Cl2. Calculate the amount of CH2Cl2 required to achieve the same volume impregnation state. The calculated amount of CH2Cl2 is 3g.
[0065] (3) Prepare Pt-Ni2P / Al2O3, wherein the loading of Pt is 10 wt.%;
[0066] The calculation shows that C needs to be added to Ni2P / Al2O3 to load 10 wt.% of the active component Pt. 10 H 14 The quality of O4Pt;
[0067] Calculation method: The loading is 10 wt.%, and the mass ratio of Pt (the sum of the mass of Pt and the mass of 3g Ni2P / Al2O3) is 10 wt.%, so the mass of Pt is first calculated to be 0.333g. Then, based on the equality of the amounts of substance and the fact that Pt and C... 10 H 14 The molecular weight of O4Pt was obtained, and C was calculated. 10 H 14 The mass of O4Pt is 0.671g:
[0068] 0.671g of C 10 H 14 O4Pt was dissolved in 3g of CH2Cl2, dried at room temperature for 12h, and then calcined in a muffle furnace at 250℃ for 2h (heating rate of 1℃ / min) to obtain Pt-Ni2P / Al2O3 with a Pt loading of 10wt.%.
[0069] Figure 1The XRD patterns of the Pt-Ni2P / Al2O3 catalysts are shown below; (a) is the Ni2P / Al2O3 obtained in Example 2, (b) is Pt-Ni2P / Al2O3 with a Pt loading of 0.5 wt.%, (c) is Pt-Ni2P / Al2O3 with a Pt loading of 2 wt.%, (d) is Pt-Ni2P / Al2O3 with a Pt loading of 5 wt.%, and (e) is Pt-Ni2P / Al2O3 with a Pt loading of 10 wt.%. The diffraction peaks of Pt are shown to gradually decrease from 39.82°, 46.29°, and 67.62° with increasing Pt loading, indicating that Pt is well attached to Ni2P / Al2O3.
[0070] Figure 2 The left and right images are HRTEM images of the Pt-Ni2P / Al2O3 catalyst with a Pt loading of 5 wt.% at 100 nm. The images show that Pt is uniformly dispersed on the catalyst.
[0071] Figure 3 The figure shows the 4,6-DMDBT HDS conversion of the Pt-Ni2P / Al2O3 catalyst, where (a) Ni2P / Al2O3, (b) Pt-Ni2P / Al2O3 with a Pt loading of 0.5 wt.%, (c) Pt-Ni2P / Al2O3 with a Pt loading of 2 wt.%, (d) Pt-Ni2P / Al2O3 with a Pt loading of 5 wt.%, and (e) Pt-Ni2P / Al2O3 with a Pt loading of 10 wt.%. The figure shows that the 4,6-DMDBT HDS conversion gradually increases with increasing Pt loading, but the effect is not necessarily more significant with higher loading. At loadings of 5% and 10%, the change is not significant, indicating that a good conversion rate has already been achieved at a Pt loading of 5%, and further increases do not significantly improve the effect.
[0072] Note: The above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention. Therefore, although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention. All technical solutions and improvements that do not depart from the spirit and scope of the present invention should be covered within the scope of the claims of the present invention.
Claims
1. A preparation method of a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst, characterized in that, Includes the following steps: (1) Under magnetic stirring, Al[OCH(CH3)2]3 was added to ethanol and stirred for a period of time. Then concentrated nitric acid was added dropwise. After the temperature dropped to room temperature, a mixture of P123 and ethanol was added. Finally, the product was dried and calcined. The product obtained was denoted as carrier A. (2) Using the carrier A obtained in step (1), an impregnation experiment was conducted. The liquid reagent used was deionized water. The amount of deionized water required to achieve the same volume of impregnation was recorded as V1. Then, Ni(NO3)2 and (NH4)2HPO4 were dissolved in V1 of the deionized water. The resulting mixture was dried at room temperature. After drying, it was dried and calcined to obtain the solid product, which is Ni2P / Al2O3. (3) An impregnation experiment was conducted on the Ni2P / Al2O3 obtained in step (2). The liquid reagent used was dichloromethane. The amount of dichloromethane required to achieve the same volume impregnation state was obtained and denoted as M1. Then, platinum acetylacetonate was dissolved in dichloromethane with a mass of M1. The resulting mixed solution was dried at room temperature and then placed in a muffle furnace for calcination. After calcination, the Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst was obtained and denoted as Pt-Ni2P / Al2O3. The loading of Pt in the Pt-Ni2P / Al2O3 was 0.5 wt.% ~ 10 wt.%.
2. The preparation method of the Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 1, characterized in that, In step (1), the amounts of Al[OCH(CH3)2]3, ethanol, concentrated HNO3, and P123 are in the following ratio: 8.16 g : 60.0 mL : 3.2 mL : 4.00 g. The concentrated HNO3 is added dropwise over 10 to 15 minutes. The mixture of P123 and ethanol is added dropwise over 5 to 10 minutes.
3. The preparation method of the Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 1, characterized in that, In step (1), the stirring time is 4 hours and the stirring speed is 800 rpm; the drying temperature is 120~140℃ and the time is 48 hours.
4. The preparation method of the Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 1, characterized in that, In step (1), the calcination temperature is 550 ~ 560℃, the time is 4 h, and the heating rate is 1℃ / min.
5. The preparation method of a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 1, characterized in that, In step (2), V1 ≥ 30 mL, and the ratio of the amounts of Ni(NO3)3, (NH4)2HPO4 to deionized water is 0.257 g : 0.234 g : V1 mL.
6. The preparation method of a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 5, characterized in that, The ratio of Ni(NO3)3, (NH4)2HPO4 to deionized water is 0.257 g : 0.234 g : 30 mL.
7. The preparation method of a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 1, characterized in that, In step (2), the drying time at room temperature is 12 h, the drying temperature is 120℃, and the time is 12 h; the calcination temperature is 550℃, the time is 4 h, and the heating rate is 1℃ / min.
8. The method for preparing a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 1, characterized in that, In step (3), the ratio of the amount of platinum acetylacetonate to dichloromethane is 0.0304 g ~ 0.671 g : 3 g.
9. The method for preparing a Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst according to claim 1, characterized in that, In step (3), the drying time at room temperature is 12 h, the calcination temperature is 250℃, the calcination time is 2 h, and the heating rate is 1℃ / min.
10. The use of the Pt-doped Ni2P / Al2O3 hydrodesulfurization catalyst prepared by any one of claims 1 to 9 for oil desulfurization.