A catalyst for catalytic hydrogenation of nitro groups, resistant to sulfur, and a method for its preparation and use

Abstract

The application relates to a nitro catalytic hydrogenation sulfur-resistant catalyst and a preparation method and application thereof, and belongs to the technical field of nickel-based catalyst preparation. The catalyst is prepared by adopting a deposition precipitation method and takes nickel as an active component, adds a certain amount of molybdenum additives and takes diatomite as a carrier; the catalyst is suitable for a catalytic hydrogenation production process of a p-nitrophenyl-beta-hydroxyethyl sulfone or m-nitrophenyl-beta-hydroxyethyl sulfone. The catalyst can be recycled and applied for multiple times while maintaining high activity and high selectivity, the efficiency of the catalyst is improved with the increase of the molybdenum content, and the catalyst can be recycled and applied for multiple times, which shows that the addition of molybdenum is beneficial to the sulfur resistance of the catalyst. The catalyst has the characteristics of high catalytic activity, good stability and easy separation; compared with a traditional Raney nickel catalyst, the catalyst can still maintain high activity after being used for multiple times, and has important significance for realizing the nitro catalytic hydrogenation sulfur resistance.

Description

Technical Field

[0001] This invention belongs to the field of nickel-based catalyst preparation technology, specifically relating to a catalyst for producing para-ester and meta-ester intermediates and its preparation method. Background Technology

[0002] p-Aminophenyl-β-hydroxyethyl sulfone sulfate, also known as para-ester, is an important intermediate for vinyl sulfone-type reactive dyes. Other similar reactive groups include m-β-hydroxyethyl sulfone sulfate aniline and 4-chloro-3-(β-hydroxyethyl sulfone)aniline. Reactive dyes are crucial for cellulose dye applications. As a hydroxyethyl sulfone-type intermediate for reactive dyes, it improves the solubility of the dye during application while reducing its affinity for fibers during dyeing, resulting in better bleed-through effects. Furthermore, the formation of dye-fiber ether bonds, which offer good acid resistance and thermal stability, significantly improves washing efficiency and wet fastness of printed and dyed products.

[0003] Currently, the main synthetic methods for p-aminophenyl-β-hydroxyethyl sulfone sulfate include the acetanilide-ethylene oxide method, the acetanilide-chloroethanol method, the ethylene oxide method, and the mercaptoethanol method. Considering factors such as safety, environmental protection, production costs, and product yield, the mercaptoethanol method is currently the most widely used. A European patent uses p-nitrochlorobenzene as a raw material, which is condensed with mercaptoethanol, oxidized, then hydrogenated, and finally esterified to obtain the para-ester, with an overall yield of 86%-87%.

[0004] The reduction of p-nitrophenyl-β-hydroxyethyl sulfone generally employs catalytic hydrogenation, which is also applicable to the production of related meta-esters.

[0005]

[0006] In addition, this catalyst is also suitable for other routes to produce various sulfur-containing aniline compounds such as para-esters and meta-esters. Using thiophenol as a substrate, chloroethanol substitution followed by oxidation with an oxidant can also yield phenyl hydroxyethyl sulfone compounds. However, when the nitro group is present in phenyl thiophenol (ortho, meta, para), the catalyst still faces the problem of sulfur poisoning during catalytic hydrogenation to prepare hydroxyethyl sulfone aniline compounds. Taking meta- and para-nitro groups as examples, the reaction is as follows:

[0007]

[0008] Nitro-based catalytic hydrogenation catalysts, such as Raney nickel, Pd-activated carbon, and Mo-doped Raney nickel, can be used with methanol as a solvent at 80°C and 1 MPa, achieving a yield of over 95%. While the yield and selectivity are considerable, practical applications have revealed poor catalyst lifetime when using Raney nickel and similar catalysts, necessitating frequent replacement with fresh catalyst. This leads to catalyst waste and increased production costs in industrial processes. The cause of this catalyst poisoning is as follows: regardless of the amount of mercaptoethanol added, a small amount of low-valence sulfur remains. The presence of lone pairs of electrons easily occupies empty orbitals of group VIII elements such as nickel-based elements, forming paired electrons that are difficult to desorb, resulting in sulfur poisoning of the catalyst. Noble metal catalysts not only suffer from this problem but are also expensive, making them unsuitable for large-scale production. Summary of the Invention

[0009] This invention provides a catalyst for the catalytic hydrogenation of p-aminophenyl-β-hydroxyethyl sulfone aniline and its preparation method. The catalyst uses nickel as the active component, modified with a certain amount of molybdenum, and uses diatomaceous earth as a support. Due to the synergistic catalytic effect of nickel-molybdenum and diatomaceous earth, the catalyst activity and sulfur resistance are significantly improved, and it exhibits good stability. Under relatively mild reaction conditions, high conversion and high selectivity can be achieved in the catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone to the para-ester. Furthermore, the catalyst maintains a good lifespan even after multiple reactor reuses, effectively solving the problem of sulfur poisoning in nickel-based catalysts.

[0010] This invention is achieved through the following technical solution:

[0011] A catalyst for nitro-catalyzed hydrogenation and sulfur resistance is provided. The catalyst is prepared by a deposition-precipitation method. The catalyst uses nickel as the active component, diatomaceous earth as the support, and molybdenum as an auxiliary agent. The mass percentage composition of the catalyst is 5%-20% molybdenum, 30%-50% nickel, and 30%-60% diatomaceous earth.

[0012] Furthermore, the catalyst has the following mass percentage composition: molybdenum 10%-15%, nickel 40%-50%, and diatomaceous earth 40%-55%.

[0013] A method for preparing a nitro-catalyzed hydrogenation antisulfur catalyst, the method comprising the following steps:

[0014] (1) Prepare a nickel salt solution with a mass concentration of 20-40%, add molybdenum salt and stir until dissolved, add diatomaceous earth carrier to the above mixed solution, stir at 20-35℃ for 1-2 hours; then add 500-1000μL silica sol, stir at 20-35℃ for 1-2 hours, and then heat to 80-90℃;

[0015] (2) Prepare a precipitant solution with a mass concentration of 1-40%, and add it to the mixture obtained in step 1) under the above stirring conditions using a peristaltic pump. Stir at 80-90℃ for 10-24h; the molar ratio of the precipitant to the nickel salt is 2-3; (3) After the reaction is completed, filter the filter cake, dry it at 60-80℃, grind and sieve it, and then place it in a tube furnace and reduce it at 300-700℃ in a hydrogen atmosphere for 4-6h to obtain the catalyst.

[0016] The nickel salt is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride, or nickel acetate.

[0017] The molybdenum salt is ammonium molybdate tetrahydrate.

[0018] The precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, ammonia, or urea. Application of a nitro-catalyzed hydrogenation antisulfur catalyst, said catalyst being used in the catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone.

[0019] The catalytic hydrogenation process is as follows: the catalyst is reacted with p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone in a solvent for 0.5-2 h; the mass ratio of the catalyst to p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone is 0.05-0.2:1, the reaction temperature is 50-90℃, and the hydrogen pressure is 0.5-2 MPa.

[0020] The reaction apparatus for catalytic hydrogenation can be a batch reactor, a loop reactor, or a fixed-bed reactor.

[0021] The solvent is one or more of anhydrous methanol, anhydrous ethanol, and tetrahydrofuran, and the mass ratio of the solvent to p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone is 3:1-10:1.

[0022] This invention provides a catalyst for the hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone to p-aminophenyl-β-hydroxyethyl sulfone. The catalyst uses nickel as the active component, adds a certain amount of molybdenum as an additive, and uses diatomaceous earth as a support. The catalyst's mass percentage composition is: molybdenum 5%-20%, preferably 10%-15%; nickel 30%-50%, preferably 40%-50%; and diatomaceous earth 30%-60%, preferably 40%-55%. Utilizing the synergistic catalytic effect of nickel-molybdenum and diatomaceous earth, and the principle of using molybdenum as an additive to overcome sulfur poisoning, highly efficient catalytic hydrogenation to p-aminophenyl-β-hydroxyethyl sulfone can be achieved.

[0023] Furthermore, the present invention also provides a method for using the above-mentioned nickel catalyst, the method comprising the following steps:

[0024] 1) Prepare a nickel salt solution with a mass concentration of 20-40%, add a certain amount of ammonium molybdate tetrahydrate, stir until dissolved, add the diatomaceous earth carrier to the above mixed solution, and stir at 20-35℃ for 1-2 hours;

[0025] 2) Add 50-100 μL of silica sol to step 1), stir at 20-35℃ for 1-2 h, and then raise the temperature to 80-90℃. Prepare a 1-40% precipitant solution, and add it to the mixture obtained in step 1) using a peristaltic pump under the above stirring conditions, and stir at 80-90℃ for 10-24 h; weigh 1-5 g of ammonium molybdate tetrahydrate and add it to the mixture.

[0026] 3) Filter the mixture obtained in step 2), dry the filter cake at 60-80℃, grind and sieve it, and then place it in a tube furnace and reduce it in a hydrogen atmosphere at 300-700℃ for 4-6 hours to obtain the nickel-molybdenum supported diatomite catalyst.

[0027] Furthermore, in the above preparation method, the diatomaceous earth mentioned in step 1) is selected from diatomaceous earth filter aid, and the median particle size of the solvent-calcined product is 13 μm.

[0028] The present invention also provides a method for catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone using the above-mentioned catalyst: the catalyst reacts with p-nitrophenyl-β-hydroxyethyl sulfone in a solvent for 0.5-2 h, preferably 0.5-1 h; the mass ratio of the catalyst to p-nitrophenyl-β-hydroxyethyl sulfone is 0.02-0.2:1, preferably 0.05-0.1:1; the reaction temperature is 50-90℃, preferably 60-80℃, and the hydrogen pressure is 0.5-1 MPa, preferably 0.8-1 MPa; the reaction apparatus is one of a batch reactor, a loop reactor, or a fixed-bed reactor, preferably a batch reactor.

[0029] The reaction solvent is one or a mixture of several of anhydrous methanol, anhydrous ethanol, and tetrahydrofuran, and the mass ratio of the solvent to p-nitrophenyl-β-hydroxyethyl sulfone is 5:1.

[0030] The beneficial effects of this invention are as follows:

[0031] This invention prepared 44% Ni / diatomite catalysts and 44% Ni-Mo / diatomite catalysts with different molybdenum contents using a deposition-precipitation method. Cyclic reuse experiments were then conducted on each catalyst. The 44% Ni-Mo / diatomite catalyst maintained high activity and selectivity while significantly extending its lifetime, allowing for multiple cycles. The catalyst efficiency improved with increasing molybdenum content, and it could be reused multiple times. The catalysts were characterized by SEM, TEM, XRD, BET, and XPS. The characteristics of the catalysts before and after molybdenum addition were compared from the perspectives of geometric structure and electronic effects. During the deposition-precipitation process, molybdenum and nickel synergistically interacted. Molybdenum regulated the catalyst's geometric structure and electronic effects, resulting in more uniform nickel particle dispersion, increased specific surface area, and altered nickel surface electronic effects, thereby improving catalyst activity and lifetime.

[0032] The prepared Ni-Mo / diatomite catalyst exhibits high catalytic activity, good stability, and easy separation. Under mild reaction conditions, it catalyzes the hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone, achieving high conversion and high selectivity. Compared to traditional Raney nickel catalysts, this catalyst maintains high activity even after multiple uses, which is of great significance for achieving this type of nitro catalytic hydrogenation for sulfur resistance.

[0033] (1) A supported catalyst was prepared using inexpensive metallic nickel, which has similar reactivity to Raney nickel and noble metal catalysts, greatly reducing the production cost of para-esters by mercaptoethanol method.

[0034] (2) Compared with traditional Raney nickel catalysts, this type of supported catalyst has good anti-sulfur poisoning characteristics, can be stably recycled 6-10 times, and maintains high activity, solving the problems of difficult transportation and inability to be recycled of Raney nickel.

[0035] 3) In the reaction of catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone to prepare p-aminophenyl-β-hydroxyethyl sulfone, milder reaction conditions are adopted: temperature 60-80℃, pressure 0.8-1MPa, which reduces the amount of catalyst used, improves production efficiency, and significantly reduces the overall economic cost. Attached Figure Description

[0036] Figure 1 These are scanning electron microscope (SEM) images of the Ni / diatomite and Ni-Mo / diatomite catalysts prepared in Example 1, where ac represents Ni-Mo / diatomite and df represents Ni / diatomite.

[0037] Figure 2 is Transmission electron microscopy images of the Ni / diatomite and Ni-Mo / diatomite catalysts prepared in Example 1, wherein: ab represents Ni / diatomite and ci represents Ni-Mo / diatomite.

[0038] Figure 3 These are XRD images of the Ni / diatomite and Ni-Mo / diatomite catalysts prepared in Example 1, wherein: (a) Ni / diatomite characterization, (b) Ni-Mo / diatomite.

[0039] Figure 4 These are BET images of the Ni / diatomite and Ni-Mo / diatomite catalysts prepared in Example 1, wherein: (a) diatomite, (b) Ni / diatomite, and (c) Ni-Mo / diatomite.

[0040] Figure 5 These are XPS images of the Ni / diatomite and Ni-Mo / diatomite catalysts prepared in Example 1, wherein: (a) Ni / diatomite, (b) Ni-Mo / diatomite. Detailed Implementation

[0041] The reaction apparatus used in this invention is a batch reactor. Suitable process conditions are as follows: the catalyst reacts with p-nitrophenyl-β-hydroxyethyl sulfone in a solvent for 0.5-2 h, preferably 0.5-1 h; the mass ratio of the catalyst to p-nitrophenyl-β-hydroxyethyl sulfone is 0.02-0.2:1, preferably 0.05-0.1:1; the reaction temperature is 50-90℃, preferably 60-80℃; the hydrogen pressure is 0.5-1 MPa, preferably 0.8-1 MPa; the reaction apparatus is one of a batch reactor, a loop reactor, or a fixed-bed reactor, preferably a batch reactor.

[0042] The reaction selectivity and conversion rate described in this invention are achieved using the following methods and standards: high performance liquid chromatography, C18 reversed-phase column; Qexactive high resolution liquid chromatography-mass spectrometry system;

[0043] The present invention will be further described below with reference to embodiments.

[0044] Nickel nitrate was purchased from Dalian General Chemical Co., Ltd.: the Ni(NO3)2·6H2O content was not less than 98%;

[0045] Diatomaceous earth was purchased from Dalian General Chemical Co., Ltd.: diatomaceous earth filter aid, flux calcined product, median particle size: 13μm;

[0046] Urea was purchased from Guangdong Guanghua Technology Co., Ltd.: H2NCONH2 content not less than 99.0%;

[0047] Raney nickel was purchased from Dalian General Chemical Co., Ltd.: RTH-2146, with an active ingredient Ni content greater than 90%;

[0048] The Pd / C was purchased from Shaanxi Ruike New Materials Co., Ltd.: 5% Pd / C, with the active component Pd content being 5%.

[0049] Example 1

[0050] Preparation of Ni-Mo / diatomaceous earth catalyst: 14.2 g of nickel nitrate and 1.2 g of ammonium molybdate tetrahydrate were dissolved in 50 ml of distilled water and stirred at 25 °C for 1 h. 3 g of diatomaceous earth was added and stirring continued for 1 h. 600 μL of silica sol was added and stirring continued for 1 h, then the temperature was raised to 90 °C. 7.50 g of urea was dissolved in 50 ml of distilled water to prepare a 13% urea solution, which was added to the above solution using a peristaltic pump and stirred at 90 °C for 24 h. The resulting solution was filtered and washed three times to obtain a solid, which was then dried in an oven for 20 h to obtain the precursor. The precursor was ground and sieved, and then reduced at 500 °C for 4 h under a hydrogen atmosphere to obtain 44% Ni-Mo. 10 Diatomaceous earth catalyst. Its scanning electron microscope image is shown below. Figure 1 (ac is Ni-Mo / diatomite), transmission electron microscopy image can be found here. Figure 2 ci is Ni-Mo / diatomite).

[0051] Preparation of Ni / diatomaceous earth: 11.7 g of nickel nitrate was dissolved in 41 ml of distilled water to prepare a 22.2% nickel nitrate aqueous solution. The solution was stirred at 25 °C for 1 h, and an appropriate amount of diatomaceous earth was added, with stirring continuing for another h. 600 μL of silica sol was added, and stirring continued for another h, followed by heating to 90 °C. 6.2 g of urea was dissolved in 41 ml of distilled water to prepare a 13.1% solution, which was added to the above solution using a peristaltic pump. The solution was stirred at 90 °C for 24 h. The resulting solution was filtered and washed three times to obtain a solid, which was then dried in an oven for 20 h to obtain a precursor. The precursor was then ground and sieved. The precursor was then reduced at 500 °C for 4 h under a hydrogen atmosphere to obtain a 44% Ni / diatomaceous earth catalyst. Scanning electron micrographs are shown below. Figure 1 (df ​​represents Ni / diatomite), transmission electron microscopy image can be found here. Figure 2 ab represents Ni / diatomite.

[0052] Catalyst performance testing: Four different catalysts were applied to the hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone using a batch reactor. The reaction conditions were: 3.0 g p-nitrophenyl-β-hydroxyethyl sulfone, 15.0 g anhydrous methanol solvent, and 0.3 g catalyst. The reaction results are shown in the table below. Catalytic hydrogenation experiments were conducted using four catalysts: Raney nickel, Pd / C, Ni / diatomaceous earth, and Ni-Mo / diatomaceous earth, at 80 °C and 1.0 MPa. Based on the results of a single application, Raney nickel and Pd / C showed the highest activity, followed by Ni-Mo / diatomaceous earth, while Ni / diatomaceous earth showed the lowest activity. However, the comparison indicates that the addition of molybdenum has a certain effect on improving the activity of the supported nickel catalyst.

[0053] Table 1. Results of hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone

[0054] catalyst Reaction temperature / °C Reaction pressure / MPa Reaction time / min Conversion rate / % Selectivity / % Ni-Mo / Diatomite 80.0 1.0 36.0 100.0 100.0 Raney nickel 80.0 1.0 25.2 100.0 100.0 Ni / diatomaceous earth 80.0 1.0 66.0 99.8 100.0 Pd / C 80.0 1.0 25.8 100.0 98.6

[0055] Example 2

[0056] Ni-Mo 10 Preparation of diatomaceous earth catalyst: 14.2 g of nickel nitrate and 1.2 g of ammonium molybdate tetrahydrate were dissolved in 50 ml of distilled water and stirred at 25 °C for 1 h. 3 g of diatomaceous earth was added and stirring continued for 1 h. 600 μL of silica sol was added and stirring continued for 1 h, then the temperature was raised to 90 °C. 7.5 g of urea was dissolved in 50 ml of distilled water to prepare a 13% urea solution, which was added to the above solution using a peristaltic pump and stirred at 90 °C for 24 h. The resulting solution was filtered and washed three times to obtain a solid, which was dried in an oven for 20 h to obtain a precursor. This precursor was then ground and sieved. The precursor was then reduced at 500 °C for 4 h under a hydrogen atmosphere to obtain 44% Ni-Mo. 10 Diatomaceous earth catalyst.

[0057] Catalyst performance testing: A batch reactor was used to apply the catalyst to the hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone. The reaction conditions were: 3g p-nitrophenyl-β-hydroxyethyl sulfone, 15g anhydrous methanol solvent, and 0.3g Ni-Mo. 10％ The diatomaceous earth catalyst was used at a reaction pressure of 1 MPa. The catalyst activity was investigated at different temperatures, and the results are shown in the table below. As the temperature increased, the catalytic hydrogenation rate gradually increased. When the temperature reached 80℃, the reaction time was only 0.5 h. Further increasing the temperature did not significantly improve the reaction rate, and the increased temperature required higher heating, which was not conducive to saving resources. Therefore, 80℃ was the optimal reaction temperature.

[0058] Table 2. Investigation of hydrogenation temperature of p-nitrophenyl-β-hydroxyethyl sulfone

[0059] catalyst Temperature / °C Reaction time / min Conversion rate / % Selectivity / % <![CDATA[Ni-Mo 10 Diatomaceous earth 60.0 88.8 100.0 100.0 <![CDATA[Ni-Mo 10 Diatomaceous earth 70.0 64.2 100.0 100.0 <![CDATA[Ni-Mo 10 Diatomaceous earth 80.0 36.0 100.0 100.0 <![CDATA[Ni-Mo 10 Diatomaceous earth 90.0 32.4 100.0 100.0 <![CDATA[Ni-Mo 10 Diatomaceous earth 100.0 31.2 100.0 100.0

[0060] Example 3

[0061] Preparation of Ni-Mo5 / diatomaceous earth catalyst: 12.8 g of nickel nitrate and 0.54 g of ammonium molybdate tetrahydrate were dissolved in 45 ml of distilled water and stirred at 25 °C for 1 h. 3 g of diatomaceous earth was added and stirring was continued for 1 h. 600 μL of silica sol was added and stirring was continued for 1 h, then the temperature was raised to 90 °C. 6.8 g of urea was dissolved in 45 ml of distilled water to prepare a 13% urea solution, which was added to the above solution using a peristaltic pump and stirred at 90 °C for 24 h. The resulting solution was filtered and washed three times to obtain a solid, which was dried in an oven for 20 h to obtain a precursor. The precursor was then ground and sieved. The precursor was placed under a hydrogen atmosphere and reduced at 500 °C for 4 h to obtain a 44% Ni-Mo5 / diatomaceous earth catalyst.

[0062] Catalyst performance testing: A batch reactor was used to apply the catalyst to the hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone. The reaction conditions were: 3g p-nitrophenyl-β-hydroxyethyl sulfone, 15g anhydrous methanol solvent, and 0.3g Ni-Mo5 / diatomaceous earth catalyst. The reaction results are as follows:

[0063] Table 4. Lifetime Experiment of Ni-Mo5 / Diatomite

[0064] Number of times to apply catalyst Reaction time / min Conversion rate / % Selectivity / % 1 <![CDATA[Ni-Mo5 / Diatomaceous earth]]> 58.8 100.0 100.0 2 <![CDATA[Ni-Mo5 / Diatomaceous earth]]> 49.8 100.0 100.0 3 <![CDATA[Ni-Mo5 / diatomaceous earth]]> 58.2 100.0 100.0 4 <![CDATA[Ni-Mo5 / Diatomaceous earth]]> 81.0 100.0 100.0 5 <![CDATA[Ni-Mo5 / diatomaceous earth]]> 103.8 86.4 100.0

[0065] Example 4

[0066] Ni-Mo 10 Preparation of diatomaceous earth catalyst: 14.2 g of nickel nitrate and 1.2 g of ammonium molybdate tetrahydrate were dissolved in 50 ml of distilled water and stirred at 25 °C for 1 h. 3 g of diatomaceous earth was added and stirring continued for 1 h. 600 μL of silica sol was added and stirring continued for 1 h, then the temperature was raised to 90 °C. 7.5 g of urea was dissolved in 50 ml of distilled water to prepare a 13% urea solution, which was added to the above solution using a peristaltic pump and stirred at 90 °C for 24 h. The resulting solution was filtered and washed three times to obtain a solid, which was then dried in an oven for 20 h to obtain the precursor. The precursor was then reduced at 500 °C for 4 h under a hydrogen atmosphere to obtain 44% Ni-Mo. 10 Diatomaceous earth catalyst.

[0067] Catalyst performance testing: A batch reactor was used to apply the catalyst to the catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone. The reaction conditions were: 3g p-nitrophenyl-β-hydroxyethyl sulfone, 15ml anhydrous methanol solvent, and 0.3g Ni-Mo. 10 The reaction was carried out using diatomaceous earth catalyst at a temperature of 80℃ and a pressure of 1MPa. The reaction results are as follows:

[0068] Table 5.Ni-Mo 10 / Diatomite lifetime experiment

[0069] Number of times to apply catalyst Reaction time / min Conversion rate / % Selectivity / % 1 <![CDATA[Ni-Mo 10 Diatomaceous earth 36.0 100 100 2 <![CDATA[Ni-Mo 10 Diatomaceous earth 34.2 100 100 3 <![CDATA[Ni-Mo 10 Diatomaceous earth 34.2 100 100 4 <![CDATA[Ni-Mo 10 Diatomaceous earth 39.0 100 100 5 <![CDATA[Ni-Mo 10 Diatomaceous earth 42.0 100 100 6 <![CDATA[Ni-Mo 10 Diatomaceous earth 43.8 100 100

[0070] Example 5

[0071] Ni-Mo 15Preparation of diatomaceous earth catalyst: 16.0 g of nickel nitrate and 2.0 g of ammonium molybdate tetrahydrate were dissolved in 55.5 ml of distilled water and stirred at 25 °C for 1 h. 3 g of diatomaceous earth was added and stirring continued for 1 h. 600 μL of silica sol was added and stirring continued for 1 h, then the temperature was raised to 90 °C. 8.4 g of urea was dissolved in 55.5 ml of distilled water to prepare a 13% urea solution, which was added to the above solution using a peristaltic pump and stirred at 90 °C for 24 h. The resulting solution was filtered and washed three times to obtain a solid, which was then dried in an oven for 20 h to obtain the precursor. The precursor was then reduced at 500 °C for 4 h under a hydrogen atmosphere to obtain 44% Ni-Mo. 15 Diatomaceous earth catalyst.

[0072] Catalyst performance testing: A batch reactor was used to apply the catalyst to the catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone. The reaction conditions were: 3g p-nitrophenyl-β-hydroxyethyl sulfone, 15g anhydrous methanol solvent, and 0.3g Ni-Mo. 15 The reaction was carried out using diatomaceous earth catalyst at a temperature of 80℃ and a pressure of 1MPa. The reaction results are as follows:

[0073] Table 6.Ni-Mo 15 / Diatomite lifespan test results

[0074]

[0075]

[0076] Example 6

[0077] Ni-Mo 20 Preparation of diatomaceous earth catalyst: 17.7 g of nickel nitrate and 2.8 g of ammonium molybdate tetrahydrate were dissolved in 62 ml of distilled water and stirred at 25 °C for 1 h. 3 g of diatomaceous earth was added and stirring continued for 1-3 h. 600 μL of silica sol was added and stirring continued for 1 h, then the temperature was raised to 90 °C. 9.4 g of urea was dissolved in 62 ml of distilled water to prepare a 13% urea solution, which was added to the above solution using a peristaltic pump and stirred at 90 °C for 1 h. The resulting solution was filtered and washed three times to obtain a solid, which was then dried in an oven for 20 h to obtain the precursor. The precursor was then reduced at 500 °C for 4 h under a hydrogen atmosphere to obtain 44% Ni-Mo. 20 Diatomaceous earth catalyst.

[0078] Catalyst performance testing: A batch reactor was used to apply the catalyst to the catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone. The reaction conditions were: 3g p-nitrophenyl-β-hydroxyethyl sulfone, 15g anhydrous methanol solvent, and 0.3g Ni-Mo. 20 The reaction was carried out using diatomaceous earth catalyst at a temperature of 80℃ and a pressure of 1MPa. The reaction results are as follows:

[0079] Table 7.Ni-Mo 20 / Diatomite lifespan test results

[0080] Number of times to apply catalyst Reaction time / min Conversion rate / % Selectivity / % 1 <![CDATA[Ni-Mo 20 Diatomaceous earth 49.2 100 100 2 <![CDATA[Ni-Mo 20 Diatomaceous earth 38.4 100 100 3 <![CDATA[Ni-Mo 20 Diatomaceous earth 42.6 100 100 4 <![CDATA[Ni-Mo 20 Diatomaceous earth 44.4 100 100 5 <![CDATA[Ni-Mo 20 Diatomaceous earth 48.0 100 100 6 <![CDATA[Ni-Mo 20 Diatomaceous earth 42.6 100 100 7 <![CDATA[Ni-Mo 20 Diatomaceous earth 48.6 100 100 8 <![CDATA[Ni-Mo 20 Diatomaceous earth 52.2 100 100

[0081] A 44% Ni / diatomite catalyst and 44% Ni-Mo / diatomite catalysts with different molybdenum contents were prepared and subjected to cyclic reuse experiments. A comparative test was conducted on the catalysts before and after molybdenum addition. The results showed that adding molybdenum significantly extended the catalyst's lifetime while maintaining high activity and selectivity, enabling multiple cycles. The catalyst efficiency improved with increasing molybdenum content, and multiple cycles were also possible, indicating that molybdenum addition is beneficial for the catalyst's sulfur resistance. The catalysts were characterized by SEM, TEM, XRD, BET, and XPS. The characteristics of the catalysts before and after molybdenum addition were compared from the perspectives of geometric structure and electronic effects. Molybdenum addition modulated the catalyst's geometric structure and electronic effects, resulting in more uniform nickel particle dispersion, increased specific surface area, and altered nickel surface electronic effects, thereby improving catalyst activity and lifetime.

[0082] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. The application of a catalyst for nitro-catalyzed hydrogenation and sulfur resistance, characterized in that: The catalyst is used in the catalytic hydrogenation of p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone; The catalyst is prepared by a deposition-precipitation method, which includes the following steps: (1) Prepare a nickel salt solution with a mass concentration of 20-40%, add molybdenum salt and stir until dissolved, add diatomaceous earth carrier to the above mixed solution, stir at 20-35 ℃ for 1-2 h; then add 500-1000 μL of silica sol, stir at 20-35 ℃ for 1-2 h, and then raise the temperature to 80-90 ℃; (2) Prepare a precipitant solution with a mass concentration of 1-40%, and add it to the mixture obtained in step (1) under the above stirring conditions using a peristaltic pump, and stir at 80-90 °C for 10-24 h; the molar ratio of the precipitant to the nickel salt is 2-3; (3) After the reaction is completed, filter the filter cake, dry it at 60-80 °C, grind and sieve it, and then place it in a tube furnace and reduce it at 300-700 °C in a hydrogen atmosphere for 4-6 h to obtain the catalyst. The catalyst uses nickel as the active component, diatomaceous earth as the carrier, and molybdenum as an auxiliary agent; the mass percentage composition of the catalyst is 5%-20% molybdenum, 30%-50% nickel, and 30%-60% diatomaceous earth.

2. The application of the nitro-catalyzed hydrogenation antisulfur catalyst according to claim 1, characterized in that: The catalyst has the following composition by mass percentage: 10%-15% molybdenum, 40%-50% nickel, and 40%-55% diatomaceous earth.

3. The application of the nitro-catalyzed hydrogenation antisulfur catalyst according to claim 1, characterized in that: The nickel salt is selected from one or more of nickel nitrate, nickel sulfate, nickel chloride, or nickel acetate.

4. The application of the nitro-catalyzed hydrogenation antisulfur catalyst according to claim 1, characterized in that: The molybdenum salt is ammonium molybdate tetrahydrate.

5. The application of the nitro-catalyzed hydrogenation antisulfur catalyst according to claim 1, characterized in that: The precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonium carbonate, ammonia, or urea.

6. The application of the nitro-catalyzed hydrogenation antisulfur catalyst according to claim 1, characterized in that: The catalytic hydrogenation process is as follows: the catalyst is reacted with p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone in a solvent for 0.5-2 h; the mass ratio of the catalyst to p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone is 0.05-0.2:1, the reaction temperature is 50-90 ℃, and the hydrogen pressure is 0.5-2 MPa.

7. The application of the nitro-catalyzed hydrogenation antisulfur catalyst according to claim 1, characterized in that: The reaction apparatus for catalytic hydrogenation can be a batch reactor, a loop reactor, or a fixed-bed reactor.

8. The application of the catalyst for nitro-catalyzed hydrogenation and sulfur resistance according to claim 6, characterized in that: The solvent is one or more of anhydrous methanol, anhydrous ethanol, and tetrahydrofuran, and the mass ratio of the solvent to p-nitrophenyl-β-hydroxyethyl sulfone or m-nitrophenyl-β-hydroxyethyl sulfone is 3:1-10:1.

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