Process for the hydrogenation of a tert-butylphenol and catalyst used

Abstract

The application discloses a kind of tert-butyl phenol hydrogenation method and catalyst used.The hydrogenation method with tert-butyl phenol and hydrogen as raw material, in the presence of catalyst hydrogenation reaction, generate tert-butyl cyclohexanol, the catalyst is supported catalyst, and include carrier, nickel-based alloy and alkali earth metal oxide, the nickel-based alloy and alkali earth metal oxide are loaded on the carrier, the nickel-based alloy includes nickel and metal M, the metal M is selected from the combination of one or more of Fe, Co, Cu, Zn, Ga, In, Mo, W.The active metal is alloyed with Ni in the application, to use nickel-based alloy as the main component of catalyst, while using alkali earth metal oxide to modify nickel-based alloy, can significantly improve the selectivity of cis-ortho tert-butyl cyclohexanol and cis-para tert-butyl cyclohexanol;While can effectively inhibit the shedding of tert-butyl, reduce the content of byproduct cyclohexanol.

Description

Technical Field

[0001] This invention relates to a method for hydrogenating tert-butylphenol and the catalyst used therein. Background Technology

[0002] o- / p-tert-butylcyclohexyl acetate, as one of the most in-demand synthetic fragrances, is widely used in the formulation of perfumes, cosmetics, and soap fragrances. o- / p-tert-butylcyclohexyl acetate is not found in nature. The common production method uses phenol as a starting material, alkylating it with isobutylene gas in an acidic catalyst to obtain o- / p-tert-butylphenol, followed by catalytic hydrogenation to synthesize o- / p-tert-butylcyclohexanol, and finally esterification with acetate to obtain o- / p-tert-butylcyclohexyl acetate. Tert-butylcyclohexyl acetate exists as a cis-trans isomer; compared to trans-tert-butylcyclohexyl acetate, cis-tert-butylcyclohexyl acetate has a more delicate and milder aroma. The fragrance industry generally requires products to contain more than 82% cis-o-tert-butylcyclohexyl acetate and more than 23% cis-p-tert-butylcyclohexyl acetate. Related experiments show that the esterification process of tert-butylcyclohexanol does not cause a change in the cis-trans ratio; therefore, the content of cis-tert-butylcyclohexyl acetate in the product is determined by the content of cis-tert-butylcyclohexanol. The cis-trans ratio of tert-butylcyclohexanol is determined by the hydrogenation reaction of tert-butylphenol.

[0003] Chinese patent CN201711038858.7 discloses a catalyst using Pd / C for the hydrogenation reaction of tert-butylphenol, which can completely convert o-tert-butylphenol with a selectivity of greater than 85% for cis-o-tert-butylcyclohexanol in the hydrogenation product. Chinese patent CN201010183161.0 discloses a catalyst using Ru / Al₂O₃ for the hydrogenation reaction of tert-butylphenol, achieving a selectivity of 88% for cis-o-tert-butylcyclohexanol. It also found that adding sodium hydroxide or water to the reaction system can further improve the selectivity for cis-o-tert-butylcyclohexanol. All of the above catalysts are precious metal catalysts, which are expensive, and the precious metals are easily lost, further increasing production costs, especially for continuous reactions, resulting in excessively high one-time catalyst input costs.

[0004] Non-precious metal catalysts are inexpensive and significantly reduce costs. However, Jiri Tobicik (J. Mol. Catal. Achem., 2003, 194, 249-254) compared the activity differences between Pd / Al2O3 and Ni / Al2O3 catalysts in the hydrogenation of o-tert-butylphenol. He found that under the same conditions, the hydrogenation rate of the Ni / Al2O3 catalyst was much lower than that of the Pd / Al2O3 catalyst, indicating that Ni-based catalysts have poorer activity. Oemer MK (Ind. Eng. Chem. Res., 1988, 27, 219-225) studied the kinetics of the hydrogenation of o-tert-butylphenol using precious metal catalysts and Ni / Al2O3 catalysts. He found that the hydrogenation step of the intermediate o-tert-butylcyclohexanone was the rate-determining step for both types of catalysts, and that the adsorption of o-tert-butylcyclohexanone affected the cis-trans structure of o-tert-butylcyclohexanol. Furthermore, the hydrogenation rate of o-tert-butylcyclohexanone on noble metal catalysts is faster than that on Ni / Al₂O₃ catalysts. DJ Murzin (Stud. Surf. Sci. Catal., 1993, 78, 243-250) found that increasing the reaction temperature can accelerate the hydrogenation rate of tert-butylphenol, but high temperatures easily lead to the desorption of the tert-butyl group. Simultaneously, since trans-tert-butylcyclohexanol is thermodynamically more stable than cis-tert-butylcyclohexanol, high temperatures make it easier to form trans-tert-butylcyclohexanol during hydrogenation, resulting in a decrease in the selectivity of cis-tert-butylcyclohexanol. In other words, although increasing the temperature can increase the reactivity of Ni-based catalysts, it leads to a decrease in the selectivity of cis-tert-butylcyclohexanol. Summary of the Invention

[0005] To address the shortcomings and deficiencies of existing technologies, this invention provides an improved hydrogenation method for tert-butylphenol. This hydrogenation method uses a non-precious metal catalyst, which is inexpensive and can catalyze the hydrogenation reaction of tert-butylphenol with high activity and high cis-selectivity, while also exhibiting good catalyst stability.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] A method for hydrogenating tert-butylphenol, using tert-butylphenol and hydrogen as raw materials, involves a hydrogenation reaction in the presence of a catalyst to produce tert-butylcyclohexanol. The catalyst is a supported catalyst and includes a support, a nickel-based alloy, and an alkaline earth metal oxide. The nickel-based alloy and the alkaline earth metal oxide are supported on the support. The nickel-based alloy includes nickel and metal M, wherein metal M is selected from one or more combinations of Fe, Co, Cu, Zn, Ga, In, Mo, and W.

[0008] In this invention, the alkaline earth metals mentioned above refer to one or more of Ca, Mg, Ba, and Sr.

[0009] In this invention, tert-butylphenol is one of o-tert-butylphenol or p-tert-butylphenol.

[0010] In some embodiments, the catalyst contains, by weight percentage, 1%-50% nickel-based alloy, 0.5%-10% alkaline earth metal oxide, and 40%-98.5% support.

[0011] In some embodiments, the catalyst contains, by weight percentage, 1%-20% nickel-based alloy, 0.5%-10% alkaline earth metal oxide, and the balance being a support.

[0012] In some embodiments, the molar ratio of nickel to metal M in the nickel-based alloy is 0.5 to 20:1.

[0013] In some embodiments, the molar ratio of nickel to metal M in the nickel-based alloy is 0.5 to 3:1.

[0014] In some embodiments, the carrier is selected from one or more combinations of alumina, silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide, molecular sieve, and carbon.

[0015] In some embodiments, the molecular sieve is ZSM-5 molecular sieve.

[0016] In some embodiments, the mass ratio of the catalyst to tert-butylphenol is 1:5 to 1000.

[0017] In some embodiments, the mass hourly space velocity (HHSV) of the tert-butylphenol is 0.2–5 h⁻¹. -1 .

[0018] In some embodiments, the molar ratio of hydrogen to tert-butylphenol is 3 to 50:1.

[0019] In some embodiments, the temperature of the hydrogenation reaction is 80–200°C.

[0020] In some embodiments, the pressure of the hydrogenation reaction is 1 to 6 MPa.

[0021] In some embodiments, the hydrogenation method includes the following steps: 1) adding the tert-butylphenol and the catalyst to a reaction vessel, and introducing an inert gas into the reaction vessel; 2) heating the reaction vessel, introducing hydrogen gas into the reaction vessel, and carrying out the hydrogenation reaction to obtain tert-butylcyclohexanol. This method is a batch synthesis method.

[0022] In some embodiments, hydrogen gas is continuously or intermittently introduced into the reactor during the above-described batch reaction process to maintain a stable pressure inside the reactor.

[0023] In some embodiments, the reaction time of the above-mentioned intermittent reaction is 1-64 hours.

[0024] In some embodiments, the hydrogenation method includes the following steps: 1) loading the catalyst into a fixed-bed reactor and introducing an inert gas into the fixed-bed reactor; 2) heating the fixed-bed reactor and introducing hydrogen gas into the fixed-bed reactor to raise the pressure in the fixed-bed reactor to the reaction pressure; 3) continuously introducing hydrogen gas and tert-butylphenol into the fixed-bed reactor to carry out the hydrogenation reaction to obtain tert-butylcyclohexanol. This method is a continuous synthesis method.

[0025] The present invention also provides the aforementioned catalyst. This catalyst is a non-precious metal catalyst, inexpensive, and can catalyze the hydrogenation reaction of tert-butylphenol with high activity and high cis-selectivity.

[0026] The present invention also provides a method for preparing the aforementioned catalyst.

[0027] In some embodiments, the preparation method includes the steps of impregnating a support with a compound of metal M and a compound of alkaline earth metal to obtain a catalyst precursor, and calcining and reducing the catalyst precursor to obtain the catalyst.

[0028] Furthermore, the impregnation can be carried out using an equal-volume impregnation method or an excessive impregnation method.

[0029] Furthermore, the impregnation temperature is 20–95°C.

[0030] Furthermore, the soaking time is 0.5 to 64 hours.

[0031] In some embodiments, the preparation method includes the steps of ball milling a support with a compound of metal M and a compound of alkaline earth metal to obtain a catalyst precursor, and calcining and reducing the catalyst precursor to obtain the catalyst.

[0032] Furthermore, the temperature of the ball mill is 20–95°C.

[0033] Furthermore, the ball milling time is 0.5 to 64 hours.

[0034] In some embodiments, the preparation method includes the steps of precipitating and aging a support, an aqueous solution of a compound of metal M, an aqueous solution of a compound of alkaline earth metal, and a precipitant to obtain a catalyst precursor, and the steps of calcining and reducing the catalyst precursor to obtain the catalyst.

[0035] Furthermore, the molar concentration of the compound of metal M in the aqueous solution is 0.05–10 mol / L.

[0036] Furthermore, the molar concentration of the alkaline earth metal compound in the aqueous solution is 0.05–10 mol / L.

[0037] Furthermore, the precipitant is selected from one or more combinations of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, and ammonia water.

[0038] Furthermore, the precipitant is added in the form of an aqueous solution.

[0039] Furthermore, the molar concentration of the precipitant in the aqueous solution is 0.02–5 mol / L.

[0040] Furthermore, the precipitation temperature is 20–90°C.

[0041] Furthermore, the precipitation time is 0.5 to 24 hours.

[0042] Furthermore, the aging temperature is 20–90°C.

[0043] Furthermore, the aging time is 0.5 to 24 hours.

[0044] In some embodiments, the preparation method includes the steps of subjecting a support, a compound of metal M, and a compound of alkaline earth metal to a hydrothermal reaction to obtain a catalyst precursor, and the steps of calcining and reducing the catalyst precursor to obtain the catalyst.

[0045] Furthermore, the precipitant used in the hydrothermal reaction is selected from one or more combinations of ammonia, urea, isopropylamine, diisopropylamine, and hexamethylenetetramine.

[0046] Furthermore, the precipitant is added in the form of an aqueous solution.

[0047] Furthermore, the molar concentration of the precipitant in the aqueous solution is 0.02–5 mol / L.

[0048] Furthermore, the temperature of the hydrothermal reaction is 20–200°C.

[0049] Furthermore, the hydrothermal reaction time is 0.5 to 24 hours.

[0050] Furthermore, the pressure of the hydrothermal reaction is 0.1–10 MPa.

[0051] In the above four preparation methods, the calcination temperature is further described as 300–600°C.

[0052] Furthermore, the roasting time is 0.5 to 24 hours.

[0053] Furthermore, the reduction temperature is 300–600°C.

[0054] Furthermore, the restoration time is 1 to 24 hours.

[0055] Compared with the prior art, the present invention has the following advantages:

[0056] This invention alloys an active metal with Ni, using a nickel-based alloy as the main component of the catalyst. This significantly improves the selectivity of cis-o-tert-butylcyclohexanol or cis-p-tert-butylcyclohexanol (i.e., cis products) in the hydrogenation reaction products. Furthermore, the use of a nickel-based alloy effectively inhibits the shedding of the tert-butyl group, reducing the content of the byproduct cyclohexanol.

[0057] This invention uses alkaline earth metal oxides to modify nickel-based alloys, which can significantly improve the activity of the catalyst. This catalyst can achieve the complete hydrogenation of tert-butylphenol under mild conditions.

[0058] The hydrogenation reaction of this invention has a wide operating temperature range. In continuous hydrogenation reactions, it exhibits excellent tert-butylphenol conversion and cis-tert-butylcyclohexanol selectivity within the reaction temperature range of 110–170 °C.

[0059] The catalyst of this invention is a non-precious metal, which is inexpensive and effectively reduces the production cost of hydrogenation reaction. Moreover, the catalyst has good stability and no signs of deactivation were observed after being used 10 times in batch reaction and after 1200 hours in continuous reaction. Attached Figure Description

[0060] Figure 1 The X-ray diffraction pattern of the CaO-FeNi3 / Al2O3 catalyst prepared by precipitation method in Example 1 is shown.

[0061] Figure 2 The performance of the Ni / Al2O3 catalyst prepared in Comparative Example 2 in the hydrogenation reaction of o-tert-butylphenol at different temperatures is shown.

[0062] Figure 3 The performance of the CaO-FeNi3 / Al2O3 catalyst prepared by precipitation method in Example 1 for the hydrogenation reaction of o-tert-butylphenol at different temperatures;

[0063] Figure 4 The figure shows the stability test results of the CaO-FeNi3 / Al2O3 catalyst prepared by precipitation method in Example 1 in the hydrogenation of o-tert-butylphenol for 1200 h.

[0064] Figure 5 The figure shows the stability test results of the CaO-FeNi3 / Al2O3 catalyst prepared by precipitation method in Example 1 during the hydrogenation of p-tert-butylphenol for 1200 h. Detailed Implementation

[0065] The present invention will be further described below with reference to embodiments. However, the present invention is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific applications, and the implementation conditions not specified are conventional conditions in the industry. The technical features involved in the various embodiments of the present invention can be combined with each other as long as they do not conflict with each other.

[0066] Example 1

[0067] 1) Weigh 1.04 kg of nickel nitrate hexahydrate, 0.493 kg of ferric nitrate nonahydrate, 0.06 kg of calcium nitrate tetrahydrate, and 10 kg of deionized water and place them in a 50 L reactor. Dissolve them by stirring at room temperature, then add 1 kg of alumina and continue stirring for 30 min. Heat the reactor to 80 °C and keep the temperature inside the reactor constant. Add 20 kg of sodium carbonate aqueous solution (0.5 mol / L) to the reactor using a peristaltic pump over a period of 6 h. After precipitation, maintain the reactor at 80 °C for aging treatment for 12 h. Filter and wash the material in the reactor until the filtrate is neutral. Dry the filter cake in a 100 °C oven and calcine it in air at 450 °C for 4 h to obtain the CaO-Fe2O3-NiO / Al2O3 precursor.

[0068] 2) The CaO-Fe2O3-NiO / Al2O3 precursor sample from step 1) is loaded into a rotary furnace, H2 is introduced at a rate of 100 mL / min, and the temperature is raised to 550 °C for reduction. After 12 h, the sample is removed to obtain the CaO-FeNi3 / Al2O3 catalyst.

[0069] Plasma-inductively coupled atomic absorption spectrometry analysis revealed that the prepared CaO-FeNi3 / Al2O3 catalyst contained 15.4% Ni, 5.07% Fe, and 7.4% by mass, with a Ni / Fe molar ratio of 3.01. Figure 1 It can be seen that, in addition to the characteristic diffraction peaks of amorphous alumina, diffraction peaks of FeNi3 were observed at 2θ positions of 44.3°, 51.5°, and 75.9°, belonging to the (111), (200), and (220) crystal planes of FeNi3 (JCPDS No. 38-0419), proving that the main active metal alloy on the alumina support is FeNi3 alloy. Furthermore, in Figure 1 No characteristic diffraction peaks of calcium oxide were observed, indicating that calcium oxide is highly dispersed on the catalyst in the form of nanoparticles.

[0070] In this embodiment, in step 1), ferric nitrate can be replaced with cobalt nitrate, molybdenum nitrate, copper nitrate, zinc nitrate, gallium nitrate, zinc nitrate, indium nitrate, or tungsten nitrate, respectively. With the other conditions unchanged, catalysts with different compositions can be prepared, which are respectively denoted as CaO-MoNi / Al2O3, CaO-CoNi / Al2O3, CaO-CuNi / Al2O3, CaO-ZnNi / Al2O3, CaO-GaNi / Al2O3, CaO-InNi / Al2O3, and CaO-WNi / Al2O3.

[0071] In this embodiment, in step 1), alumina can be replaced by any one of silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide, activated carbon, and ZSM-5 molecular sieve, while keeping the other conditions unchanged. CaO-FeNi / Al2O3 catalysts with different supports can be prepared, which are respectively denoted as CaO-FeNi3 / SiO2, CaO-FeNi3 / TiO2, CaO-FeNi3 / ZrO2, CaO-FeNi3 / CeO2, CaO-FeNi3 / C, and CaO-FeNi3 / ZSM-5.

[0072] In this embodiment, calcium nitrate in step 1) can be replaced by any one of magnesium nitrate, barium nitrate, or strontium nitrate, while keeping the other conditions unchanged. This allows the preparation of FeNi3 / Al2O3 catalysts modified with different alkaline earth metal oxides, which are denoted as BaO-FeNi3 / Al2O3, MgO-FeNi3 / Al2O3, and SrO-FeNi3 / Al2O3, respectively.

[0073] Example 2

[0074] 1) Weigh 1.04 kg of nickel nitrate hexahydrate, 0.493 kg of ferric nitrate nonahydrate, 0.06 kg of calcium nitrate tetrahydrate, 0.3 kg of urea, and 10 kg of deionized water and place them in a 50 L high-pressure reactor. After stirring and dissolving, add 1 kg of alumina and continue stirring for 30 min. After sealing the high-pressure reactor, heat it to 160 °C and maintain the temperature inside the reactor for 24 h of hydrothermal reaction. After the hydrothermal reaction is completed, filter and wash the material in the reactor until the filtrate shows neutrality. Place the filter cake in a 100 °C oven to dry and calcine it in air at 450 °C for 4 h to obtain the CaO-Fe2O3-NiO / Al2O3 precursor.

[0075] 2) The CaO-Fe2O3-NiO / Al2O3 precursor sample from step 1) is loaded into a rotary furnace, H2 is introduced at a rate of 100 mL / min, and the temperature is raised to 550 °C for reduction. After 12 h, the sample is removed to obtain the CaO-FeNi3 / Al2O3-hydrothermal catalyst.

[0076] Example 3

[0077] 1) Weigh 1.04 kg of nickel nitrate hexahydrate, 0.493 kg of ferric nitrate nonahydrate, 0.06 kg of calcium nitrate tetrahydrate, and 4 kg of deionized water and place them in a 10 L reactor. Stir and dissolve the mixture at 50 °C. Then add 1 kg of alumina and continue stirring for 60 min. The mixture is then dried in a 100 °C oven and calcined in air at 450 °C for 4 h to obtain the CaO-Fe2O3-NiO / Al2O3 precursor.

[0078] 2) The CaO-Fe2O3-NiO / Al2O3 precursor sample from step 1) is loaded into a rotary furnace, H2 is introduced at a rate of 100 mL / min, and the temperature is raised to 550 °C for reduction. After 12 h, the sample is removed to obtain the CaO-FeNi3 / Al2O3-impregnated catalyst.

[0079] Example 4

[0080] 1) Weigh 1.04 kg of nickel nitrate hexahydrate, 0.493 kg of ferric nitrate nonahydrate, 0.06 kg of calcium nitrate tetrahydrate, and 1 kg of alumina and add them to a ball mill for ball milling. The ball milling temperature is 50℃ and the ball milling time is 2 h. Then, calcine the above mixture in air at 450℃ for 4 h to obtain the CaO-Fe2O3-NiO / Al2O3 precursor.

[0081] 2) The CaO-Fe2O3-NiO / Al2O3 precursor sample from step 1) is loaded into a rotary furnace, H2 is introduced at a rate of 100 mL / min, and the temperature is raised to 550 °C for reduction. After 12 h, the sample is removed to obtain the CaO-FeNi3 / Al2O3-ball milled catalyst.

[0082] Comparative Example 1

[0083] 1) Weigh 1.04 kg of nickel nitrate hexahydrate, 0.493 kg of ferric nitrate nonahydrate, and 10 kg of deionized water and place them in a 50 L reactor. Dissolve them by stirring at room temperature, then add 1 kg of alumina and continue stirring for 30 min. Heat the reactor to 80 °C and keep the temperature inside the reactor constant. Add 20 kg of sodium carbonate aqueous solution (0.5 mol / L) to the reactor using a peristaltic pump over a period of 6 h. After precipitation, maintain the reactor at 80 °C for aging treatment for 12 h. Filter and wash the material in the reactor until the filtrate is neutral. Dry the filter cake in a 100 °C oven and calcine it in air at 450 °C for 4 h to obtain the Fe2O3-NiO / Al2O3 precursor.

[0084] 2) The Fe2O3-NiO / Al2O3 precursor sample from step 1) is loaded into a rotary furnace, H2 is introduced at a rate of 100 mL / min, and the temperature is raised to 550 °C for reduction. After 12 h, the FeNi3 / Al2O3 catalyst is obtained.

[0085] Comparative Example 2

[0086] 1) Weigh 1.04 kg of nickel nitrate hexahydrate and 10 kg of deionized water into a 50 L reactor and stir to dissolve at room temperature. Then add 1 kg of alumina and continue stirring for 30 min. Heat the reactor to 80 °C and keep the temperature inside the reactor constant. Add 20 kg of sodium carbonate aqueous solution (0.5 mol / L) into the reactor using a peristaltic pump over a period of 6 h. After precipitation, maintain the reactor at 80 °C for aging treatment for 12 h. Filter and wash the material in the reactor until the filtrate is neutral. Dry the filter cake in a 100 °C oven and calcine it in air at 450 °C for 4 h to obtain the NiO / Al2O3 precursor.

[0087] 2) The NiO / Al2O3 precursor sample from step 1) is loaded into a rotary furnace, H2 is introduced at a rate of 100 mL / min, and the temperature is raised to 550 °C for reduction. After 12 h, the sample is removed to obtain the Ni / Al2O3 catalyst.

[0088] Comparative Example 3

[0089] 1) Weigh 1.04 kg of nickel nitrate hexahydrate, 0.06 kg of calcium nitrate tetrahydrate, and 10 kg of deionized water into a 50 L reactor and stir to dissolve at room temperature. Then add 1 kg of alumina and continue stirring for 30 min. Heat the reactor to 80 °C and keep the temperature inside the reactor constant. Add 20 kg of sodium carbonate aqueous solution (0.5 mol / L) into the reactor using a peristaltic pump over a period of 6 h. After precipitation, maintain the reactor at 80 °C for aging treatment for 12 h. Filter and wash the material in the reactor until the filtrate is neutral. Dry the filter cake in a 100 °C oven and calcine it in air at 450 °C for 4 h to obtain the CaO-NiO / Al2O3 precursor.

[0090] 2) The CaO-NiO / Al2O3 precursor sample from step 1) is loaded into a rotary furnace, H2 is introduced at a rate of 100 mL / min, and the temperature is raised to 550 °C for reduction. After 12 h, the sample is removed to obtain the CaO-Ni / Al2O3 catalyst.

[0091] Application Example 1

[0092] The catalysts of Example 1 and Comparative Examples 1-3 were used for the batch hydrogenation reaction of o-tert-butylphenol:

[0093] 0.3 kg of each of the above catalysts and 30 kg of o-tert-butylphenol were added to a 50 L stainless steel reactor. After purging with nitrogen five times, the reactor was heated to 120 °C, and hydrogen was introduced to control the reactor pressure at 4 MPa. Heating was stopped after 4 hours of reaction. After cooling, the catalysts were separated from the reaction solution by filtration. Quantitative analysis of the reaction solution was performed on an Agilent 7890 gas chromatograph using an HP-INNOWax column and an FID detector.

[0094] Table 1 shows the reaction performance results of the catalyst CaO-FeNi3 / Al2O3 prepared by the precipitation method in Example 1, the catalyst FeNi3 / Al2O3 prepared in Comparative Example 1, the catalyst Ni / Al2O3 prepared in Comparative Example 2, and the catalyst CaO-Ni / Al2O3 prepared in Comparative Example 3 in the hydrogenation of o-tert-butylphenol. Note that the sum of the selectivity of o-tert-butylcyclohexanone, cis-o-tert-butylcyclohexanol, trans-o-tert-butylcyclohexanol, and cyclohexanol is not 100% because other byproduct impurities are generated (similar to the results in the following tables).

[0095] Comparing the FeNi3 / Al2O3 and Ni / Al2O3 catalysts, the conversion rate of tert-butylphenol on the FeNi3 / Al2O3 catalyst is lower than that on the Ni / Al2O3 catalyst, indicating that alloying reduces the catalyst conversion rate. The selectivity of cis-o-tert-butylcyclohexanol on the FeNi3 / Al2O3 catalyst is 82.5%, and the ratio of cis-o-tert-butylcyclohexanol to trans-o-tert-butylcyclohexanol is 9.59, significantly higher than that of the Ni / Al2O3 catalyst (74.7% selectivity and 3.99 ratio), indicating that alloying improves the selectivity of cis-o-tert-butylcyclohexanol. Modifying Ni / Al₂O₃ and FeNi₃ / Al₂O₃ catalysts with alkaline earth metal oxides revealed that the conversion rates of o-tert-butylphenol on Ni / Al₂O₃ and CaO-Ni / Al₂O₃ catalysts were essentially equivalent, indicating that alkaline earth metals could not improve the activity of Ni / Al₂O₃ catalysts. However, the conversion rate of o-tert-butylphenol on the CaO-FeNi₃ / Al₂O₃ catalyst was 99.9%, significantly higher than that on the FeNi₃ / Al₂O₃ catalyst, demonstrating that alkaline earth metal oxide modification can significantly improve the activity of nickel-based alloy catalysts. Alkaline earth metal oxides had little effect on the selectivity of cis-o-tert-butylcyclohexanol. Furthermore, the selectivity for the byproduct cyclohexanol on CaO-FeNi₃ / Al₂O₃ and FeNi₃ / Al₂O₃ catalysts was significantly lower than that on the corresponding CaO-Ni / Al₂O₃ and Ni / Al₂O₃ catalysts, indicating that the alloying strategy suppressed the shedding of the tert-butyl group and significantly reduced the formation of the byproduct cyclohexanol.

[0096] Table 1: Reaction performance of catalysts prepared by precipitation method in Example 1 and Comparative Examples 1-3

[0097]

[0098] Table 2 shows the reaction performance of different Ni-based alloy catalysts in Example 1. As can be seen from Table 2, the selectivity of cis-o-tert-butylcyclohexanol was significantly improved after alloying, while the selectivity of the byproduct cyclohexanol was reduced.

[0099] Table 2: Catalyst performance of different active components in Example 1

[0100]

[0101] Table 3 shows the reaction performance of catalysts prepared with different supports in Example 1. As can be seen from Table 3, catalysts prepared with different supports all have excellent o-tert-butylphenol conversion and cis-o-tert-butylcyclohexanol selectivity, among which alumina and molecular sieve (ZSM-5) have the best reaction performance.

[0102] Table 3: Reaction performance of catalysts with different supports in Example 1

[0103]

[0104]

[0105] Table 4 shows the reaction performance of catalysts modified with different alkaline earth metal oxides in Example 1. As can be seen from Table 4, modification with alkaline earth metal oxides can significantly improve catalyst activity, with CaO and BaO showing the best effects.

[0106] Table 4: Reaction performance of different alkaline earth metal oxide modified catalysts in Example 1

[0107]

[0108] Table 5 shows the reaction performance of the CaO-FeNi3 / Al2O3 catalysts prepared by different methods in Examples 1-4. As can be seen from Table 5, the catalysts prepared by the precipitation method and the hydrothermal method exhibit better reaction performance.

[0109] Table 5: Catalyst Reaction Performance Obtained by Different Preparation Methods in Examples 1-4

[0110]

[0111]

[0112] The CaO-FeNi3 / Al2O3 catalyst prepared by the precipitation method in Example 1 was subjected to intermittent hydrogenation of o-tert-butylphenol. The results are shown in Table 6. It can be seen that after 10 cycles of catalyst re-application, the CaO-FeNi3 / Al2O3 catalyst did not show any signs of deactivation, indicating that the catalyst has excellent stability.

[0113] Table 6: Performance of CaO-FeNi3 / Al2O3 catalyst in batch hydrogenation of o-tert-butylphenol

[0114]

[0115]

[0116] Example 2

[0117] The catalysts of Example 1 and Comparative Examples 1-3 were used in the batch hydrogenation reaction of p-tert-butylphenol:

[0118] 0.3 kg of catalyst and 30 kg of p-tert-butylphenol were added to a 50 L stainless steel reactor. After purging with nitrogen five times, the reactor was heated to 120 °C, and hydrogen was introduced to control the reactor pressure at 4 MPa. Heating was stopped after 4 hours of reaction. After cooling, the catalyst was separated from the reaction solution by filtration. Quantitative analysis of the reaction solution was performed on an Agilent 7890 gas chromatograph using an HP-INNOWax column and an FID detector.

[0119] Table 7 shows the reaction performance of the catalyst CaO-FeNi3 / Al2O3 prepared by precipitation method in Example 1, the catalyst FeNi3 / Al2O3 prepared in Comparative Example 1, the catalyst Ni / Al2O3 prepared in Comparative Example 2, and the catalyst CaO-Ni / Al2O3 prepared in Comparative Example 3 in the hydrogenation of tert-butylphenol. As shown in Table 7, the modification with alkaline earth metal oxides significantly improved the catalyst activity, enabling complete hydrogenation of tert-butylphenol under mild conditions. The alloying strategy improved the selectivity for cis-tert-butylcyclohexanol and inhibited the removal of the tert-butyl group, reducing the content of the byproduct cyclohexanol in the target product.

[0120] Table 7: Performance of CaO-FeNi3 / Al2O3 catalyst in batch hydrogenation of tert-butylphenol

[0121]

[0122] Example 3

[0123] The catalysts of Example 1 and Comparative Examples 1-3 were used for the continuous hydrogenation reaction of o-tert-butylphenol:

[0124] A stainless steel tube was used as the reactor, with an outer diameter of 45 mm, an inner diameter of 37 mm, and a length of 2200 mm. The catalyst (cylindrical: 3 mm in diameter, 5 mm in height; bulk density 0.8 g / mL) was loaded in a quantity of 1450 g. The reaction pressure was 4 MPa, and the liquid hourly space velocity (LISH) of o-tert-butylphenol was 1 h⁻¹. -1 Hydrogen is used as the hydrogenating agent, and the molar ratio of hydrogen to o-tert-butylphenol is 5.

[0125] Depend on Figure 2 It can be seen that, within the temperature range of 110–170 °C, the conversion rate of o-tert-butylphenol using the Ni / Al₂O₃ catalyst increases with increasing temperature, and complete conversion of o-tert-butylphenol is achieved at a reaction temperature not lower than 140 °C. Meanwhile, at 110 °C, the selectivity for cis-o-tert-butylcyclohexanol is 80.4%, and the selectivity for trans-o-tert-butylcyclohexanol is 15.3%. The selectivity for cis-o-tert-butylcyclohexanol decreases significantly with increasing reaction temperature. Figure 3 It can be seen that the CaO-FeNi3 / Al2O3 catalyst can achieve complete conversion of o-tert-butylphenol within a temperature range of 110–170℃. At 110℃, the selectivity for cis-o-tert-butylcyclohexanol is 87.1%, and the selectivity for trans-o-tert-butylcyclohexanol is 12.6%. Furthermore, the selectivity for cis-o-tert-butylcyclohexanol does not decrease significantly with increasing reaction temperature; at 170℃, the selectivity for cis-o-tert-butylcyclohexanol is still 84.4%. Based on the above data analysis, the CaO-FeNi3 / Al2O3 catalyst exhibits excellent hydrogenation activity of o-tert-butylphenol, high selectivity for cis-o-tert-butylcyclohexanol, and a wide operating temperature range.

[0126] Figure 4 It can be seen that during the 1200-hour stability test, o-tert-butylphenol was almost completely converted, the selectivity of cis-o-tert-butylcyclohexanol remained at about 87%, and the selectivity of trans-o-tert-butylcyclohexanol remained at about 12%. The o-tert-butylcyclohexanol was >99.5%, and the catalyst showed no signs of deactivation. This indicates that the CaO-FeNi3 / Al2O3 catalyst prepared by the precipitation method in Preparation Example 1 has excellent reactivity, product selectivity, and stability.

[0127] Example 4

[0128] The catalyst from Example 1 was used in the continuous hydrogenation reaction of p-tert-butylphenol:

[0129] A stainless steel tube was used as the reactor, with an outer diameter of 45 mm, an inner diameter of 37 mm, and a length of 2200 mm. The catalyst (cylindrical: 3 mm in diameter, 5 mm in height; bulk density 0.8 g / mL) was added in a quantity of 1450 g. The reaction pressure was 4 MPa, the reaction temperature was 140–145 °C, and the liquid hourly space velocity (LISH) of p-tert-butylphenol was 1 h⁻¹. -1Hydrogen is used as the hydrogenating agent, and the molar ratio of hydrogen to p-tert-butylphenol is 5.

[0130] Depend on Figure 5 It can be seen that in the 1200-hour stability test, p-tert-butylphenol was almost completely converted, the selectivity of cis-p-tert-butylcyclohexanol was maintained at about 28%, the selectivity of trans-p-tert-butylcyclohexanol was maintained at about 71%, and the selectivity of p-tert-butylcyclohexanol was >99%. The catalyst did not show any signs of deactivation, indicating that the CaO-FeNi3 / Al2O3 catalyst prepared by the precipitation method in Preparation Example 1 has excellent reactivity, product selectivity and stability.

[0131] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.

[0132] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A method for hydrogenating tert-butylphenol, comprising using tert-butylphenol and hydrogen as raw materials, and carrying out a hydrogenation reaction in the presence of a catalyst to produce tert-butylcyclohexanol, characterized in that: The catalyst is a supported catalyst and includes a support, a nickel-based alloy, and an alkaline earth metal oxide. The nickel-based alloy and the alkaline earth metal oxide are supported on the support. The nickel-based alloy includes nickel and metal M, wherein metal M is selected from one or more combinations of Fe, Co, Cu, Zn, Ga, In, Mo, and W. By weight percentage, the catalyst contains 1%-50% nickel-based alloy, 0.5%-10% alkaline earth metal oxide, and 40%-98.5% support. The molar ratio of nickel to metal M in the nickel-based alloy is 0.5-20:

1.

2. The hydrogenation method for tert-butylphenol according to claim 1, characterized in that: The carrier is selected from one or more combinations of alumina, silicon dioxide, titanium dioxide, zirconium dioxide, cerium dioxide, molecular sieve, and carbon.

3. The hydrogenation method for tert-butylphenol according to claim 1, characterized in that: The mass ratio of the catalyst to tert-butylphenol is 1:5 to 1000.

4. The hydrogenation method for tert-butylphenol according to claim 1, characterized in that: The mass hourly space velocity (MSV) of the tert-butylphenol is 0.2–5 h⁻¹. -1 .

5. The hydrogenation method for tert-butylphenol according to claim 1, characterized in that: The molar ratio of hydrogen to tert-butylphenol is 3 to 50:

1.

6. The hydrogenation method for tert-butylphenol according to claim 1, characterized in that: The temperature of the hydrogenation reaction is 80–200°C; and / or the pressure of the hydrogenation reaction is 1–6 MPa.

7. The hydrogenation method for tert-butylphenol according to claim 1, characterized in that: The hydrogenation method includes the following steps: 1) adding the tert-butylphenol and the catalyst to the reaction vessel, and introducing an inert gas into the reaction vessel; 2) heating the reaction vessel, introducing hydrogen gas into the reaction vessel, and carrying out the hydrogenation reaction to obtain tert-butylcyclohexanol.

8. The hydrogenation method for tert-butylphenol according to claim 1, characterized in that: The hydrogenation method includes the following steps: 1) loading the catalyst into a fixed-bed reactor and introducing an inert gas into the fixed-bed reactor; 2) heating the fixed-bed reactor and introducing hydrogen into the fixed-bed reactor to raise the pressure in the fixed-bed reactor to the reaction pressure; 3) continuously introducing hydrogen and tert-butylphenol into the fixed-bed reactor to carry out the hydrogenation reaction and obtain tert-butylcyclohexanol.

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