Heterogeneous catalyst, preparation method thereof and application of heterogeneous catalyst in preparation of cyclohexylamine through phenol reductive ammoniation

Abstract

The invention discloses a heterogeneous catalyst and a preparation method and application thereof in preparation of cyclohexylamine through phenol reductive ammoniation, the heterogeneous catalyst comprises a carrier and active metal loaded on the carrier, the supported non-noble metal catalyst is used for catalyzing preparation of cyclohexylamine through phenol reductive ammoniation, the conversion rate of phenol is 100%, and the conversion rate of cyclohexylamine is 100%. The selectivity of cyclohexylamine is as high as 95%, and no obvious inactivation phenomenon is generated after the catalyst is used for five times.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, specifically to a heterogeneous catalyst, its preparation method, and its application in the reduction and amination of phenol to prepare cyclohexylamine. Background Technology

[0002] Cyclohexylamine (CAS: 108-91-8) is an important chemical raw material and fine chemical intermediate used in the production of petroleum product additives, metal corrosion inhibitors, bactericides and insecticides, antistatic agents, rubber accelerators and antioxidants, food and feed additives, and syngas desulfurizers. In recent years, with the continuous development of downstream products of cyclohexylamine, the market demand for cyclohexylamine has been gradually increasing.

[0003] Currently, cyclohexylamine is mainly synthesized through the following methods:

[0004] (1) Synthesis of cyclohexylamine by gas-phase catalytic hydrogenation of aniline. US Patent (US3196179A) discloses a method for preparing cyclohexylamine from aniline under the action of a rhodium catalyst.

[0005] (2) Cyclohexanol and cyclohexanone are hydrogenated and ammoniated to synthesize cyclohexylamine. Chinese patent (CN114805088A) uses a supported Co, Ni, Mg, Cu, Zn metal catalyst and cyclohexanol and cyclohexanone as raw materials in a fixed-bed reactor.

[0006] (3) One-step catalytic hydrogenation of nitrobenzene to prepare cyclohexylamine. Chinese patent (CN103772207A) discloses a rhodium-nickel catalyst supported on a carbon material. However, the above-mentioned cyclohexylamine synthesis routes all have limitations: either the raw materials are expensive (aniline) or difficult to obtain (nitrobenzene), or expensive metal catalysts (such as rhodium) are required, or the hydrogenation product of nitrobenzene has insufficient selectivity. These problems increase the synthesis cost of cyclohexylamine. Therefore, from the perspective of industrial application, developing a new process route that uses inexpensive and readily available raw materials, uses hydrogen as the hydrogen source, and has high product selectivity is of great practical significance. Summary of the Invention

[0007] The purpose of this section is to outline some aspects of the embodiments of the present invention and to briefly describe some preferred embodiments.

[0008] The present invention provides a heterogeneous catalyst, wherein the catalyst comprises a support, an active component supported on the support, and an auxiliary agent;

[0009] The carrier is alumina, the active component is nickel, and the additives include tin and cerium;

[0010] The active component is 12-52 wt% of the mass of the catalyst, preferably 22-52:1, and more preferably 22-42:1.

[0011] The mass of the auxiliary agent is 7 to 47 wt% of the mass of the catalyst, preferably 7 to 37:1, more preferably 17 to 37:1;

[0012] The mass ratio of tin to cerium in the additive is 0.5 to 3.5:1, preferably 1 to 3.5:1, and more preferably 1.5 to 3:1.

[0013] As a preferred embodiment of the heterogeneous catalyst described in this invention, the catalyst has a specific surface area of ​​50–300 m². 2 / g, preferably 50-250m 2 / g, more preferably 50-200m 2 / g.

[0014] The present invention also provides a method for preparing the heterogeneous catalyst, which includes the following steps: adding the support precursor, active component precursor and auxiliary agent precursor to a solvent to obtain a mixed solution; adding a precipitant; aging; washing; drying; calcining; and reducing to obtain the heterogeneous catalyst; wherein the precipitant includes one or more of sodium hydroxide, sodium carbonate, ammonia, sodium bicarbonate and urea.

[0015] As a preferred embodiment of the preparation method of the heterogeneous catalyst of the present invention: the support precursor includes one or more of aluminum nitrate, chloride, sulfate, acetate, and acetylacetonate, preferably one or more of nitrate, chloride, acetate, and acetylacetonate, and more preferably one or more of nitrate, chloride, and acetate.

[0016] The active component precursor includes one or more of nickel nitrate, chloride, sulfate, acetate, and acetylacetonate, preferably one or more of nickel nitrate, chloride, acetate, and acetylacetonate, and more preferably one or more of nickel nitrate, chloride, and acetate.

[0017] The auxiliary precursor includes one or more of tin and cerium nitrates, chlorides, sulfates, acetates, and acetylacetones, preferably one or more of tin and cerium nitrates, chlorides, sulfates, and acetates, and more preferably one or more of tin and cerium nitrates, chlorides, and sulfates.

[0018] The solvent is one or a mixture of several of the following: water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, and tert-pentanol. Preferably, it is one or a mixture of several of the following: water, methanol, ethanol, isopropanol, tert-butanol, and tert-pentanol. More preferably, it is one or a mixture of several of the following: water, methanol, and ethanol.

[0019] As a preferred embodiment of the preparation method of the heterogeneous catalyst of the present invention, the aging temperature is 25-100℃, preferably 25-80℃, more preferably 25-60℃, and the aging time is 1-24h, preferably 1-12h, more preferably 4-12h.

[0020] As a preferred embodiment of the preparation method of the heterogeneous catalyst of the present invention: the calcination temperature is 300-900℃, preferably 300-600℃, more preferably 400-600℃, and the calcination time is 1-24h, preferably 1-8h, more preferably 4-8h;

[0021] The reduction process uses one or more of the following reducing gases: hydrogen, hydrogen-argon mixture, and hydrogen-nitrogen mixture. The reduction temperature is 300–800°C, preferably 300–600°C, more preferably 400–600°C, and the reduction time is 1–8 hours, preferably 1–6 hours, more preferably 4–6 hours.

[0022] The present invention also provides a method for preparing the heterogeneous catalyst, which includes the following steps: adding an active component precursor and an auxiliary agent precursor to a solvent to obtain a mixed solution, adding an alumina support, aging, drying, calcining, and reducing to obtain a heterogeneous catalyst;

[0023] The active component precursor includes one or more of nickel nitrate, chloride, sulfate, acetate, and acetylacetonate, preferably one or more of nickel nitrate, chloride, acetate, and acetylacetonate, and more preferably one or more of nickel nitrate, chloride, and acetate.

[0024] The auxiliary precursor includes one or more of tin and cerium nitrates, chlorides, sulfates, acetates, and acetylacetones, preferably one or more of tin and cerium nitrates, chlorides, sulfates, and acetates, and more preferably one or more of tin and cerium nitrates, chlorides, and sulfates.

[0025] The solvent is one or a mixture of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, and tert-pentanol, preferably one or a mixture of several of water, methanol, ethanol, isopropanol, tert-butanol, and tert-pentanol, and more preferably one or a mixture of several of water, methanol, and ethanol.

[0026] The aging temperature is 25–100°C, preferably 25–80°C, more preferably 25–60°C, and the aging time is 0.5–12 hours, preferably 0.5–12 hours, more preferably 4–12 hours.

[0027] The calcination temperature is 300–900℃, preferably 300–600℃, more preferably 400–600℃, and the calcination time is 0.5–24h, preferably 0.5–8h, more preferably 4–8h;

[0028] The reduction process uses one or more of the following reducing gases: hydrogen, hydrogen-argon mixture, and hydrogen-nitrogen mixture. The reduction temperature is 300–800°C, preferably 300–600°C, more preferably 400–600°C, and the reduction time is 1–8 hours, preferably 1–6 hours, more preferably 4–6 hours.

[0029] The present invention also provides the application of the heterogeneous catalyst in the preparation of cyclohexylamine by reducing ammoniation of phenol, wherein phenol or its derivatives and the heterogeneous catalyst are added to a pressure vessel, and ammonia and hydrogen are introduced to carry out the reducing ammoniation reaction.

[0030] Preferably, the ammonia and hydrogen are introduced for a reductive ammoniation reaction, wherein the mass ratio of phenol to catalyst is 1:0.1-0.5, preferably 1:0.1-0.4, more preferably 1:0.1-0.3; the ammonia pressure is 0.1-0.6 MPa, preferably 0.2-0.6 MPa, more preferably 0.3-0.6 MPa, and the hydrogen pressure is 0.6-6 MPa, preferably 0.6-4.5 MPa, more preferably 1-4.5 MPa; the reductive ammoniation reaction temperature is 155-175°C, and the time is 10-15 h.

[0031] Preferably, the phenol derivative includes one of the formulas 1 to 7:

[0032]

[0033] in, 1 R, 2 R, 3 R, 4 R, 5 R, 6 R, 7 R is independently one of hydrogen, a straight-chain alkyl group having 1 to 18 carbon atoms, an isoalkyl group having 1 to 18 carbon atoms, phenyl, methoxy, phenoxy, nitro, trifluoromethyl, methyl ester, methanol, fluorine, chlorine, bromine, and iodine.

[0034] The beneficial effects of this invention are as follows: The heterogeneous catalyst provided by this invention includes a support and an active metal and an auxiliary metal supported on the support. In this invention, the supported catalyst system has the function of inhibiting product deamination, suppressing the occurrence of deamination coupling byproducts (dicyclohexylamine). When the supported non-precious metal-based catalyst provided by this invention catalyzes the reduction and amination of phenol to prepare cyclohexylamine under solvent-free conditions, the conversion rate of phenol reaches 100%, the selectivity of cyclohexylamine is as high as 95%, and there is no obvious deactivation phenomenon after five reuses of the catalyst. Attached Figure Description

[0035] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below, wherein:

[0036] Figure 1 This is a gas chromatogram of the product of the NiSnCeAlOx / 30 catalytic reduction and amination reaction of phenol according to the present invention. Detailed Implementation

[0037] To make the above-mentioned objectives, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to specific examples.

[0038] The reaction route for the synthesis of cyclohexylamine by hydrogenation of phenol is as follows:

[0039]

[0040] Example 1:

[0041] A method for preparing NiOx catalyst for the reduction and amination of phenol to cyclohexylamine includes the following steps:

[0042] Step 1: Dissolve 1.55g of Ni(NO3)2·6H2O in 100mL of deionized water to obtain solution A.

[0043] Step 2: Dissolve 0.424g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0044] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0045] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the NiOx catalyst.

[0046] Example 2:

[0047] The preparation method of AlOx catalyst for the reductive amination of phenol to cyclohexylamine includes the following steps:

[0048] Step 1: Dissolve 1g of Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0049] Step 2: Dissolve 0.64g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0050] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0051] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced using a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the AlOx catalyst.

[0052] Example 3:

[0053] A method for preparing CeOx, a catalyst for the reductive amination of phenol to cyclohexylamine, includes the following steps:

[0054] Step 1: Dissolve 0.985g of CeCl3 in 100mL of deionized water to obtain solution A.

[0055] Step 2: Dissolve 0.954g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0056] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0057] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain CeOx catalyst.

[0058] Example 4:

[0059] A method for preparing SnOx, a catalyst for the reductive amination of phenol to cyclohexylamine, includes the following steps:

[0060] Step 1: Dissolve 0.926g of SnCl2·2H2O in 100mL of deionized water to obtain solution A.

[0061] Step 2: Dissolve 0.636g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0062] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0063] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the SnOx catalyst.

[0064] Example 5:

[0065] The method for preparing CeAlOx catalyst for the reductive amination of phenol to cyclohexylamine includes the following steps:

[0066] Step 1: Dissolve 0.065g CeCl3 and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0067] Step 2: Dissolve 0.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0068] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0069] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain CeAlOx catalyst.

[0070] Example 6:

[0071] The preparation method of NiCeAlOx catalyst for the reduction and amination of phenol to prepare cyclohexylamine includes the following steps:

[0072] Step 1: Dissolve 1.55g Ni(NO3)2·6H2O, 0.065g CeCl3, and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0073] Step 2: Dissolve 1.6g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0074] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0075] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the NiCeAlOx catalyst.

[0076] Example 7:

[0077] The preparation method of NiSnCeAlOx catalyst for the reduction and amination of phenol to prepare cyclohexylamine includes the following steps:

[0078] Step 1: Dissolve 1.55g Ni(NO3)2·6H2O, 0.181g SnCl2·2H2O, 0.065g CeCl3, and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0079] Step 2: Dissolve 1.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0080] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0081] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the NiSnCeAlOx catalyst.

[0082] Example 8:

[0083] The preparation method of the catalyst CoSnCeAlOx for the reductive amination of phenol to cyclohexylamine includes the following steps:

[0084] Step 1: Dissolve 1.55g Co(NO3)2·6H2O, 0.181g SnCl2·2H2O, 0.065g CeCl3, and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0085] Step 2: Dissolve 1.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0086] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0087] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the CoSnCeAlOx catalyst.

[0088] Example 9:

[0089] The preparation method of CuSnCeAlOx catalyst for the reductive amination of phenol to cyclohexylamine includes the following steps:

[0090] Step 1: Dissolve 1.58g Cu(NO3)2·3H2O, 0.181g SnCl2·2H2O, 0.065g CeCl3, and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0091] Step 2: Dissolve 1.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0092] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0093] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain CuSnCeAlOx catalyst.

[0094] Example 10:

[0095] The preparation method of NiCaCeAlOx catalyst for the reduction and amination of phenol to prepare cyclohexylamine includes the following steps:

[0096] Step 1: Dissolve 1.55g Ni(NO3)2·6H2O, 0.150g Ca(NO3)2·6H2O, 0.065g CeCl3, and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0097] Step 2: Dissolve 1.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0098] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0099] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the NiCaCeAlOx catalyst.

[0100] Example 11:

[0101] The preparation method of NiWCeAlOx catalyst for the reduction and amination of phenol to prepare cyclohexylamine includes the following steps:

[0102] Step 1: Take 1.55g Ni(NO3)26H2O and 0.193g (NH4)6H2W 12 O 40 ·xH2O (CAS: 11120-25-5), 0.065g CeCl3, and 1g Al(NO3)3·9H2O were dissolved sequentially in 100mL of deionized water to obtain solution A.

[0103] Step 2: Dissolve 1.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0104] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0105] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the NiWCeAlOx catalyst.

[0106] Example 12:

[0107] The preparation method of NiSnZrAlOx catalyst for the reductive amination of phenol to cyclohexylamine includes the following steps:

[0108] Step 1: Dissolve 1.55g Ni(NO3)2·6H2O, 0.181g SnCl2·2H2O, 0.114g Zr(NO3)4·5H2O, and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0109] Step 2: Dissolve 1.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0110] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0111] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced with a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the NiSnZrAlOx catalyst.

[0112] Example 13:

[0113] The preparation method of NiSnCrAlOx catalyst for the reduction and amination of phenol to prepare cyclohexylamine includes the following steps:

[0114] Step 1: Dissolve 1.55g Ni(NO3)2·6H2O, 0.181g SnCl2·2H2O, 0.107g Cr(NO3)3·9H2O, and 1g Al(NO3)3·9H2O in 100mL of deionized water to obtain solution A.

[0115] Step 2: Dissolve 1.7g of Na2CO3 in 50mL of deionized water to obtain solution B.

[0116] Step 3: Slowly add solution B dropwise to solution A. After titration, stir vigorously and then age the solution at 60°C for 6 hours. Wash the resulting suspension with deionized water by centrifugation until neutral, and then dry it overnight at 120°C.

[0117] Step 4: The dried catalyst was calcined at 450℃ for 4 hours, and then the catalyst was reduced using a hydrogen-argon mixture with a hydrogen molar concentration of 5%, the hydrogen-argon mixture flow rate was 20 mL / min, the reduction temperature was 600℃, and the reduction time was 2 hours to obtain the NiSnCrAlOx catalyst.

[0118] Examples 14-27:

[0119] The catalysts prepared in Examples 1-13 were used to prepare cyclohexylamine by the reductive amination of phenol, and the specific steps are as follows:

[0120] 0.94 g of phenol and 0.188 g of one of the catalysts obtained in Examples 1-13 were added to a high-pressure reactor. After sealing the reactor, it was purged with argon gas at 0.5 MPa three times, followed by ammonia gas to 0.45 MPa and hydrogen gas to 1.5 MPa. The temperature was set at 165 °C and the reaction was carried out for 10 h. After the reaction was completed, it was cooled to room temperature and the liquid product was collected by centrifugation.

[0121] Gas chromatography analysis of product distribution.

[0122] Table 1. Study on the reductive amination performance of phenol using different active metals and supported catalysts in Examples 14-27

[0123]

[0124] Examples 28-38:

[0125] Using the catalyst NiSnCeAlO from Example 21 x Using the same reaction conditions as in Example 21, different reaction temperatures, ammonia pressures, hydrogen pressures, and reaction times were investigated to study the synthesis of cyclohexylamine by the reduction and amination of phenol. The results are listed in Table 2.

[0126] Table 2. Study on the phenol reduction and amination performance of Examples 28-38 using different reaction temperatures, ammonia pressures, hydrogen pressures, and reaction times.

[0127]

[0128] Examples 39-43:

[0129] Using the catalyst NiSnCeAlO from Example 21 x Using the same reaction conditions as in Example 21, and examining different numbers of repetitions, the synthesis of cyclohexylamine by phenol reduction amination was studied, and the results are listed in Table 3.

[0130] Table 3. Study on the number of times the catalyst is reused for the reductive amination performance of phenol in Examples 39-43.

[0131]

[0132] As shown in Table 3, the catalyst provided by this invention does not show significant deactivation after five cycles, and the conversion rate of phenol can reach 100% and the yield of cyclohexylamine can reach 94% in the fifth reaction.

[0133] Examples 44-49:

[0134] Using the catalyst NiSnCeAlO from Example 21 xUsing the same reaction conditions as in Example 21, the selective reduction and amination reactions of phenolic compounds were investigated with different substrates. The results are listed in Table 4.

[0135] Table 4 shows the effects of Examples 44-49 on the supported catalyst NiSnCeAlO. x Universality study

[0136]

[0137] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A heterogeneous catalyst, characterized in that: The catalyst comprises a support, an active component supported on the support, and an auxiliary agent; The carrier is alumina, the active component is nickel, and the additives include tin and cerium; The mass of the active component is 12 to 52 wt% of the mass of the catalyst; The mass of the auxiliary agent is 7 to 47 wt% of the mass of the catalyst; The mass ratio of tin to cerium in the additive is 0.5 to 3.5:

1.

2. The heterogeneous catalyst according to claim 1, characterized in that: The catalyst has a specific surface area of ​​50–300 m². 2 / g.

3. The method for preparing a heterogeneous catalyst according to claim 1, characterized in that: The process includes the following steps: adding the carrier precursor, active component precursor, and auxiliary agent precursor to a solvent to obtain a mixed solution; adding a precipitant; aging; washing; drying; calcining; and reducing to obtain a heterogeneous catalyst; wherein the precipitant includes one or more of sodium hydroxide, sodium carbonate, ammonia, sodium bicarbonate, and urea.

4. The method for preparing a heterogeneous catalyst according to claim 3, characterized in that: The carrier precursor includes one or more of aluminum nitrates, chlorides, sulfates, acetates, and acetylacetones. The active component precursor includes one or more of nickel nitrates, chlorides, sulfates, acetates, and acetylacetones. The auxiliary precursor includes one or more of the following: nitrates, chlorides, sulfates, acetates, and acetylacetones of tin and cerium. The solvent is one or a mixture of several of the following: water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, and tert-pentanol.

5. The method for preparing the heterogeneous catalyst according to claim 3 or 4, characterized in that: The aging temperature is 25–100℃, and the aging time is 1–24 hours.

6. The method for preparing a heterogeneous catalyst according to claim 3 or 4, characterized in that: The calcination temperature is 300–900℃, and the calcination time is 1–24 h; The reduction process uses one or more of the following reducing gases: hydrogen, hydrogen-argon mixture, and hydrogen-nitrogen mixture. The reduction temperature is 300–800°C, and the reduction time is 1–8 hours.

7. The method for preparing a heterogeneous catalyst according to claim 1, characterized in that: The process includes the following steps: adding the active component precursor and the auxiliary agent precursor to a solvent to obtain a mixed solution, adding the alumina support, aging, drying, calcining, and reducing to obtain a heterogeneous catalyst; The active component precursor includes one or more of nickel nitrates, chlorides, sulfates, acetates, and acetylacetones. The auxiliary precursor includes one or more of the following: nitrates, chlorides, sulfates, acetates, and acetylacetones of tin and cerium. The solvent is one or a mixture of water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, isopentanol, and tert-pentanol. The aging temperature is 25–100℃, and the aging time is 0.5–12 hours. The calcination temperature is 300–900℃, and the calcination time is 0.5–24 h; The reduction process uses one or more of the following reducing gases: hydrogen, hydrogen-argon mixture, and hydrogen-nitrogen mixture. The reduction temperature is 300–800°C, and the reduction time is 1–8 hours.

8. The application of the heterogeneous catalyst according to claim 1 in the preparation of cyclohexylamine by the reductive amination of phenol, characterized in that: Phenol or its derivatives and the heterogeneous catalyst are added to a pressure vessel, and ammonia and hydrogen are introduced to carry out a reduction ammoniation reaction.

9. The application according to claim 8, characterized in that: The mass ratio of phenol to catalyst is 1:0.1-0.

5. Ammonia and hydrogen are introduced to carry out the reductive ammoniation reaction, wherein the ammonia pressure is 0.1-0.6 MPa and the hydrogen pressure is 0.6-6 MPa; the reductive ammoniation reaction temperature is 155-175℃ and the time is 10-15 h.

10. The application according to claim 8, characterized in that: The phenol derivatives include one of those shown in Formulas 1 to 7: in, 1 R, 2 R, 3 R, 4 R, 5 R, 6 R, 7 R is independently one of hydrogen, a straight-chain alkyl group having 1 to 18 carbon atoms, an isoalkyl group having 1 to 18 carbon atoms, phenyl, methoxy, phenoxy, nitro, trifluoromethyl, methyl ester, methanol, fluorine, chlorine, bromine, and iodine.

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