Dehydrogenation catalyst, preparation method thereof and method for preparing o-phenylphenol

Abstract

The invention relates to the technical field of catalysts, and discloses a dehydrogenation catalyst, a preparation method thereof and a method for preparing o-phenylphenol. The catalyst comprises an alumina carrier, and a main active component and an auxiliary agent which are loaded on the alumina carrier, wherein the main active component comprises Cu and Ni; wherein the weight ratio of Cu to Ni is 1: (0.1-10); the auxiliary agent comprises Mg and / or P; the weight ratio of the main active component to the auxiliary agent to the alumina carrier is (8-70): (0.5-10): 100. The catalyst has the characteristics of high cyclohexenyl cyclohexanone conversion rate, high ortho-phenylphenol selectivity and good activity stability in a reaction for preparing ortho-phenylphenol through cyclohexenyl cyclohexanone dehydrogenation, and the use cost is relatively low.

Description

Technical Field

[0001] The present invention relates to the technical field of catalysts, and particularly to a dehydrogenation catalyst, a preparation method thereof, and a method for preparing o-phenylphenol. Background Art

[0002] o-Phenylphenol (OPP) is an important organic fine chemical product, which is applied in the fields of sterilization and antisepsis, printing and dyeing auxiliaries, and surfactants, and is also used for synthesizing stabilizers for polymer materials and halogen-free flame retardants for environmental protection, with wide uses and broad market prospects.

[0003] Previously, the production of o-phenylphenol was mainly to recover OPP from the distillation residue of phenol produced by the sulfonation method. This method has a low yield and the obtained OPP has low purity. With the shutdown and transformation of the phenol production process by the sulfonation method, this method has been basically phased out. In view of the market demand for o-phenylphenol, it is urgent to develop a mature new process for synthesizing o-phenylphenol. Currently, the most widely used process is the cyclohexanone self-condensation dehydrogenation method. Among them, the catalysts for dehydrogenating cyclohexanone dimers mainly focus on noble metal catalysts, which have a short lifespan and are difficult to recycle after use, resulting in the catalyst cost accounting for most of the entire production cost.

[0004] CN102399135A discloses a method for preparing, separating and refining o-phenylphenol. The Ni-Cr-Al catalyst prepared by the co-precipitation method achieves a conversion rate of 2-(1-cyclohexenyl)cyclohexanone higher than 98% and an OPP selectivity of up to more than 93%, but the problem of catalyst lifespan is not solved.

[0005] Ding Jielian et al. (Research on Ni-Cu catalysts for preparing o-phenylphenol [J], Modern Chemical Industry, 26 (S1), 2006) used Ni and Cu as the active components of the catalyst and added different additives. Among them, the Ni / Cu / Cr / K catalyst prepared by stepwise impregnation had the best effect, achieving a conversion rate of 2-(1-cyclohexenyl)cyclohexanone of 96% and an OPP yield of 75%, but the OPP selectivity was not high. In addition, Ding Jielian et al. (Effect of different precipitants on the performance of Cu / Mg catalysts for preparing o-phenylphenol [J], Industrial Catalysis, 16 (5), 2008) prepared a Cu / Mg bimetallic dehydrogenation catalyst by the co-precipitation method. The activity and selectivity of the catalyst were relatively ideal in the initial stage of the reaction, but the stability of the catalyst decreased rapidly and it was difficult to be actually promoted and used industrially.

[0006] Zhang Tianchi (Research on the Catalytic Performance of Copper-based Catalysts for the Synthesis of o-Phenylphenol [J], Yangzhou University, 2016) prepared Cu / Mg / Al hydrotalcite-like compounds by the coprecipitation method and investigated the influence of introducing Ni and Zr on the catalyst performance. It was found that the combination of Cu and Ni could improve the stability of the catalyst, but it would also affect the initial activity. The introduction of Zr could improve the initial activity of the catalyst, but the lifespan was poor, the activity decreased rapidly, and the stability was insufficient.

[0007] Li Qian et al. (Preparation of Ce-Cu / ZnAl Hydrotalcite Composite Dehydrogenation Catalysts and Their Catalytic Performance for the Synthesis of o-Phenylphenol [J], Modern Chemical Industry, 2019) synthesized ZnAl-LDHs on the surface of γ-Al2O3 by the in-situ synthesis method and then prepared Cu-Ce / ZnAl-LDHs by the impregnation method. At the initial stage of the reaction, the conversion rate of the catalyst was close to 100%, and the selectivity could reach 98%. However, as the reaction proceeded, the activity of the catalyst decreased rapidly, the stability of the catalyst was poor, and the catalyst preparation process was cumbersome, which was not suitable for large-scale industrial applications.

[0008] Therefore, the development of non-noble metal catalysts with high activity, high selectivity, high stability, and low cost is of great significance for reducing costs and increasing efficiency in the preparation of OPP by the self-condensation dehydrogenation method of cyclohexanone. Summary of the Invention

[0009] Aiming at the problems that the existing catalysts for the preparation of o-phenylphenol by the self-condensation dehydrogenation method of cyclohexanone have unsatisfactory activity and stability of noble metal catalysts and high production costs, and the non-noble metal catalysts with lower costs are difficult to balance high activity, high selectivity, and high activity stability, the present invention provides a dehydrogenation catalyst, a preparation method thereof, and a method for preparing o-phenylphenol.

[0010] To achieve the above object, in the first aspect of the present invention, a dehydrogenation catalyst is provided. The dehydrogenation catalyst includes an alumina carrier, and a main active component and a promoter supported on the alumina carrier; wherein,

[0011] The main active component includes Cu and Ni; wherein, the weight ratio of Cu:Ni is 1:(0.1 - 10);

[0012] The promoter includes Mg and / or P;

[0013] The weight ratio of the main active component: promoter: alumina carrier is (8 - 70):(0.5 - 10):100.

[0014] In the second aspect of the present invention, a preparation method of the catalyst described in the first aspect is provided. The method includes:

[0015] (1) Mix and deposit a solution containing a copper source and a nickel source with a slurry containing alumina powder to obtain a slurry containing a deposited product;

[0016] (2) Carry out a precipitation reaction on the slurry containing the deposition product and a precipitant, and subject the product obtained from the precipitation reaction to an aging treatment to obtain an aged precipitation product;

[0017] (3) Carry out a first calcination on the aged precipitation product to obtain a catalyst intermediate;

[0018] (4) Load a magnesium source and / or a phosphorus source onto the catalyst intermediate, and then successively carry out a second calcination and a reduction treatment to obtain a dehydrogenation catalyst.

[0019] The third aspect of the present invention provides a method for preparing o-phenylphenol, the method comprising:

[0020] Carry out a dehydrogenation reaction on cyclohexenyl cyclohexanone in the presence of the catalyst described in the first aspect above to obtain o-phenylphenol.

[0021] The dehydrogenation catalyst provided by the present invention uses an alumina support and specific main active components and promoters supported on the support, and can have the characteristics of high conversion rate of cyclohexenyl cyclohexanone, high selectivity of o-phenylphenol, and good activity stability in the reaction of dehydrogenating cyclohexenyl cyclohexanone to prepare o-phenylphenol (OPP), and the use cost is relatively low. Specific Embodiments

[0022] The endpoints and any values within the ranges disclosed herein are not limited to the exact 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 each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0023] The first aspect of the present invention provides a dehydrogenation catalyst, the dehydrogenation catalyst comprising an alumina support, and main active components and promoters supported on the alumina support; wherein,

[0024] The main active components include Cu and Ni; wherein, the weight ratio of Cu:Ni is 1:(0.1 - 10);

[0025] The promoters include Mg and / or P;

[0026] The weight ratio of the main active components: promoters: alumina support is (8 - 70):(0.5 - 10):100.

[0027] The dehydrogenation catalyst provided by the present invention is based on an alumina support, and a specific amount of double main active components (elemental Cu and elemental Ni) and promoters (elemental Mg and / or elemental P) are loaded on the alumina support. With the joint cooperation of the support, the main active components and the promoters, the catalyst is endowed with the characteristics of high conversion rate of cyclohexenyl cyclohexanone, high selectivity of o-phenylphenol and good activity stability in the dehydrogenation reaction of cyclohexenyl cyclohexanone. This catalyst is used for the dehydrogenation of cyclohexenyl cyclohexanone to prepare o-phenylphenol, and it can achieve a conversion rate of cyclohexenyl cyclohexanone of more than 90% and a selectivity of o-phenylphenol of more than 74% at the initial stage of the reaction (when the reaction proceeds for 6 h). When the reaction proceeds for 100 h, the conversion rate of cyclohexenyl cyclohexanone still reaches more than 88%, and the selectivity of o-phenylphenol still reaches more than 70%. The active components of this catalyst use non-precious metals, and the use cost is relatively low.

[0028] According to the present invention, in the dehydrogenation catalyst, the phase composition of the alumina support is defined relatively widely, and preferably, the alumina support is in the γ-Al2O3 phase.

[0029] According to the present invention, in the dehydrogenation catalyst, for the main active components, on the basis of satisfying the above proportional relationship, preferably, in the main active components, the weight ratio of Cu:Ni is 1:(0.3 - 5), which can bring better dehydrogenation performance of the catalyst and improve the selectivity of the target product.

[0030] According to the present invention, in the dehydrogenation catalyst, on the basis of satisfying the above proportional relationship among the main active components, the promoters and the alumina support, preferably, the weight ratio of the main active components: the promoters: the alumina support is (25 - 60):(1 - 5):100. By adopting the above preferred component proportional relationship, the dehydrogenation catalyst can better have the characteristics of high conversion rate of cyclohexenyl cyclohexanone, high selectivity of o-phenylphenol and good activity stability.

[0031] According to the present invention, in the dehydrogenation catalyst, preferably, the promoter contains both Mg and P, and the two are used together. Compared with the case where the promoter contains only Mg (without P) or only P (without Mg), it can improve the dispersion degree of the active components, inhibit the deactivation rate of the catalyst, and improve the stability and selectivity of the catalyst.

[0032] According to the present invention, in the dehydrogenation catalyst, preferably, in the promoter, the weight ratio of Mg:P is 1:(0.1 - 3).

[0033] According to the present invention, the dehydrogenation catalyst has a relatively large specific surface area. Preferably, the specific surface area of the dehydrogenation catalyst is 180 - 260m 2 / g.

[0034] In the present invention, the specific surface area of the catalyst is measured by N2 physical adsorption-desorption and calculated using the BET formula.

[0035] According to the present invention, the dehydrogenation catalyst has a relatively large pore size. Preferably, the average pore size of the dehydrogenation catalyst is 15 - 40 nm.

[0036] In the present invention, the average pore size of the catalyst is measured by N2 physical adsorption-desorption and calculated using the BJH method.

[0037] According to a particularly preferred embodiment of the present invention, the dehydrogenation catalyst comprises an alumina support, and a main active component and a promoter supported on the alumina support; wherein, the main active component comprises Cu and Ni, and the weight ratio of Cu:Ni is 1:(0.4 - 3); the promoter comprises Mg and P, and the weight ratio of Mg:P is 1:(0.4 - 2.5); the weight ratio of the main active component:promoter:alumina support is (28 - 40):(1.2 - 3):100; the specific surface area of the dehydrogenation catalyst is 220 - 240 m 2 / g, and the average pore size is 20 - 30 nm. The dehydrogenation catalyst of this particularly preferred embodiment can have further improved comprehensive performance in the reaction of dehydrogenating cyclohexenyl cyclohexanone to prepare o-phenylphenol, with high cyclohexenyl cyclohexanone conversion rate, high o-phenylphenol selectivity, and good catalyst activity stability. It can achieve a cyclohexenyl cyclohexanone conversion rate of more than 99% and an o-phenylphenol selectivity of more than 90% at the initial stage of the reaction (after 6 h of reaction), and the cyclohexenyl cyclohexanone conversion rate still reaches more than 98% and the o-phenylphenol selectivity still reaches more than 85% after 100 h of reaction.

[0038] The second aspect of the present invention provides a preparation method of the catalyst described in the first aspect above, and the method comprises:

[0039] (1) Mix and deposit a solution containing a copper source and a nickel source with a slurry containing alumina powder to obtain a slurry containing a deposited product;

[0040] (2) Carry out a precipitation reaction on the slurry containing the deposited product with a precipitant, and subject the product obtained from the precipitation reaction to an aging treatment to obtain an aged precipitation product;

[0041] (3) Carry out a first calcination on the aged precipitation product to obtain a catalyst intermediate;

[0042] (4) Load a magnesium source and / or a phosphorus source on the catalyst intermediate, and then successively carry out a second calcination and a reduction treatment to obtain a dehydrogenation catalyst.

[0043] According to the present invention, in the preparation method of the composite catalyst, preferably, the copper source, nickel source, magnesium source, and phosphorus source respectively adopt water-soluble salts containing the corresponding elements. For example, the copper source can adopt at least one of nitrates, sulfates, and chlorides including but not limited to Cu, and preferably adopts nitrate. The nickel source can adopt at least one of nitrates, sulfates, and chlorides including but not limited to Ni, and preferably adopts nitrate. The magnesium source can adopt at least one of nitrates, sulfates, and chlorides including but not limited to Mg, and preferably adopts nitrate. The phosphorus source can adopt at least one of NaH2PO2, NaH2PO4, (NH4)3PO4, H3PO4, and K3PO4, and preferably adopts NaH2PO2.

[0044] According to the present invention, in the preparation method of the composite catalyst, preferably, the specific surface area of the alumina powder is 250-300 m 2 / g, which is beneficial to increasing the contact area between the reaction raw materials and the prepared catalyst, improving the reaction rate, and at the same time increasing more active sites and improving the selectivity of the reaction.

[0045] According to the present invention, in the preparation method of the composite catalyst, the precipitant can be selected from conventional basic precipitants capable of precipitating metal cations. Preferably, the precipitant can be selected from at least one of KOH, NaOH, K2CO3, and Na2CO3.

[0046] According to the present invention, in the preparation method of the composite catalyst, preferably, the precipitant can be fed in the form of an aqueous solution.

[0047] According to the present invention, in step (1) of the preparation method of the composite catalyst, the solution containing the copper source and nickel source can be obtained by fully dissolving the copper source and nickel source in water. Preferably, in the solution containing the copper source and nickel source, the concentration of metal cations (Cu 2+ and Ni 2+ ) is 0.1-1.5 mol / L.

[0048] According to the present invention, in step (1) of the preparation method of the composite catalyst, the slurry containing the alumina powder can be obtained by fully dispersing the alumina powder in water. Preferably, in the slurry containing the alumina powder, the concentration of the alumina powder is 5-15% by weight.

[0049] According to the present invention, in step (1) of the preparation method of the composite catalyst, the mixed deposition can be achieved by stirring and mixing the solution containing the copper source and nickel source with the slurry containing the alumina powder. Preferably, the conditions for the mixed deposition include: the temperature is 60-90 °C, and the time is 30-60 min.

[0050] According to the present invention, in the preparation method of the composite catalyst, in step (2), preferably, the precipitation reaction can be carried out by gradually adding (for example, gradually dropping) the precipitant into the slurry containing the deposition product. Preferably, the conditions of the precipitation reaction include: the temperature is 60-90 °C, the time is 10-30 min, and the pH value at the end of the reaction is 7-9.

[0051] According to the present invention, in the preparation method of the composite catalyst, in step (2), the aging treatment can be carried out by static setting. Through the aging treatment, the precipitate is further crystallized, promoting the growth of crystal grains and improving the crystallinity. Preferably, the conditions of the aging include: the temperature is 60-90 °C, and the time is 8-12 h.

[0052] According to the present invention, in the preparation method of the composite catalyst, in step (3), before the first calcination, preferably, the aged precipitate product is filtered and first dried in sequence.

[0053] Preferably, the conditions of the first drying include: the temperature is 80-120 °C, and the time is 6-24 h.

[0054] According to the present invention, in the preparation method of the composite catalyst, in step (3), preferably, the first calcination is carried out in an oxygen-containing atmosphere (for example, air atmosphere), and a first composite oxide (catalyst intermediate product) is obtained by calcination. Preferably, the conditions of the first calcination include: the temperature is 450-650 °C, and the time is 4-6 h.

[0055] According to the present invention, in the preparation method of the composite catalyst, in step (4), there is no particular limitation on the loading method. For example, preferably, the impregnation method can be adopted. Specifically, the catalyst intermediate product can be impregnated in a solution containing a magnesium source and / or a phosphorus source (which can be obtained by fully dissolving the magnesium source and / or the phosphorus source in water. Preferably, in the solution containing the magnesium source and / or the phosphorus source, the concentration of Mg 2+ is 0-2 mol / L, and the concentration of element P is 0-2 mol / L, and the two concentrations are not both 0), and then the impregnated product is second dried to load the magnesium source and / or the phosphorus source on the catalyst intermediate product. The present invention does not particularly limit the impregnation method and the conditions adopted, and conventional impregnation methods and impregnation parameters can be adopted. For example, the impregnation temperature is 0-60 °C, and the impregnation time is 2-6 h.

[0056] Preferably, the conditions of the second drying include: the temperature is 80-120 °C, and the time is 6-24 h.

[0057] According to the present invention, in the preparation method of the composite catalyst, in step (4), preferably, the second calcination is carried out in an oxygen-containing atmosphere (for example, air atmosphere), and the second composite oxide is obtained by calcination. Preferably, the conditions of the second calcination include: the temperature is 450 - 650 °C, and the time is 2 - 6 h.

[0058] According to the present invention, in the preparation method of the composite catalyst, in step (4), through the reduction treatment, activation is achieved, and the main active component and the promoter in the elemental state are obtained. Preferably, the conditions of the reduction treatment include: carried out in a hydrogen-containing atmosphere, the temperature is 250 - 650 °C, and the time is 2 - 6 h.

[0059] According to the present invention, in the preparation method of the composite catalyst, the types and feeding amounts of the raw materials are such that the composition of the dehydrogenation catalyst prepared includes an alumina support, and a main active component and a promoter supported on the alumina support; wherein, the main active component includes Cu and Ni; wherein, the weight ratio of Cu:Ni is 1:(0.1 - 10); the promoter includes Mg and / or P; the weight ratio of the main active component: the promoter: the alumina support is (8 - 70):(0.5 - 10):100. The dehydrogenation catalyst prepared by this preparation method is used for the dehydrogenation of cyclohexenyl cyclohexanone to prepare o-phenylphenol, showing comprehensive performance of both high conversion rate of cyclohexenyl cyclohexanone, high selectivity of o-phenylphenol and good activity stability of the catalyst, and the preparation cost is relatively low.

[0060] The third aspect of the present invention provides a method for preparing o-phenylphenol, and the method includes:

[0061] In the presence of the catalyst described in the foregoing first aspect, cyclohexenyl cyclohexanone is subjected to a dehydrogenation reaction to obtain o-phenylphenol.

[0062] According to the present invention, preferably, the method for preparing o-phenylphenol is carried out in a fixed-bed reactor.

[0063] According to the present invention, in the method for preparing o-phenylphenol, preferably, the conditions of the dehydrogenation reaction include: the temperature is 290 - 380 °C, and the space velocity of the cyclohexenyl cyclohexanone feed liquid is 0.4 - 1 h -1 .

[0064] In the method for preparing o-phenylphenol provided by the present invention, by using the dehydrogenation catalyst provided in the first aspect of the present invention, the conversion rate of cyclohexenyl cyclohexanone can reach more than 90% in the initial stage of the reaction (the reaction proceeds for 6 h), the selectivity of o-phenylphenol reaches more than 74%, the conversion rate of cyclohexenyl cyclohexanone still reaches more than 88% when the reaction proceeds for 100 h, and the selectivity of o-phenylphenol still reaches more than 70%. This method has the characteristics of high conversion rate of cyclohexenyl cyclohexanone, high selectivity of o-phenylphenol and good activity stability of the catalyst.

[0065] The present invention will be described in detail below through examples. In the following examples and comparative examples, unless otherwise specified, all are conventional methods; the reagents and materials, unless otherwise specified, can be obtained from commercial sources.

[0066] In the following examples and comparative examples, the weight ratios of the components in the prepared catalysts are calculated from the feed amounts of the raw materials.

[0067] Aluminum oxide powder (γ-Al2O3): specific surface area is 250 - 300 m 2 / g, purchased from Linqu Henghui New Materials Co., Ltd.

[0068] Example 1

[0069] (1) A solution containing a copper source and a nickel source (obtained by dissolving 3.802 g of Cu(NO3)2·3H2O and 9.909 g of Ni(NO3)2·6H2O in 100 g of deionized water) and a slurry containing aluminum oxide powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) were poured into a reactor for mixing deposition (temperature was 80 °C, time was 30 min) to obtain a slurry containing a deposition product;

[0070] (2) A precipitating agent (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) was dropped into the above-obtained slurry containing the deposition product drop by drop through a peristaltic pump for precipitation reaction (reaction temperature was 80 °C, reaction time was 30 min, the pH value at the end of the precipitation reaction was 8); then the product obtained from the precipitation reaction was subjected to an aging treatment (standing temperature was 80 °C, standing time was 10 h) to obtain an aged precipitation product;

[0071] (3) The above-obtained aged precipitation product was filtered and dried (drying temperature was 120 °C, drying time was 8 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature was 550 °C, calcination time was 4 h) to obtain a catalyst intermediate;

[0072] (4) The above-obtained catalyst intermediate was impregnated in a solution containing a magnesium source and a phosphorus source (obtained by dissolving 0.527 g of Mg(NO3)2·6H2O and 0.284 g of NaH2PO2 in 10.099 g of deionized water), shaken well, impregnated at 30 °C for 2 h and then dried (drying temperature was 120 °C, drying time was 2 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature was 550 °C, calcination time was 4 h); the obtained calcined product was subjected to a reduction treatment under a H2 atmosphere (reduction temperature was 350 °C, reduction time was 4 h) to obtain a dehydrogenation catalyst (denoted as C1).

[0073] C1 has an alumina support, a main active component (Cu and Ni, where the weight ratio of Cu:Ni is 1:2) and promoters (Mg and P, where the weight ratio of Mg:P is 1:2) supported on the alumina support; the weight ratio of the main active component: promoters: alumina support is 30:1.5:100.

[0074] The specific surface area of C1 is 229 m 2 / g, and the average pore diameter is 24 nm.

[0075] Example 2

[0076] (1) A solution containing a copper source and a nickel source (obtained by dissolving 7.605 g of Cu(NO3)2·3H2O and 4.955 g of Ni(NO3)2·6H2O in 100 g of deionized water) and a slurry containing alumina powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) are poured into a reactor for mixed deposition (temperature is 80 °C, time is 30 min) to obtain a slurry containing the deposited product;

[0077] (2) A precipitating agent (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) is added dropwise into the slurry containing the deposited product obtained above through a peristaltic pump for precipitation reaction (reaction temperature is 80 °C, reaction time is 30 min, the pH value at the end of the precipitation reaction is 8); then the product obtained from the precipitation reaction is subjected to aging treatment (standing temperature is 80 °C, standing time is 10 h) to obtain an aged precipitation product;

[0078] (3) The aged precipitation product obtained above is filtered and dried (drying temperature is 120 °C, drying time is 8 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h) to obtain a catalyst intermediate;

[0079] (4) The catalyst intermediate obtained above is impregnated in a solution containing a magnesium source and a phosphorus source (obtained by dissolving 0.527 g of Mg(NO3)2·6H2O and 0.284 g of NaH2PO2 in 10.099 g of deionized water), shaken well, dried at 30 °C for 2 h and then dried (drying temperature is 120 °C, drying time is 2 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h); the obtained calcined product is subjected to reduction treatment under a H2 atmosphere (reduction temperature is 350 °C, reduction time is 4 h) to obtain a dehydrogenation catalyst (denoted as C2).

[0080] C2 has an alumina support, as well as a main active component (Cu and Ni, where the weight ratio of Cu:Ni is 1:0.5) and promoters (Mg and P, where the weight ratio of Mg:P is 1:2) supported on the alumina support; the weight ratio of the main active component: promoters: alumina support is 30:1.5:100.

[0081] The specific surface area of C2 is 230 m 2 / g, and the average pore diameter is 25 nm.

[0082] Example 3

[0083] (1) A solution containing a copper source and a nickel source (obtained by dissolving 1.901 g of Cu(NO3)2·3H2O and 14.864 g of Ni(NO3)2·6H2O in 100 g of deionized water) and a slurry containing alumina powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) are poured into a reactor for mixed deposition (temperature is 80 °C, time is 30 min) to obtain a slurry containing the deposited product.

[0084] (2) A precipitant (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) is gradually added dropwise into the slurry containing the deposited product obtained above through a peristaltic pump for precipitation reaction (reaction temperature is 80 °C, reaction time is 30 min, and the pH value at the end of the precipitation reaction is 8); then the product obtained from the precipitation reaction is subjected to aging treatment (standing temperature is 80 °C, standing time is 10 h) to obtain an aged precipitate product.

[0085] (3) The aged precipitate product obtained above is filtered and dried (drying temperature is 120 °C, drying time is 8 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h) to obtain a catalyst intermediate product.

[0086] (4) The catalyst intermediate product obtained above is impregnated in a solution containing a magnesium source and a phosphorus source (obtained by dissolving 0.422 g of Mg(NO3)2·6H2O and 0.114 g of NaH2PO2 in 10.099 g of deionized water), shaken well, dried at 30 °C for 2 h (drying temperature is 120 °C, drying time is 2 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h); the obtained calcined product is subjected to reduction treatment under a H2 atmosphere (reduction temperature is 350 °C, reduction time is 4 h) to obtain a dehydrogenation catalyst (denoted as C3).

[0087] C3 has an alumina support, a main active component (Cu and Ni, where the weight ratio of Cu:Ni is 1:6) and promoters (Mg and P, where the weight ratio of Mg:P is 1:1) supported on the alumina support; the weight ratio of the main active component: promoters: alumina support is 35:0.8:100.

[0088] The specific surface area of C3 is 225 m 2 / g, and the average pore diameter is 22 nm.

[0089] Example 4

[0090] (1) A solution containing a copper source and a nickel source (obtained by dissolving 3.802 g of Cu(NO3)2·3H2O and 7.432 g of Ni(NO3)2·6H2O in 100 g of deionized water) and a slurry containing alumina powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) were poured into a reactor for mixing deposition (temperature: 80 °C, time: 30 min) to obtain a slurry containing the deposited product.

[0091] (2) A precipitating agent (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) was gradually added dropwise into the slurry containing the deposited product obtained above through a peristaltic pump for precipitation reaction (reaction temperature: 80 °C, reaction time: 30 min, pH value at the end of the precipitation reaction: 8); then the product obtained from the precipitation reaction was subjected to aging treatment (standing temperature: 80 °C, standing time: 10 h) to obtain an aged precipitation product.

[0092] (3) The aged precipitation product obtained above was filtered and dried (drying temperature: 120 °C, drying time: 8 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h) to obtain a catalyst intermediate.

[0093] (4) The catalyst intermediate obtained above was impregnated in a solution containing a magnesium source and a phosphorus source (obtained by dissolving 2.637 g of Mg(NO3)2·6H2O and 0.994 g of NaH2PO2 in 10.099 g of deionized water), shaken well, dried at 30 °C for 2 h (drying temperature: 120 °C, drying time: 2 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h); the obtained calcined product was subjected to reduction treatment under a H2 atmosphere (reduction temperature: 350 °C, reduction time: 4 h) to obtain a dehydrogenation catalyst (denoted as C4).

[0094] C4 has an alumina support, a main active component (Cu and Ni, where the weight ratio of Cu:Ni is 1:1.5) and a promoter (Mg and P, where the weight ratio of Mg:P is 1:1.4) supported on the alumina support; the weight ratio of the main active component: the promoter: the alumina support is 25:6:100.

[0095] The specific surface area of C4 is 228 m 2 / g, and the average pore diameter is 23 nm.

[0096] Example 5

[0097] (1) A solution containing a copper source and a nickel source (obtained by dissolving 3.802 g of Cu(NO3)2·3H2O and 7.432 g of Ni(NO3)2·6H2O in 100 g of deionized water) and a slurry containing alumina powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) are poured into a reactor for mixing deposition (temperature is 80 °C, time is 30 min) to obtain a slurry containing the deposited product;

[0098] (2) A precipitant (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) is gradually dropped into the slurry containing the deposited product obtained above through a peristaltic pump for precipitation reaction (reaction temperature is 80 °C, reaction time is 30 min, the pH value at the end of the precipitation reaction is 8); then the product obtained from the precipitation reaction is subjected to aging treatment (standing temperature is 80 °C, standing time is 10 h) to obtain an aged precipitation product;

[0099] (3) The aged precipitation product obtained above is filtered and dried (drying temperature is 120 °C, drying time is 8 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h) to obtain a catalyst intermediate;

[0100] (4) The catalyst intermediate obtained above is impregnated in a solution containing a magnesium source (obtained by dissolving 2.637 g of Mg(NO3)2·6H2O in 6 g of deionized water), shaken well, dried at 30 °C for 2 h (drying temperature is 120 °C, drying time is 2 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h); the obtained calcined product is subjected to reduction treatment under a H2 atmosphere (reduction temperature is 350 °C, reduction time is 4 h) to obtain a dehydrogenation catalyst (denoted as C5).

[0101] C5 has an alumina support, a main active component (Cu and Ni, where the weight ratio of Cu:Ni is 1:1.5) and a promoter (metal Mg) supported on the alumina support; the weight ratio of the main active component: the promoter: the alumina support is 25:2.5:100.

[0102] The specific surface area of C5 is 231 m 2 / g, and the average pore diameter is 24 nm.

[0103] Example 6

[0104] (1) A solution containing a copper source and a nickel source (obtained by dissolving 3.802 g of Cu(NO3)2·3H2O and 7.432 g of Ni(NO3)2·6H2O in 100 g of deionized water) and a slurry containing alumina powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) were poured into a reactor for mixed deposition (temperature: 80 °C, time: 30 min) to obtain a slurry containing the deposited product;

[0105] (2) A precipitant (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) was gradually added dropwise into the slurry containing the deposited product obtained above through a peristaltic pump for precipitation reaction (reaction temperature: 80 °C, reaction time: 30 min, pH value at the end of the precipitation reaction: 8); then the product obtained from the precipitation reaction was subjected to an aging treatment (standing temperature: 80 °C, standing time: 10 h) to obtain an aged precipitate product;

[0106] (3) The aged precipitate product obtained above was filtered and dried (drying temperature: 120 °C, drying time: 8 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h) to obtain a catalyst intermediate;

[0107] (4) The catalyst intermediate obtained above was impregnated in a solution containing a phosphorus source (obtained by dissolving 3.5 g of NaH2PO2 in 6 g of deionized water) and shaken well. After impregnation at 30 °C for 2 h, it was dried (drying temperature: 120 °C, drying time: 2 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h); the obtained calcined product was subjected to a reduction treatment under a H2 atmosphere (reduction temperature: 350 °C, reduction time: 4 h) to obtain a dehydrogenation catalyst (denoted as C6).

[0108] C6 has an alumina support and a main active component (Cu and Ni, where the weight ratio of Cu:Ni is 1:1.5) and a promoter (elemental P) supported on the alumina support; the weight ratio of the main active component: promoter: alumina support is 25:3.5:100.

[0109] The specific surface area of C6 is 230 m 2 / g, and the average pore diameter is 25 nm.

[0110] Comparative Example 1

[0111] (1) A solution containing a copper source and a nickel source (obtained by dissolving 3.802 g of Cu(NO3)2·3H2O and 0.248 g of Ni(NO3)2·6H2O in 100 g of deionized water) and a slurry containing alumina powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) were poured into a reactor for mixed deposition (temperature: 80 °C, time: 30 min) to obtain a slurry containing the deposited product;

[0112] (2) A precipitant (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) was added dropwise into the slurry containing the deposited product obtained above through a peristaltic pump for precipitation reaction (reaction temperature: 80 °C, reaction time: 30 min, pH value at the end of precipitation reaction: 8); then the product obtained from the precipitation reaction was subjected to aging treatment (standing temperature: 80 °C, standing time: 10 h) to obtain an aged precipitate product;

[0113] (3) The aged precipitate product obtained above was filtered and dried (drying temperature: 120 °C, drying time: 8 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h) to obtain a catalyst intermediate;

[0114] (4) The catalyst intermediate obtained above was impregnated in a solution containing a magnesium source and a phosphorus source (obtained by dissolving 2.637 g of Mg(NO3)2·6H2O and 0.994 g of NaH2PO2 in 6 g of deionized water), shaken well, dried at 30 °C for 2 h (drying temperature: 120 °C, drying time: 2 h), and then calcined in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h); the obtained calcined product was subjected to reduction treatment under a H2 atmosphere (reduction temperature: 350 °C, reduction time: 4 h) to obtain a dehydrogenation catalyst (denoted as DC1).

[0115] DC1 has an alumina support and main active components (Cu and Ni, where the weight ratio of Cu:Ni is 1:0.05) and promoters (Mg and P, where the weight ratio of Mg:P is 1:1.4) supported on the alumina support; the weight ratio of the main active components: promoters: alumina support is 10.5:6:100.

[0116] The specific surface area of DC1 is 231 m 2 / g, and the average pore diameter is 26 nm.

[0117] Comparative Example 2

[0118] (1) Pour the solution containing copper source and nickel source (obtained by dissolving 3.802 g of Cu(NO₃)₂·3H₂O and 7.432 g of Ni(NO₃)₂·6H₂O in 100 g of deionized water) and the slurry containing alumina powder (obtained by dispersing 10 g of γ-Al₂O₃ in 100 g of deionized water) into a reactor, and carry out mixed deposition (temperature is 80 °C, time is 30 min) to obtain a slurry containing the deposited product;

[0119] (2) Dropwise add the precipitant (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) into the slurry containing the deposited product obtained above through a peristaltic pump to carry out precipitation reaction (reaction temperature is 80 °C, reaction time is 30 min, the pH value at the end of the precipitation reaction is 8); then carry out aging treatment on the product obtained from the precipitation reaction (standing temperature is 80 °C, standing time is 10 h) to obtain an aged precipitation product;

[0120] (3) Filter and dry the aged precipitation product obtained above (drying temperature is 120 °C, drying time is 8 h), and then carry out calcination in a muffle furnace under air atmosphere (calcination temperature is 550 °C, calcination time is 4 h) to obtain a catalyst intermediate;

[0121] (4) Immerse the catalyst intermediate obtained above in the solution containing magnesium source and phosphorus source (obtained by dissolving 0.211 g of Mg(NO₃)₂·6H₂O and 0.028 g of NaH₂PO₂ in 6 g of deionized water), shake well, after impregnating for 2 h at 30 °C, carry out drying (drying temperature is 120 °C, drying time is 2 h), and then carry out calcination in a muffle furnace under air atmosphere (calcination temperature is 550 °C, calcination time is 4 h); carry out reduction treatment on the obtained calcined product under H₂ atmosphere (reduction temperature is 350 °C, reduction time is 4 h) to obtain a dehydrogenation catalyst (denoted as DC2).

[0122] DC2 has an alumina carrier and the main active components (Cu and Ni, where the weight ratio of Cu:Ni is 1:1.5) and promoters (Mg and P, where the weight ratio of Mg:P is 1:0.5) supported on the alumina carrier; the weight ratio of the main active components: promoters: alumina carrier is 25:0.3:100.

[0123] The specific surface area of DC2 is 234 m 2 ² / g, and the average pore diameter is 26 nm.

[0124] Comparative Example 3

[0125] (1) Pour the solution containing copper source and nickel source (obtained by dissolving 3.802 g of Cu(NO3)2·3H2O and 7.432 g of Ni(NO3)2·6H2O in 100 g of deionized water) and the slurry containing alumina powder (obtained by dispersing 10 g of γ-Al2O3 in 100 g of deionized water) into a reactor, and carry out mixed deposition (temperature is 80 °C, time is 30 min) to obtain a slurry containing the deposited product;

[0126] (2) Dropwise add the precipitant (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) into the slurry containing the deposited product obtained above through a peristaltic pump for precipitation reaction (reaction temperature is 80 °C, reaction time is 30 min, the pH value at the end of the precipitation reaction is 8); then carry out aging treatment on the product obtained from the precipitation reaction (static temperature is 80 °C, static time is 10 h) to obtain an aged precipitation product;

[0127] (3) Filter and dry the aged precipitation product obtained above (drying temperature is 120 °C, drying time is 8 h), and then carry out calcination in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 5 h) to obtain a catalyst intermediate;

[0128] (4) Immerse the catalyst intermediate obtained above in the solution containing cobalt source and iron source (obtained by dissolving 1.235 g of Co(NO3)2·6H2O and 2.532 g of Fe(NO3)3·9H2O in 6 g of deionized water), shake well, after impregnating for 2 h at 30 °C, carry out drying (drying temperature is 120 °C, drying time is 2 h), and then carry out calcination in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h); carry out reduction treatment on the obtained calcined product under a H2 atmosphere (reduction temperature is 350 °C, reduction time is 4 h) to obtain a dehydrogenation catalyst (denoted as DC3).

[0129] DC3 has an alumina support and the main active components (Cu and Ni, where the weight ratio of Cu:Ni is 1:1.5) and promoters (Co and Fe, where the weight ratio of Co:Fe is 1:1.4) supported on the alumina support; the weight ratio of the main active components: promoters: alumina support is 25:6:100.

[0130] The specific surface area of DC3 is 231 m 2 / g, and the average pore diameter is 25 nm.

[0131] Comparative Example 4

[0132] (1) Pour the solution containing copper source and nickel source (obtained by dissolving 3.802 g of Cu(NO3)2·3H2O and 7.432 g of Ni(NO3)2·6H2O in 100 g of deionized water) and the slurry containing Hβ zeolite (obtained by dispersing 10 g of Hβ zeolite in 100 g of deionized water) into a reactor for mixing deposition (temperature: 80 °C, time: 30 min) to obtain a slurry containing the deposition product;

[0133] (2) Dropwise add the precipitant (obtained by dissolving 3.968 g of NaOH in 100 g of deionized water) into the slurry containing the deposition product obtained above through a peristaltic pump for precipitation reaction (reaction temperature: 80 °C, reaction time: 30 min, pH value at the end of precipitation reaction: 8); then age the product obtained from the precipitation reaction (standing temperature: 80 °C, standing time: 10 h) to obtain an aged precipitation product;

[0134] (3) Filter and dry the aged precipitation product obtained above (drying temperature: 120 °C, drying time: 8 h), and then calcine it in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h) to obtain a catalyst intermediate;

[0135] (4) Immerse the catalyst intermediate obtained above in the solution containing magnesium source and phosphorus source (obtained by dissolving 2.637 g of Mg(NO3)2·6H2O and 0.994 g of NaH2PO2 in 6 g of deionized water), shake well, dry it at 30 °C for 2 h (drying temperature: 120 °C, drying time: 2 h), and then calcine it in a muffle furnace under an air atmosphere (calcination temperature: 550 °C, calcination time: 4 h); reduce the obtained calcined product under a H2 atmosphere (reduction temperature: 350 °C, reduction time: 4 h) to obtain a dehydrogenation catalyst (denoted as DC4).

[0136] DC4 has an Hβ zeolite support and the main active components (Cu and N, where the weight ratio of Cu:Ni is 1:1.5) and promoters (Mg and P, where the weight ratio of Mg:P is 1:1.4) supported on the Hβ zeolite support; the weight ratio of the main active components: promoters: Hβ zeolite support is 25:6:100.

[0137] The specific surface area of DC4 is 230 m 2 / g, and the average pore diameter is 24 nm.

[0138] Comparative Example 5

[0139] (1) Dissolve 2.694 g of Pd(NO3)2 in 7.406 g of deionized water to obtain a solution containing Pd;

[0140] (2) Immerse 10 g of γ-Al2O3 in the above Pd-containing solution and stir evenly. Immerse for 2 h at 30 °C, then conduct drying (drying temperature is 120 °C, drying time is 2 h). After drying, conduct calcination in a muffle furnace under an air atmosphere (calcination temperature is 550 °C, calcination time is 4 h); conduct reduction treatment on the obtained calcined product under an H2 atmosphere (reduction temperature is 350 °C, reduction time is 4 h) to obtain a dehydrogenation catalyst (denoted as DC5).

[0141] The specific surface area of DC5 is 233 m 2 / g, and the average pore diameter is 27 nm.

[0142] Test example

[0143] Performance evaluation test of the catalyst

[0144] Use the catalysts C1-C6 and DC1-DC5 prepared in the above Examples 1-6 and Comparative Examples 1-5 to conduct the dehydrogenation reaction of diketone in a fixed-bed reactor. Reaction conditions: The space velocity of the cyclohexenyl cyclohexanone feed liquid is 0.6 h -1 , the flow rate of the H2 accompanying gas is 100 mL / min, and the reaction temperature is 380 °C. After the reaction proceeds for 6 h and 100 h, the products are analyzed by off-line chromatography. The results are shown in Table 1.

[0145] Table 1

[0146]

[0147]

[0148] As can be seen from Table 1, for the dehydrogenation catalysts C1-C6 provided by the present invention, in the dehydrogenation reaction of cyclohexenyl cyclohexanone under the above conditions, the conversion rate of cyclohexenyl cyclohexanone can reach more than 90% after the reaction proceeds for 6 h, and the selectivity of o-phenylphenol can reach more than 74%. After the reaction proceeds for 100 h, the conversion rate of cyclohexenyl cyclohexanone still reaches more than 88%, and the selectivity of o-phenylphenol still reaches more than 70%. It has the advantages of high conversion rate of cyclohexenyl cyclohexanone, high selectivity of o-phenylphenol, and good catalytic activity stability. Among them, Examples 1-2 show particularly prominent effect advantages. The catalysts DC1-DC5 do not have the catalyst composition of the present invention and cannot obtain the above comprehensive effects.

[0149] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, including any other suitable combination of each technical feature. These simple modifications and combinations should also be regarded as the content disclosed by the present invention and fall within the protection scope of the present invention.

Claims

1. A dehydrogenation catalyst, characterized in that, The dehydrogenation catalyst comprises an alumina support, and a main active component and a promoter supported on the alumina support; wherein, the main active component comprises Cu and Ni; wherein, the weight ratio of Cu:Ni is 1:(0.1 - 10); the promoter comprises Mg and / or P; the weight ratio of the main active component:promoter:alumina support is (8 - 70):(0.5 - 10):

100.

2. The dehydrogenation catalyst according to claim 1, wherein, In the main active component, the weight ratio of Cu:Ni is 1:(0.3 - 5).

3. The dehydrogenation catalyst according to claim 1 or 2, wherein the weight ratio of the main active component:promoter:alumina support is (25 - 60):(1 - 5):

100.

4. The dehydrogenation catalyst according to any one of claims 1-3, wherein, the promoter comprises Mg and P; Preferably, in the promoter, the weight ratio of Mg:P is 1:(0.1 - 3).

5. The dehydrogenation catalyst according to any one of claims 1-4, wherein, The specific surface area of the dehydrogenation catalyst is 180 - 260 m 2 / g; and / or, the average pore diameter of the dehydrogenation catalyst is 15 - 40 nm.

6. The preparation method of the dehydrogenation catalyst according to any one of claims 1-5, characterized in that, The method comprises: (1) Mixing and depositing a solution containing a copper source and a nickel source with a slurry containing alumina powder to obtain a slurry containing a deposited product; (2) Carrying out a precipitation reaction on the slurry containing the deposited product with a precipitant, and aging the product obtained from the precipitation reaction to obtain an aged precipitation product; (3) Carrying out a first calcination on the aged precipitation product to obtain a catalyst intermediate; (4) Loading a magnesium source and / or a phosphorus source on the catalyst intermediate, and then successively carrying out a second calcination and a reduction treatment to obtain a dehydrogenation catalyst.

7. The preparation method according to claim 6, wherein, The copper source, nickel source, magnesium source, and phosphorus source are respectively water-soluble salts containing the corresponding elements; and / or, the specific surface area of the alumina powder is 250-300 m 2 / g; and / or, the precipitant is an alkaline precipitant, preferably at least one of KOH, NaOH, K2CO3, and Na2CO3.

8. The preparation method according to claim 6 or 7, wherein In step (1), the conditions for the mixing and deposition include: temperature is 60 - 90°C, time is 30 - 60 min; and / or, in step (2), the conditions for the precipitation reaction include: temperature is 60 - 90°C, time is 10 - 30 min, and the pH value at the reaction end point is 7 - 9; and / or, in step (2), the conditions for the aging include: temperature is 60 - 90°C, time is 8 - 12 h; and / or, in step (3), the conditions for the first calcination include: temperature is 450 - 650°C, time is 4 - 6 h; and / or, in step (4), the conditions for the second calcination include: temperature is 450 - 650°C, time is 2 - 6 h; and / or, in step (4), the conditions for the reduction treatment include: carried out in a hydrogen-containing atmosphere, temperature is 250 - 650°C, time is 2 - 6 h.

9. A method for preparing o-phenylphenol, characterized in that, The method comprises: In the presence of the catalyst according to any one of claims 1 - 4, carrying out a dehydrogenation reaction on cyclohexenyl cyclohexanone to obtain o-phenylphenol.

10. The method according to claim 9, wherein, The conditions of the dehydrogenation reaction include: the temperature is 290 - 380 °C, and the liquid hourly space velocity of the cyclohexenyl cyclohexanone feed liquid is 0.4 - 1 h -1 .

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