Catalyst for the production of isopropylbenzene and the method of production and use thereof.

Abstract

This invention relates to a catalyst for the production of isopropylbenzene and the method of production and use thereof. The catalyst comprises a support and an active component supported on the support, wherein the support comprises a supporting substrate and a modifying auxiliary component supported on the supporting substrate, wherein the active component includes metallic palladium and / or its oxides and the modifying auxiliary component is phosphorus and / or its oxides; optionally, the active component also includes metallic copper and / or its oxides; the catalyst further comprises a sulfur-containing compound.When used in the production of isopropylbenzene, the catalyst of the present invention can better inhibit local overheating of the catalyst caused by a relatively high initial catalyst activity, prevents the growth of metallic grains and excessive hydrogenation of isopropylbenzene to isopropylcyclohexane, while effectively controlling the generation of dimerized isopropylbenzene and significantly improving the operating stability of the catalyst while enhancing the selectivity of isopropylbenzene.

Description

Descriptive Report of the Invention Patent for Catalyst for the production of isopropylbenzene and the method of production and use thereof. Technical Field

[001] The present invention relates to a catalyst for the production of isopropylbenzene, in particular, to a catalyst for the production of isopropylbenzene using α,α-dimethylbenzyl alcohol (DMBA), and the method of production and use thereof. Background of the Technique

[002] Propylene oxide (PO for short) is an important organic industrial chemical material that is mainly used for the production of polyether polyols, propylene glycols, propanediol ethers, etc., with polyether polyol consumption accounting for approximately 70%. Currently, commercially available processes for PO production mainly include the chlorohydrin process, the co-oxidation process (PO / SM), and the isopropylbenzene hydroperoxide (CHP) recycling process. The CHP process has the following advantages: the conversion and selectivity of the entire process are very high; the process leads to the single product PO and is not affected by price fluctuations of the styrene byproduct, thus providing more stable economic benefits for manufacturers; the technological process is relatively simple, with fixed investment being two-thirds of the value of the PO / SM process. Furthermore, the anti-corrosion requirements for devices in the CHP process are relatively low.In the technique for producing propylene oxide by the CHP process, a large amount of α,α-dimethylbenzyl alcohol (DMBA) is generated in the epoxidation process of propylene. The α,α-dimethylbenzyl alcohol needs to be hydrogenated to produce isopropylbenzene to reparticipate in the reaction cycle.

[003] U.S. Patent 6646139B2 provides a. Petition 870220025896, dated 03 / 25 / 2022, page 21 / 106 2 / 76 process for the production of isopropylbenzene by catalytic hydrogenolysis of α,α-dimethylbenzyl alcohol with H2 as the hydrogen source and copper-Cr as the catalyst. Although the conversion of α,α-dimethylbenzyl alcohol can be up to 99%, the selectivity is less than 98%. Furthermore, the use of the element Cr in the catalyst production results in serious environmental pollution. Chinese patent CN101733093 B reported that the reaction of alumina-supported or zeolite-supported metallic palladium or a mixture of palladium and Pt at a reaction temperature below 160°C achieved a conversion of α,α-dimethylbenzyl alcohol greater than 99.5% and a selectivity of isopropylbenzene greater than 99.5%. The stronger acidity of the support in the patent significantly led to the polymerization of methylstyrene – an intermediate product of the dehydration of α,α-dimethylbenzyl alcohol. The patent does not mention the technical problem of catalyst stability.Chinese patent application CN104230640 A indicates that the use of a palladium / SiO2 catalyst can achieve 100% conversion of α,α-dimethylbenzyl alcohol, but an isopropylbenzene selectivity of less than 98.5% at a reaction temperature of 180°C.

[004] A well-known method for the production of isopropylbenzene is the dehydration of cumyl alcohol to alpha-methyl styrene in the presence of a dehydration catalyst and the hydrogenation of alpha-methyl styrene to cumene in the presence of a hydrogenation catalyst (e.g., European Chemical News Volume 74 Number 19475-11 March 2001). Chinese patent CN1732139A discloses supplying cumyl alcohol and hydrogen to a dehydration catalyst to obtain a mixture comprising the resulting alpha-methyl styrene and water and hydrogen; supplying the mixture to a hydrogenation catalyst, Petition 870220025896, dated 03 / 25 / 2022, page 22 / 106 3 / 76 where the reaction temperature and pressure are selected so that the water contained in the α-methylstyrene solution after dehydration is not agglomerated. The reaction temperature is preferably from 150 to 300°C, and the reaction pressure is preferably from 100 to 2000 kPa. When the temperature is below 150°C and the pressure is above 2000 kPa, water agglomeration sometimes occurs at the outlet of the dehydration reaction, which degrades the performance of the hydrogenation catalyst. However, the well-known method cannot meet the requirements for low-cost and efficient production of isopropylbenzene.

[005] In the prior art, there are problems that include catalyst activity and selectivity that also need to be improved, low stability and serious environmental pollution in the production of isopropylbenzene by catalysis of the dehydration and hydrogenation of α,α-dimethylbenzyl alcohol. Content of the Invention

[006] The present invention provides a highly active and highly selective supported palladium catalyst having excellent catalytic activity and selectivity, excellent resistance to hydration and good stability to solve the technical problems of low activity and selectivity, low stability and serious environmental pollution of catalysts in the prior art.

[007] An object of the present invention is to provide a catalyst for producing isopropylbenzene, in particular, a catalyst for producing isopropylbenzene from α,α-dimethylbenzyl alcohol, comprising a support and an active component supported on the support, wherein the support comprises a supporting substrate, and an auxiliary modifying component supported on the supporting substrate, wherein the active component Petition 870220025896, dated 03 / 25 / 2022, page 23 / 106 4 / 76 includes metallic palladium and / or its oxides, and the auxiliary modifying component includes phosphorus and / or its oxides.

[008] The support substrate here is not particularly limited and may be a common catalyst support in this field unless otherwise specified. In a preferred embodiment, the support substrate is at least one selected from the group consisting of silica, alumina and activated carbon, preferably alumina.

[009] In a preferred embodiment, the support substrate has a pore size of 10-25 nm and a specific surface area of ​​50-180 m2 / g; more preferably, the support substrate has a pore size of 12-18 nm and a specific surface area of ​​120-160 m2 / g.

[010] In a preferred embodiment, the content of palladium metal and / or oxides thereof in the catalyst is 0.01-5% by weight. In another preferred embodiment, the content of metallic palladium and / or oxides thereof in the catalyst is 0.05-1% by weight, for example, 0.05-0.5% by weight, wherein the content of metallic palladium and / or oxides thereof is based on the content of the element palladium therein.

[011] In the present invention, the source of the metal palladium is not particularly limited, preferably, but not limited to, at least one selected from the group consisting of palladium chloride, palladium nitrate and chloropalladic acid.

[012] In a preferred embodiment, the catalyst has a palladium dispersion of 5-10%, preferably 6.5-8.5%.

[013] Here, the hydrogenolysis of α,α-dimethylbenzyl alcohol is the coupling of two steps: dehydration and hydrogenation. Studies have found that dehydration is the rate-determining step of the reaction. Therefore, we must first improve the dehydration activity of the catalyst in catalyst regulation, so as to Petition 870220025896, dated 03 / 25 / 2022, page 24 / 106 5 / 76 improve the overall reaction rate. The dispersion of metallic palladium has a certain relationship with grain size. Generally, the larger the grain, the smaller the dispersion. Studies have also found that Pd dispersion is not linearly related to grain size because TEM analysis found that the Pd grain size did not increase significantly in a catalyst with reduced dispersion. Furthermore, appropriate grain growth of a Pd catalyst is useful for improving reaction selectivity. Therefore, it is necessary to control the dispersion within a reasonable range.

[014] The dispersion of Pd metal is determined by the hydrogen-oxygen titration method. The specific analysis steps include: raising the catalyst temperature to 120°C (heating rate 10°C / min) in a given hydrogen flow, maintaining the temperature constant for 2 hours; then raising the temperature to 145°C, purging with argon for 1 hour and then lowering the temperature to room temperature (in an argon atmosphere). Chemical adsorption of oxygen: at room temperature, pulsed oxygen is introduced into a sample tube until saturation; then purging with argon for 40 min. Determination of the amount of hydrogen titrated: quantitative hydrogen pulse is performed with a six-way feed valve (quantitative tube volume of 0.3 mL).The amount of hydrogen consumed can be calculated based on the area difference between the front and back peaks in the chromatographic instrument, so that the dispersion of the Pd metal in the catalyst can be calculated.

[015] In a preferred embodiment, the active component further includes an active auxiliary metal and / or its oxides. Preferably, the active auxiliary metal is at least one selected from the group that Petition 870220025896, dated 03 / 25 / 2022, page 25 / 106 6 / 76 consists of metallic copper, metallic zinc, metallic cobalt, metallic tin, metallic nickel and metallic silver, for example, metallic copper. In another preferred embodiment, the content of the active auxiliary metal and / or oxides thereof in the catalyst is 0.0001-0.2% by weight, preferably 0.0007-0.2% by weight, wherein the content of the active auxiliary metal and / or oxides thereof is based on the content of the auxiliary metallic element therein.

[016] In the present invention, the source of the active auxiliary metal is not particularly limited, for example, but not limited to at least one selected from the group consisting of active auxiliary metal chlorides, active auxiliary metal nitrate compounds and active auxiliary metal acetate compounds, etc.

[017] A Pd-based bimetallic / polymetallic catalyst modified with an active auxiliary metal (e.g., Cu) can improve the isopropylbenzene selectivity of the catalyst, particularly in the initial stage. Preferably, the Pd content by weight in the catalyst is greater than that of the active auxiliary metal (e.g., Cu). That is, the weight ratio of Pd to the active auxiliary metal (e.g., Cu) is > 1.

[018] In a preferred embodiment, the content of the modifying auxiliary component (phosphorus and / or its oxides) in the catalyst is 0.2-20% by weight. In another preferred embodiment, the content of the modifying auxiliary component (phosphorus and / or oxides thereof) in the catalyst is 1-15% by weight, more preferably 1-7% by weight, wherein the content of phosphorus and / or oxides thereof is based on the content of the element phosphorus therein.

[019] The source of phosphorus in the present invention is not particularly limited, preferably but not limited to at least one selected from the group consisting of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid and calcium phosphate. Petition 870220025896, dated 03 / 25 / 2022, page 26 / 106 7 / 76

[020] Based on extensive experimental studies, the inventor discovered that modifying the support with phosphorus could significantly improve the hydrogenation activity and stability of the catalyst, in particular the hydrothermal stability. In particular, the simultaneous introduction of an active auxiliary component (active auxiliary metal) into the catalyst had notable technical effects with regard to improving the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene.

[021] In a preferred embodiment, if the support substrate is not silica, the auxiliary modifying component may still include silica.

[022] In the catalyst of the present invention, modification with silica (especially to modify the alumina support substrate) can improve the catalyst's activity and stability. Preferably, alumina is used as the support substrate here.

[023] In a preferred embodiment (where the supporting substrate is not silica), the silica content in the catalyst is >0-60% by weight, preferably >0-40% by weight, for example, >0-20% by weight, wherein the silica content is based on the content of its molecules.

[024] Here, the pore size of the catalyst increases after modification with silicon, as it improves the diffusion rate of reactants and product, thus improving conversion and selectivity. In addition, it was also found that a catalyst containing silicon has better dehydration activity which is conducive to accelerating the hydrogenolysis reaction rate.

[025] In a preferred embodiment (where the support substrate is not silica), after modification with silicon, the molar ratio of silicon to phosphorus based on the element is <20, Petition 870220025896, dated 03 / 25 / 2022, page 27 / 106 8 / 76 preferably <10, more preferably <4, but not 0, wherein the content of the phosphorus modifying auxiliary component and / or oxides thereof in the catalyst is 0.2-20% by weight, preferably 115% by weight, more preferably 1-7% by weight, wherein the content of phosphorus and / or oxides thereof is based on the phosphorus element content and the silica content in the catalyst is >0-60% by weight, preferably >0-40% by weight, for example, >0-20% by weight.

[026] In this way, the high-temperature hydrothermal stability of the catalyst can be significantly improved. For example, the change in specific surface area and average pore size of the catalyst after high-temperature hydrothermal treatment is significantly reduced. For example, preferably, the change in specific surface area is less than 30% and the change in average pore size is less than 20%; more preferably, the change in specific surface area of ​​the catalyst is less than 10% and the change in average pore size is less than 10%.

[027] Here, the high-temperature hydrothermal treatment temperature is 100-300°C and the treatment period is 20-300 hours.

[028] High-temperature hydrothermal stability is determined according to the following steps: (a) Specific steps of high-temperature hydrothermal treatment of a catalyst: the catalyst is dispersed in excess water; then the catalyst along with the water is placed in a crystallization kettle; after the crystallization kettle is sealed, it is placed in a 200°C oven for 240 hours. (b) A method for determining the specific surface area and pore size of the catalyst comprises Petition 870220025896, dated 03 / 25 / 2022, page 28 / 106 9 / 76 The following specific analysis steps are performed: the physical properties of the catalyst support and the catalyst (such as specific surface area, pore size, pore volume, and the like) are analyzed by physical nitrogen adsorption (ASAP 2020M, Micromeritics). Before analysis and testing, the sample is degassed in a vacuum at 300°C for 3 hours to remove adsorbed impurities and moisture from the sample. After that, the nitrogen adsorption-desorption isotherm of the test sample is analyzed under a liquid nitrogen environment (-196°C).

[029] The specific surface area (Sbet) of the sample is calculated based on nitrogen adsorption data under relative pressure P / Po in the range of 0.05 - 0.20 according to the BET equation (3-1): p (3-Ί) hnC VmCPQV 7em where P is the practically measured pressure; P0 is the saturated vapor pressure at the adsorption temperature; V is the volume of nitrogen adsorption under pressure P; Vm is the volume of nitrogen required for saturated monolayer adsorption; C is the heat constant of adsorption.

[030] The pore size distribution (Dp) of the sample is calculated using the BJH (Barret-Joyner-Halensa) method, which is based on the phenomenon of capillary condensation. That is, the vapor pressure P and the radius of curvature of the liquid rk are related as follows: _ ir-Vm-cose^ (3-2) xfo / ' where r is the surface tension of liquid nitrogen of 10-5 N / cm; Vm is the molar volume of liquid nitrogen; 0k is the contact angle between the meniscus and the solid wall of the hole; R is the ideal gas constant; T is the test temperature. The adsorption capacity V under different pressures P / P0 was obtained in Petition 870220025896, dated 03 / 25 / 2022, page 29 / 106 10 / 76 experiments. The relationship between V and rk is obtained by formula (3-2). Plotting rk with dV / drk results in the pore size distribution curve of the sample.

[031] In a preferred embodiment, the catalyst further includes a co-catalyst; more preferably, the co-catalyst is a sulfur-containing compound that is preferably derived from a sulfur-containing organic matter.

[032] Preferably, the support and the active component supported on it are the main body of the catalyst on which the cocatalyst is supported.

[033] In another preferred embodiment, the cocatalyst content in the catalyst is >0-1% by weight, preferably >0-0.8% by weight, wherein the amount of cocatalyst is based on the amount of effective elements in it, for example, the amount of sulfur.

[034] In the present invention, the source of the sulfur-containing compound is not particularly limited, preferably but not limited to at least one selected from the group of tert-nonyl polysulfides, tert-butyl polysulfides, thiophenes and dimethyl disulfides etc.

[035] The sulfur-containing compound is preferentially adsorbed onto the unsaturated, low-coordination active center on the catalyst surface, which causes the phenomenon of local poisoning of an unstable active center in the catalyst. In this way, it can better inhibit local overheating of the catalyst caused by a relatively high initial catalyst activity and prevent the growth of metallic grains and excessive hydrogenation of isopropylbenzene to isopropylcyclohexane. Meanwhile, it can effectively control the generation of dimerized isopropylbenzene (2,3-dimethyl-2,3-diphenylbutane). Petition 870220025896, dated 03 / 25 / 2022, page 30 / 106 11 / 76 significantly improving the operational stability of the catalyst while enhancing the selectivity of isopropylbenzene.

[036] The palladium metal in the catalyst is free from a compressed double-bridged CO adsorption site. Preferably, there is no absorption peak in the 2000-1950 cm-1 range in the in situ infrared spectrogram of carbon monoxide adsorption of the catalyst.

[037] In a preferred embodiment, the metallic palladium in the catalyst contains a linearly linked CO adsorption site, a single-bridge linked CO adsorption site, and a face-linked CO adsorption site. In another preferred embodiment, absorption peaks are present in the ranges of 2150-2050 cm⁻¹, 1950-1900 cm⁻¹ and 1900-1850 cm⁻¹ in the in situ infrared spectrogram of carbon monoxide adsorption of the catalyst.

[038] In general, a metallic palladium catalyst has four CO adsorption sites with special characteristics that correspond respectively to the perceptible absorption peaks in the ranges of 2150-2050cm⁻¹, 2000-1950cm⁻¹, 1950-1900cm⁻¹ and 1900-1850 cm⁻¹ in the CO-FTIR spectrogram. The aforementioned absorption peaks belong, respectively, to the linearly linked CO adsorption site, the compressed double-bridge linked CO adsorption site, the single-bridge linked CO adsorption site and the face-linked CO adsorption site on the Pd surface.

[039] The infrared spectrogram of CO adsorbed on the catalyst surface is determined as follows:

[040] CO Fourier Transform Infrared Spectrogram (CO-FTIR): The CO adsorption FT-IR test is performed on a THERMO NICOLET 4700 NEXUS infrared spectrometer with a resolution of 4 cm⁻¹. A sample is subjected to a reduction pretreatment in an in situ Harrick pool. O Petition 870220025896, dated 03 / 25 / 2022, page 31 / 106 12 / 76 The background spectrogram is first scanned at the test temperature before introducing CO₂ gas for adsorption. After adsorption equilibrium, the sample is purged with nitrogen until no CO₂ absorption peak in the gas-phase infrared can be detected. The infrared spectrogram at the determination temperature is collected, and the background spectrogram at the corresponding temperature is subtracted to obtain the infrared spectrogram of CO₂ adsorbed on the catalyst surface.

[041] The second object of the present invention is to provide a method for producing the catalyst according to the first object of the present invention, comprising the following steps: Step 1: An aqueous solution of a phosphorus-containing compound is mixed with a supporting substrate, dried, and calcined to obtain a phosphorus-containing support; Step 2: the support is added to a solution of a palladium-containing compound, dried, and calcined to obtain a catalyst precursor in an oxidized state; Step 3: the catalyst precursor in the oxidized state is subjected to a reduction treatment to obtain a catalyst.

[042] In a preferred embodiment, step 1' is optionally carried out after step 1 and before step 2: Step 1: The phosphorus-containing support is mixed with an aqueous silica gel solution, dried, and calcined to obtain a support containing phosphorus and silicon.

[043] In a preferred embodiment, in stage 1, stage 2 and stage 1', drying is carried out by drying at 60-200°C for 4-36 hours, preferably at 150°C for 6 hours, or preferably at 110°C for 8 hours.

[044] In a preferred arrangement, in stage 1, step 2 and Petition 870220025896, dated 03 / 25 / 2022, page 32 / 106 13 / 76 step Γ, the calcination temperature is 400-700°C, preferably 400-500°C.

[045] In the present invention, the phosphorus-containing compound in step 1 is not particularly limited, preferably but not limited to at least one selected from the group consisting of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid, calcium phosphate and ammonium hydrogen phosphate, etc.

[046] In a preferred embodiment, the solution of a palladium-containing compound in step 2 further comprises a compound containing an active auxiliary metal.

[047] In the present invention, unless otherwise specified, the supporting substrate is not particularly limited, preferably at least one selected from the group consisting of alumina, silica and activated carbon, more preferably alumina; the palladium-containing compound is not particularly limited, preferably but not limited to at least one selected from the group consisting of palladium chloride, palladium nitrate and chloropalladic acid; the compound containing an active auxiliary metal is not particularly limited, for example, but not limited to at least one selected from the group consisting of active auxiliary metal chlorides, active auxiliary metal nitrate compounds and active auxiliary metal acetate compounds and the like; preferably, the active auxiliary metal is at least one selected from the group consisting of metallic copper, metallic zinc, metallic cobalt, metallic tin, metallic nickel and metallic silver, for example, metallic copper.

[048] In a preferred embodiment, in step 3, the reduction treatment is carried out with hydrogen. In another preferred embodiment, the reduction temperature in step 3 is 40-300°C, preferably 200-300°C, more preferably 250°C; a Petition 870220025896, dated 03 / 25 / 2022, page 33 / 106 14 / 76 The volumetric space velocity of hydrogen is 50-500h'1, preferably 80-150h'1, more preferably 100h'1.

[049] In a preferred embodiment, the method further comprises step 4: Step 4: The catalyst from step 3 is added to a solution containing cocatalyst and dried to obtain an additional catalyst.

[050] In another preferred embodiment, the cocatalyst is a sulfur-containing compound; more preferably, the sulfur-containing compound is derived from a sulfur-containing organic matter; even more preferably, the sulfur-containing organic matter is at least one selected from the group of tert-nonyl polysulfides, tert-butyl polysulfides, thiophenes and dimethyl disulfides.

[051] In the production method according to the present invention, the quantities of the palladium-containing compound and the phosphorus-containing compound based on 1 L of the support substrate are as follows: the amount of the compound containing palladium is preferably 0.06 g / L–30 g / L, more preferably 0.5 g / L–10 g / L, based on the amount of palladium element present in it; The amount of the compound containing phosphorus is preferably 2g / L-100g / L, more preferably 5g / L-80g / L, based on the amount of phosphorus element in it.

[052] If present, the quantities of the compound containing an active auxiliary metal, the silica gel and / or the sulfur-containing organic matter are based on 1 L of the supporting substrate as follows: the amount of the compound containing an active auxiliary metal is preferably 0.0006 g / L–1.2 g / L, more preferably Petition 870220025896, dated 03 / 25 / 2022, page 34 / 106 15 / 76 0.01 g / L-1.0 g / L, based on the amount of the active auxiliary metal element contained therein; The amount of silica gel is 6-300 g / L, more preferably 20-200 g / L, where the amount of silica gel is based on the amount of silica contained therein; The amount of cocatalyst, for example, a sulfur-containing compound, is 0.0001 g / L-3 g / L, preferably 0.01 g / L-1 g / L, more preferably 0.05 g / L-0.2 g / L, wherein the amount of the sulfur-containing compound is based on the amount of effective elements in it, such as the element sulfur.

[053] In the method for producing a catalyst of the present invention, all solutions are those formed by the complete dissolution of solutes in their suitable solvents, preferably aqueous solutions.

[054] The third objective of the present invention is to provide the use of the catalyst according to the first object of the present invention or the catalyst obtained by the method according to the second object of the present invention in the production of isopropylbenzene.

[055] The fourth object of the present invention is to provide a method for producing isopropylbenzene, in particular, a method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol, preferably carried out with the catalyst according to the first object of the present invention or the catalyst obtained by the method according to the second object of the present invention.

[056] In a preferred embodiment, the production method comprises: bringing the raw material into contact with hydrogen to react in the presence of the catalyst to obtain Petition 870220025896, dated 03 / 25 / 2022, page 35 / 106 16 / 76 isopropylbenzene. In another preferred embodiment, the feedstock comprises a hydrocarbon material comprising α,α-dimethylbenzyl alcohol. In another preferred embodiment, the hydrocarbon material comprising α,α-dimethylbenzyl alcohol comprises an inert solvent (preferably isopropylbenzene) and α,α-dimethylbenzyl alcohol. For example, the hydrocarbon material is the bottom liquid of the column after propylene oxide is separated in the production of propylene oxide in the isopropylbenzene hydroperoxide process and / or the material obtained from the reduction of isopropylbenzene hydroperoxide. Here, the inert solvent must be substantially inactive for the reactants and byproducts, for example, long-chain alkanes (octane, dodecane) and monocyclic aromatic hydrocarbons (benzene, toluene, ethylbenzene, n-propylbenzene, n-butylbenzene, isopropylbenzene), etc.Specifically, the inert solvent is a hydrocarbon that is substantially inactive for both the reactants and the byproducts. Furthermore, the solvent can be an organic solvent having good compatibility with dimethylbenzyl alcohol, but preferably isopropylbenzene, which does not affect the subsequent reaction.

[057] In a preferred embodiment, the raw material comprises 1-100% α,α-dimethylbenzyl alcohol and 0-99% of an inert solvent (preferably isopropylbenzene). In another preferred embodiment, the raw material comprises 50-75% α,α-dimethylbenzyl alcohol and 25-50% of an inert solvent (preferably isopropylbenzene).

[058] In the present invention, the specific content of each component in the raw material is not particularly limited. As a non-restrictive example, the raw material comprises about 55% by weight of an α,α alcohol hydrocarbon material. Petition 870220025896, dated 03 / 25 / 2022, page 36 / 106 17 / 76 dimethylbenzyl, approximately 43% by weight of isopropylbenzene and other hydrocarbons in a proportion of approximately 2% by weight, based on weight percent. The other hydrocarbons may include n-propylbenzene, methylstyrene, acetophenone and 2,3-dimethyl-2,3-diphenylbutane.

[059] In a preferred embodiment, the pressure is 0.14,0 MPa, the temperature is 130-220°C, the hourly space velocity of the liquid is 1-20 h-1 and the molar ratio of hydrogen to α,α-dimethylbenzyl alcohol is > 4 in the production method. In another preferred embodiment, the pressure is 0.5-3.0 MPa, the temperature is 150-200°C, the hourly space velocity of the liquid is 4-15 h-1 and the molar ratio of hydrogen to α,α-dimethylbenzyl alcohol is > 5.

[060] In a preferred embodiment, the production method employs the liquid-phase thermal cycle process. Preferably, the cycle ratio is 1-10, more preferably 4-8. The liquid-phase thermal cycle process here refers to a direct circulation of the liquid-phase thermal material at the outlet of a catalyst bed to the catalyst bed without cooling and water separation.

[061] In a preferred embodiment, the production method of the present invention comprises obtaining isopropylbenzene from a hydrocarbon feedstock comprising α,α-dimethylbenzyl alcohol and hydrogen through a first catalyst bed and a second catalyst bed in series, preferably by a liquid phase thermal cycle process; where the catalyst charge of the first catalyst bed is greater than or equal to that of the second catalyst bed; Petition 870220025896, dated 03 / 25 / 2022, page 37 / 106 18 / 76 the inlet temperature of the first catalyst bed is not higher than the inlet temperature of the second catalyst bed; the thermal cycle ratio of the liquid phase of the first catalyst bed is preferably 1-10;

[062] the thermal cycle ratio of the liquid phase of the second catalyst bed is preferably 0-2.

[063] In a preferred embodiment, the ratio by volume of catalyst loading of the first catalyst bed to catalyst loading of the second catalyst bed is (16): 1, preferably (2-4): 1.

[064] In the first catalyst bed, the hydrogen to liquid phase volume ratio is preferably 300-1000, more preferably 400-800, and / or; in the second catalyst bed, the hydrogen to liquid phase volume ratio is preferably 100-800, more preferably 200-400.

[065] In a preferred embodiment, the first catalyst bed has a reaction temperature of 130-190°C, a reaction pressure of 0.1-5MPa and a liquid-phase space velocity of 1.0-20h⁻¹. In another preferred embodiment, the first catalyst bed has a reaction temperature of 150-170°C, a reaction pressure of 0.5-3.0MPa, a liquid-phase space velocity of 1-5h⁻¹ and a cycle ratio of 2-8.

[066] Here, the liquid phase is a fresh oil which refers to a feedstock that has not undergone dilution by the liquid phase thermal cycling process. In a preferred embodiment, the second catalyst bed has a reaction temperature of 150-230°C, a reaction pressure of 0.1-5 MPa and a liquid phase volume space velocity of 2.0-10 h⁻¹. In another preferred embodiment, the second catalyst bed has a Petition 870220025896, dated 03 / 25 / 2022, page 38 / 106 19 / 76 reaction temperature of 160-190°C, a reaction pressure of 0.5-3MPa and a liquid hourly space velocity of 4-8 h'1.

[067] Preferably, the catalyst of the first catalyst bed comprises metallic Pd and / or oxides and a support.

[068] Preferably, the catalyst of the second catalyst bed comprises metallic Pd and / or oxides, a metallic auxiliary and / or its oxides and a support; preferably, the metal auxiliary is at least one selected from the group consisting of Fe, Co, Ni, Ca, Mg and Cu, more preferably at least one selected from the group consisting of Cu, Ni and Mg.

[069] Preferably, the catalyst for the first catalyst bed and / or the catalyst for the second catalyst bed are the catalysts for the production of isopropylbenzene as provided for in the first object of the present invention.

[070] In the present invention, the loading of the first catalyst bed is defined to be greater than or equal to, preferably significantly greater than, the loading of the second catalyst bed, so that the feedstock can react in the first catalyst bed as much as possible. If there is unreacted feedstock, it enters the second catalyst bed for a reaction at a slightly higher temperature. Specifically, when the concentration of reactants in the feedstock is high, the heat release in the reaction process is high, so the first bed adopts the liquid-phase thermal cycle mode, having a high total volume space velocity and a heat transport function to avoid overheating of the bed and the formation of local hot spots, as it is conducive to the selectivity and stability of the catalyst.The second bed, which employs a higher temperature, achieves a high conversion rate of a small amount of remaining reagents. Therefore... Petition 870220025896, dated 03 / 25 / 2022, page 39 / 106 20 / 76 form, the impurity content in the product is significantly reduced.

[071] In a preferred embodiment, the conversion of α,α-dimethylbenzyl alcohol is greater than 99.5% and the selectivity of isopropylbenzene is greater than 99.8% in the method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol.

[072] Conversion and selectivity are calculated according to the following formula: conversion of α,α-dimethylbenzyl alcohol (%) = [(W°iW'i) / W°i] x 100%; Isopropylbenzene selectivity (%)=[((Wl2- W°2) / M2) / ((W°iW'i) / Mi)]x100%; where w°i denotes the mass of α,α-dimethylbenzyl alcohol in the raw material; w'i denotes the mass of α,α-dimethylbenzyl alcohol in the product; w°2 denotes the mass of isopropylbenzene in the raw material; wl2 denotes the mass of isopropylbenzene in the product; Mi denotes the molecular weight of α,α-dimethylbenzyl alcohol; M2 denotes the molecular weight of isopropylbenzene.

[073] The method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol according to the present invention provides a suitable acid dehydration site and a hydrogenating metal active site, better inhibits local catalyst overheating caused by a relatively high initial catalyst activity, avoids metal grain growth and excessive hydrogenation of isopropylbenzene to isopropylcyclohexane in the catalytic process of producing isopropylbenzene by dehydration and hydrogenation of α,α-dimethylbenzyl alcohol in the presence of a supported palladium active component. While Petition 870220025896, dated 03 / 25 / 2022, page 40 / 106 21 / 76 This effectively controls the generation of dimerized isopropylbenzene and significantly improves the operating stability of the catalyst while enhancing the selectivity of isopropylbenzene.

[074] The present invention also provides the use of said production method in the production of propylene oxide, for example by: Step 1: Obtaining isopropylbenzene hydroperoxide by oxidation of isopropylbenzene; Step 2: obtaining propylene oxide and α,α-dimethylbenzyl alcohol from the reaction of isopropylbenzene hydroperoxide and propylene; Step 3: Obtaining a hydrocarbon material comprising α,α-dimethylbenzyl alcohol by means of a propylene oxide separation by rectification; Step 4: subject the hydrocarbon material comprising α,α-dimethylbenzyl alcohol to treatment with the catalyst and method in the present invention to obtain isopropylbenzene which is recycled to step 1 for reuse.

[075] The ends and any values ​​of the ranges described in the present invention are not limited to the precise ranges or values. These ranges or values ​​should be interpreted as including the values ​​near these ranges or these values. With respect to the number ranges, between the extremes of each range, between the extremes of each range and the individual values, and between the individual values, they can be combined with each other to obtain one or more new number ranges. It should be considered that these number ranges are specifically described in the present invention. Various technical solutions in the context can be combined with each other. Petition 870220025896, dated 03 / 25 / 2022, page 41 / 106 22 / 76 in principle to obtain new technical solutions, which should also be considered as being specifically described in the present invention.

[076] The present invention has at least the following advantageous effects compared with the prior art: (1) The addition of a P-modifying auxiliary component to the catalyst support according to the present invention can significantly improve and increase the hydrogenation activity and stability of the catalyst. In particular, the addition of the P-modifying auxiliary components and S1O2 to the support can significantly improve the hydrothermal stability of the catalyst when the molar ratio of silicon to phosphorus is of a certain value. (2) the simultaneous introduction of the active auxiliary component into the catalyst can significantly improve the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene. (3) The introduction of a co-catalyst into the catalyst prevents excessive hydrogenation of isopropylbenzene to isopropylcyclohexane. Meanwhile, it can effectively control the generation of dimerized isopropylbenzene (2,3-dimethyl-2,3-diphenylbutane) and significantly improve the operating stability of the catalyst while enhancing the selectivity of isopropylbenzene. (4) In the method of producing isopropylbenzene by the liquid-phase thermal cycle provided for in the present invention, the use of the heat of reaction is more reasonable, as it can significantly reduce energy consumption and device costs and produce isopropylbenzene efficiently. (5) the method for producing isopropylbenzene according to the present invention provides a suitable acid dehydration site and hydrogenating metal active site, better inhibits the Petition 870220025896, dated 03 / 25 / 2022, page 42 / 106 23 / 76 Over-hydrogenation of isopropylbenzene to isopropylcyclohexane due to local catalyst overheating caused by a relatively high initial catalyst activity in the catalytic process of isopropylbenzene production by dehydration and hydrogenation of α,α-dimethylbenzyl alcohol in the presence of a supported palladium active catalyst. Meanwhile, it effectively controls the generation of dimerized isopropylbenzene and significantly improves the catalyst's operating stability while enhancing the selectivity of isopropylbenzene.

[077] In conclusion, the present invention produces a hydrogenolysis catalyst with good properties, achieves the coupling of two dehydration and hydrogenation reactions, and utilizes energy more reasonably by using the liquid-phase thermal cycle process through the production of a support with good hydrothermal stability and excellent dehydration and support properties for hydrogenating metals using the support. Meanwhile, the present invention avoids the decrease in catalyst performance caused by local overheating of the catalyst bed and achieves a low-cost and highly efficient production of isopropylbenzene. Method for Carrying Out the Invention.

[078] The present invention is described in detail in combination with specific examples as below. It is necessary to emphasize that the following examples, which are used only for further illustration of the present invention, cannot be interpreted as a limitation of the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art to the present invention in accordance with the content of the present invention are still within the scope of Petition 870220025896, dated 03 / 25 / 2022, page 43 / 106 24 / 76 protection of the invention.

[079] Table 1 shows the components of the raw material used in the examples and in the comparative examples. Table 1: Components of the raw material used Raw material components Components by weight % by weight isopropylbenzene 43.25 n-propylbenzene 0.08 methylstyrene 0.12 acetophenone 1.02 α,α-dimethylbenzyl alcohol 55.26 dimerized isopropylbenzene (2,3-dimethyl-2,3-diphenylbutane) 0.27

[080] Analysis of the content of each component in the catalyst: the specific composition of the element in the catalyst is determined by the X-ray fluorescence analysis method. Different elements have characteristic X-ray spectrograms with different wavelengths, and the fluorescence intensity of each spectral line has a certain relationship with the concentration of the element. Qualitative and quantitative analysis can be performed by determining the wavelength and intensity of the characteristic X-ray spectral lines of the elements to be tested. I. Production and evaluation of catalysts Example 1 1. Catalyst production

[081] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 8.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a support. Petition 870220025896, dated 03 / 25 / 2022, page 44 / 106 25 / 76 of catalyst.

[082] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst. The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[083] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[084] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h'1 Relationship of the liquid phase thermal cycle: 4

[085] Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[086] The average results of the 200-hour assessment are shown in Table 5.

[087] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Petition 870220025896, dated 03 / 25 / 2022, page 45 / 106 26 / 76 Example 2 1. Catalyst production

[088] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 8.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[089] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[090] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[091] The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[092] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[093] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Petition 870220025896, dated 03 / 25 / 2022, page 46 / 106 27 / 76 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[094] The average results of the 200-hour assessment are shown in Table 5. Example 3 1. Catalyst production

[095] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[096] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[097] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[098] The main components and properties of the catalyst are shown in Table 2 and Table 3. The results of the CO-FTIR analysis are shown in Fig. 1. 2. Catalyst evaluation

[099] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0100] The operating conditions were as follows: Reaction temperature: 150°C Petition 870220025896, dated 03 / 25 / 2022, page 47 / 106 28 / 76 Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h'1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0101] The average results of the 200-hour assessment are shown in Table 5.

[0102] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Example 4 1. Catalyst production

[0103] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 35 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0104] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0105] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[0106] The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0107] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as Petition 870220025896, dated 03 / 25 / 2022, page 48 / 106 29 / 76 above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out continuously.

[0108] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0109] The average results of the 200-hour assessment are shown in Table 5.

[0110] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Example 5 1. Catalyst production

[0111] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 5.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0112] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0113] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst. Petition 870220025896, dated 03 / 25 / 2022, page 49 / 106 30 / 76

[0114] The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0115] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0116] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h'1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0117] The average results of the 200-hour assessment are shown in Table 5.

[0118] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Example 6 1. Catalyst production

[0119] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0120] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. Petition 870220025896, dated 03 / 25 / 2022, pp. 50 / 106 31 / 76

[0121] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst precursor II.

[0122] 1 L of the above palladium-based catalyst precursor II was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur and dried at 110°C to obtain a palladium-based catalyst.

[0123] The main components and properties of the catalyst are shown in Table 2 and Table 3. The results of the CO-FTIR analysis are shown in Fig. 1. 2. Catalyst evaluation

[0124] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0125] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0126] The average results of the 200-hour assessment are shown in Table 5.

[0127] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Example 7 Petition 870220025896, dated 03 / 25 / 2022, page 51 / 106 32 / 76 1. Catalyst production

[0128] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 35 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0129] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0130] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst precursor II.

[0131] 1 L of the above palladium-based catalyst precursor II was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur and dried at 110°C to obtain a palladium-based catalyst. The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0132] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0133] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Petition 870220025896, dated 03 / 25 / 2022, page 52 / 106 33 / 76 Space velocity of volume of fresh raw material oil: 1.6h'1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0134] The average results of the 1000-hour assessment are shown in Table 5. Example 8

[0135] The process of Example 2 was repeated, except that the aqueous solution of chloropalladium-nickel nitrate contained 10.0 g of palladium and 1.2 g of nickel. The main components of the catalyst are shown in Table 2.

[0136] The catalyst evaluation in Example 2 was repeated. Similarly, the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were both relatively high. Example 9

[0137] The process of Example 2 was repeated, except that the aqueous solution of chloropalladium-cobalt nitrate contained 0.5 g of palladium and 0.0006 g of cobalt. The main components of the catalyst are shown in Table 2.

[0138] The catalyst evaluation in Example 2 was repeated. Similarly, the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were both relatively high. Examples 10-13

[0139] The process in Example 7 was repeated, except that di-tertnonyl polysulfides containing 0.01 g, 0.05 g, 0.2 g and 1 g of sulfur were employed respectively. The main components of the catalyst are shown in Table 2.

[0140] The catalyst evaluation in Example 7 was repeated. Similarly, the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were both relatively high. Petition 870220025896, dated 03 / 25 / 2022, page 53 / 106 34 / 76 Example 14

[0141] The process in Example 6 was repeated, except that in the production of the catalyst:

[0142] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0143] 1 L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution with a mass concentration of 5% S1O2, dried and calcined at 500°C to obtain a support containing P / Si.

[0144] 1 L of the above support containing P / Si was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0145] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst precursor II.

[0146] 1 L of the above palladium-based catalyst precursor II was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst are shown in Table 2.

[0147] The catalyst evaluation in Example 6 was repeated. Similarly, the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were both relatively high.

[0148] The physical properties of the catalyst after treatment Petition 870220025896, dated 03 / 25 / 2022, page 54 / 106 35 / 76 high temperature hydrothermal systems are shown in Table 4. Example 15

[0149] The process in Example 6 was repeated, except that in the production of the catalyst:

[0150] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0151] 1 L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution having a mass concentration of 10% SiO2, dried and calcined at 500°C to obtain a support containing P / Si.

[0152] 1 L of the above support containing P / Si was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0153] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst precursor II.

[0154] 1 L of the above palladium-based catalyst precursor II was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst are shown in Table 2.

[0155] The support used in the catalyst obtained in Example 15 contained not only P, but also silicon. In the production of isopropylbenzene by hydrogenation of α,α-dimethylbenzyl alcohol Petition 870220025896, dated 03 / 25 / 2022, page 55 / 106 36 / 76 using the catalyst, the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were both superior to those of Example 6.

[0156] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Example 16

[0157] The process in Example 6 was repeated, except that in the production of the catalyst:

[0158] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0159] 1 L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution having a mass concentration of 20% S1O2, dried and calcined at 500°C to obtain a support containing P / Si.

[0160] 1 L of the above support containing P / Si was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0161] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst precursor II.

[0162] 1 L of the above palladium-based catalyst precursor II was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of Petition 870220025896, dated 03 / 25 / 2022, page 56 / 106 37 / 76 catalysts are shown in Table 2.

[0163] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Example 17

[0164] The process in Example 6 was repeated, except that in the production of the catalyst:

[0165] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0166] 1 L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution with a mass concentration of 30% S1O2, dried and calcined at 500°C to obtain a support containing P / Si.

[0167] 1 L of the above support containing P / Si was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0168] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst precursor II.

[0169] 1 L of the above palladium-based catalyst precursor II was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst are shown in Table 2.

[0170] The physical properties of the catalyst after treatment Petition 870220025896, dated 03 / 25 / 2022, page 57 / 106 38 / 76 high-temperature hydrothermal systems are shown in Table 4.

[0171] Analysis of Examples 14-17: the supports employed in the catalysts obtained in Examples 14-17 contained not only P, but also silicon and sulfur. When the above was used in the production of isopropylbenzene by hydrogenation of α,α-dimethylbenzyl alcohol, both the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were greater than those of Example 6. Example 18

[0172] The process from Example 14 was repeated, except that in the evaluation of the catalyst:

[0173] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out continuously. The material passed first through the first catalyst bed and then through the second catalyst bed. The catalyst loading volume ratio of the two catalyst beds was 4:1. The operating conditions of the two reactors were as follows: First catalyst bed: Inlet temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of fresh raw material oil volume: 2.0 h⁻¹ Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8 The second catalyst bed: Inlet temperature: 160°C Petition 870220025896, dated 03 / 25 / 2022, page 58 / 106 39 / 76 Reaction pressure: 2.0 MPa Relationship of the liquid phase thermal cycle: 0

[0174] The average results of the 200-hour assessment are shown in Table 5. Example 19 1. Catalyst production

[0175] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 8.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0176] 1 L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution having a mass concentration of 10% S1O2, dried and calcined at 500°C to obtain a support containing P / Si.

[0177] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst. The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0178] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a manner Petition 870220025896, dated 03 / 25 / 2022, page 59 / 106 40 / 76 continuous.

[0179] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0180] The average results of the 200-hour assessment are shown in Table 5.

[0181] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Example 20 1. Catalyst production

[0182] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 8.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0183] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0184] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[0185] 1 L of the palladium-based catalyst precursor above was impregnated with 550 g of cyclohexane solution of Petition 870220025896, dated 03 / 25 / 2022, pp. 60 / 106 41 / 76 tert-nonyl polysulfide containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components and properties of the catalyst are shown in Table 2. 2. Catalyst evaluation

[0186] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0187] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h'1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0188] The average results of the 200-hour assessment are shown in Table 5. Example 21 1. Catalyst production

[0189] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 8.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0190] 1L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution having a mass concentration of 10% S1O2, dried and calcined at 500°C to obtain a support containing P / Si.

[0191] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, Petition 870220025896, dated 03 / 25 / 2022, pp. 61 / 106 42 / 76 dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0192] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[0193] 1 L of the palladium-based catalyst precursor above was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0194] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0195] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0196] The average results of the 200-hour assessment are shown in Table 5.

[0197] The physical properties of the catalyst after treatment Petition 870220025896, dated 03 / 25 / 2022, pp. 62 / 106 43 / 76 high-temperature hydrothermal systems are shown in Table 4. Example 22 1. Catalyst production

[0198] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 8.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0199] 1 L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution having a mass concentration of 10% S1O2, dried and calcined at 500°C to obtain a support containing P / Si.

[0200] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0201] The palladium-based catalyst precursor I above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2. 2. Catalyst evaluation

[0202] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0203] The operating conditions were as follows: Reaction temperature: 150°C Petition 870220025896, dated 03 / 25 / 2022, pp. 63 / 106 44 / 76 Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0204] The average results of the 200-hour assessment are shown in Table 5. Example 23 1. Catalyst production

[0205] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 4.0 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0206] 1L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution having a mass concentration of 10% S1O2, dried and calcined at 500°C to obtain a support containing P / Si.

[0207] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0208] The palladium-based catalyst precursor I above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst. The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0209] The hydrogenation operation was carried out in a reactor Petition 870220025896, dated 03 / 25 / 2022, pp. 64 / 106 45 / 76 of a fixed bed that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out continuously.

[0210] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0211] The average results of the 200-hour assessment are shown in Table 5.

[0212] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Comparative Example 1 1. Catalyst production

[0213] 1 L of alumina was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[0214] The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0215] The hydrogenation operation was carried out in a reactor Petition 870220025896, dated 03 / 25 / 2022, pp. 65 / 106 46 / 76 of a fixed bed that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out continuously.

[0216] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0217] The average results of the 200-hour assessment are shown in Table 5.

[0218] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Comparative Example 2 1. Catalyst production

[0219] 1 L of alumina was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor solution I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[0220] The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0221] The hydrogenation operation was carried out in a reactor Petition 870220025896, dated 03 / 25 / 2022, pp. 66 / 106 47 / 76 of a fixed bed that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out continuously.

[0222] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0223] The average results of the 200-hour assessment are shown in Table 5. Comparative Example 3 1. Catalyst production

[0224] 1 L of alumina support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor solution I in an oxidized state.

[0225] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[0226] 1 L of the palladium-based catalyst above was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst are Petition 870220025896, dated 03 / 25 / 2022, pp. 67 / 106 48 / 76 shown in Table 2 and Table 3. 2. Catalyst evaluation

[0227] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0228] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0229] The average results of the 200-hour assessment are shown in Table 5.

[0230] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Comparative Example 4 1. Catalyst production

[0231] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in the oxidized state.

[0232] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst. Petition 870220025896, dated 03 / 25 / 2022, pp. 68 / 106 49 / 76

[0233] 1 L of the palladium-based catalyst above was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0234] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0235] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h'1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0236] The average results of the 200-hour assessment are shown in Table 5. Comparative Example 5 1. Catalyst production

[0237] 1 L of alumina support was mixed with 600 g of aqueous silica gel solution with a mass concentration of 10% SiO2, dried and calcined at 500°C to obtain a support containing Si.

[0238] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in a Petition 870220025896, dated 03 / 25 / 2022, pp. 69 / 106 50 / 76 oxidized state.

[0239] The palladium-based catalyst precursor I above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst. The main components and properties of the catalyst are shown in Table 2.

[0240] The main components and properties of the catalyst are shown in Table 2 and Table 3. 2. Catalyst evaluation

[0241] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0242] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0243] The average results of the 200-hour assessment are shown in Table 5.

[0244] The physical properties of the catalyst after high-temperature hydrothermal treatment are shown in Table 4. Comparative Example 6 1. Catalyst production

[0245] 1 L of alumina support was mixed with 600 g of aqueous silica gel solution with a mass concentration of 10% Petition 870220025896, dated 03 / 25 / 2022, pp. 70 / 106 51 / 76 of S1O2, dried and calcined at 500°C to obtain a support containing Si.

[0246] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state.

[0247] The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 250°C to produce a palladium-based catalyst.

[0248] 1 L of the palladium-based catalyst above was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst are shown in Table 2.

[0249] The main components and properties of the catalyst are shown in Table 2. 2. Catalyst evaluation

[0250] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with catalyst produced as above. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out in a continuous manner.

[0251] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h-1 Petition 870220025896, dated 03 / 25 / 2022, pp. 71 / 106 52 / 76 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8

[0252] The average results of the 200-hour assessment are shown in Table 5. Table 2: Main components of catalysts Item AI2O3 % by weight Pd % by weight M % by weight P % by weight S % by weight SiO2 % by weight Example 1 95.24 0.458 0 1.39 0 0 Example 2 95.24 0.458 CuO-0.19 1.41 0 0 Example 3 87.55 0.467 CuO-0.18 4.6 0 0 Example 4 84.45 0.466 CuO-0.19 6.12 0 0 Example 5 97.11 0.482 CuO-0.19 0.89 0 0 Example 6 87.47 0.457 CuO-0.18 4.7 0.020 0 Example 7 84.36 0.463 CuO-0.19 Example 8: 94.32 1.527 NiO-0.26 1.41 0 0 Example 9: 95.24 0.078 CoO-0.00014 1.39 0 0 Example 10: 84.22 0.456 CuO-0.226 6.28 0.0019 0 Example 11: 83.61 0.462 CuO-0.225 6.31 0.010 0 Example 12: 83.58 0.459 CuO-0.227 6.29 0.036 0 Example 13: 82.90 0.467 CuO-0.223 6.33 0.200 0 Example 14: 81.86 0.452 Example 15: 76.98 0.423 CuO-0.226 4.67 0.021 10.62 Example 16: 64.25 0.478 CuO-0.226 4.91 0.019 21.26 Example 17: 53.56 0.465 CuO-0.224 4.76 0.020 33.05 Example 19: 85.32 0.458 0 1.39 0 10.62 Example 20: 95.86 0.458 0 1.39 0.021 0 Example 21: 85.25 0.458 0 1.39 0.021 10.62 22 85.11 0.458 CuO-0.19 1.39 0 10.62 Petition 870220025896, dated 03 / 25 / 2022, pp. 72 / 106 53 / 76 Example 23 86.72 0.458 CuO-0.19 0.72 0 10.62 Comparative Example 1 99.21 0.471 0 0 0 0 Comparative Example 2 99.17 0.467 CuO-0.228 0 0 0 Comparative Example 3 99.17 0.467 CuO-0.19 0 0.021 0 Comparative Example 4 99.36 0.467 0 0 0.021 0 Comparative Example 5 88.66 0.467 0 0 0 10.62 Comparative Example 6 88.61 0.467 0 0 0.021 10.62 Table 3: Physical properties of the catalysts obtained Item Specific surface area m² / g Average pore size nm Pd dispersion % Example 1 138 13.5 9.6 Example 2 138 13.7 8.5 Example 3 133 14.8 6.9 Example 4 128 14.7 6.5 Example 5 142 13.2 8.4 Example 6 133 14.8 6.9 Example 7 128 15.2 6.5 Example 8 135 13.5 5.2 Example 11 127 14.6 7.2 Example 14 132 13.8 6.9 Example 15 141 13.6 6.5 Example 16 145 12.9 6.7 Example 17 151 13.1 6.6 Example 19 136 13.4 9.8 Petition 870220025896, dated 03 / 25 / 2022, pp. 73 / 106 54 / 76 Example 21 136 13.4 8.2 Example 23 141 13.2 8.5 Comparative Example 1 146 12.7 21.3 Comparative Example 2 146 12.7 18.3 Comparative Example 3 146 12.7 15.4 Comparative Example 4 146 12.7 12.3 Comparative Example 5 154 11.9 13.6 Table 4: Physical properties of catalysts produced after high-temperature hydrothermal treatment. Item Specific Surface Area (m² / g) Average Pore Size (nm) Example 1 10² 16.2 Example 3 10⁸ 15.8 Example 4 11⁶ 14.6 Example 5 10² 16.4 Example 6 11² 15.4 Example 14 14² 13.2 Example 15 14⁶ 12.8 Example 16 15² 12.6 Example 17 15⁶ 12.8 Example 19 15² 12.8 Example 21 15⁵ 12.6 Example 23 12⁸ 13.8 Comparative Example 1 32 24.2 Comparative Example 3 35 23.6 Comparative Example 5 86 17.6 Petition 870220025896, dated 03 / 25 / 2022, pp. 74 / 106 55 / 76

[0253] Table 4 proves that the physical properties of the catalysts of Examples 1, 3-6, 14-17, 19, 21 and 23 of the present invention after high temperature hydrothermal treatment are excellent. Table 5: Average results of the 200-hour assessment. Item | Isopropylcyclohexane Production Quantity (ppm) | α,α-dimethylbenzyl Alcohol Conversion % | Isopropylbenzene Selectivity % | Example 1 | 556 | 99.22 | 99.75 | Example 2 | 418 | 99.54 | 99.81 | Example 3 | 321 | 99.42 | 99.84 | Example 4 | 412 | 99.41 | 99.78 | Example 5 | 376 | 99.51 | 99.77 | Example 6 | 139 | 99.71 | 99.88 | Example 7 | 128 | 99.66 | 99.87 | Example 8 | 524 | 99.71 | 99.68 | Example 9 | 278 | 99.58 | 99.82 | Example 10 | 238 | 99.74 | 99.78 | Example 11 | 185 Example 12: 99.81 99.81 Example 13: 89 99.65 99.92 Example 14: 45 99.52 99.88 Example 15: 16 99.75 99.90 Example 16: 14 99.75 99.87 Example 16: 12 99.70 99.86 Example 17: 15 99.70 99.86 Example 18: 6 99.95 99.90 Example 19: 456 99.36 99.78 Example 20: 145 99.46 99.82 Example 21: 125 99.58 99.85 Example 22: 325 99.51 99.80 Example 23: 336 99.42 99.78 Comparative 1 920 97.45 99.45 Example Comparative 2 721 97.32 99.58 Petition 870220025896, dated 03 / 25 / 2022, pp. 75 / 106 56 / 76 Comparative Example 3 386 97.62 99.68 Comparative Example 4 425 97.56 99.62 Comparative Example 5 856 98.24 99.68 Comparative Example 6 125 98.56 99.72

[0254] At least the following can be seen in Table 2, Table 3, Table 4, Table 5 and Fig.1: (1) according to the comparison of Example 1 and Comparative Example 1, the hydrothermal stability of the support was significantly improved and the conversion of α,αdimethylbenzyl alcohol and the selectivity of isopropylbenzene were significantly improved after the addition of phosphorus to the support; (2) according to the comparison of Example 1 and Example 2, when a Pd-Cu compound active component was used, both the α,α-dimethylbenzyl alcohol conversion and the isopropylbenzene selectivity were greater than those of a mere Pd active component; (3) according to the comparison of Example 1 and Example 19, the hydrothermal stability of the support was further improved and the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were further improved after the introduction of silica into the support; (4) according to the comparison of Example 1 and Example 20, the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were further improved after the introduction of sulfur into the catalyst; (5) according to the comparison of Example 3 and Example 6, there was no adsorption site of compressed double-bridged CO in the CO-FTIR spectrogram (see Fig. Petition 870220025896, dated 03 / 25 / 2022, pp. 76 / 106 57 / 76 1); the amount of isopropylcyclohexane produced was significantly reduced, and the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were significantly improved after the addition of S to the catalyst; (6) according to the respective comparison of Examples 14-17 and Examples 1-13, the amount of isopropylcyclohexane production was significantly reduced by introducing Cu, S and Si to the catalyst simultaneously. (7) according to the comparison of Example 18 and of Example 14, the conversion of α,α-dimethylbenzyl alcohol and the selectivity of isopropylbenzene were significantly improved when a two-stage series catalyst bed reaction process was used compared to using a single-stage catalyst bed. (8) all catalysts in Comparative Examples 3-6 were phosphorus-free, and the conversion of alcohol to adimethylbenzyl was lower and the selectivity of isopropylbenzene was relatively low. One thousand-hour stability test:

[0255] The hydrogenation operation was carried out in a fixed-bed reactor that was filled with the catalysts produced in Example 14 and Comparative Example 1, respectively. The hydrogenation operation of a hydrocarbon material comprising α,α-dimethylbenzyl alcohol was carried out continuously.

[0256] The operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 2.0 MPa Space velocity of volume of fresh raw material oil: 1.6h'1 Petition 870220025896, dated 03 / 25 / 2022, pp. 77 / 106 58 / 76 Relationship of the liquid phase thermal cycle: 4 Molar ratio of hydrogen / α,α-dimethylbenzyl alcohol: 8 The average results from the 1,000-hour assessment are shown in Table 6. Table 6: Average results of the 1,000-hour assessment. Item Time (hours) Quantity of isopropylcyclohexane production (ppm) Conversion of α,α-dimethylbenzyl alcohol (%) Selectivity of isopropylbenzene (%) Catalyst produced in Example 14 200 16 99.75 99.90 400 15 99.76 99.89 600 6 99.72 99.88 800 6 99.78 99.88 1000 0 99.79 99.90 Catalyst produced in Comparative Example 1 200 920 97.32 99.45 400 854 97.28 99.56 600 556 97.12 99.61 800 376 96.68 99.71 1000 236 96.44 99.78

[0257] The one thousand hour stability test was performed on the catalysts prepared in Example 14 and Comparative Example 1, respectively. It can be learned from Table 6 that the catalyst of the present invention not only significantly reduced the amount of isopropylcyclohexane production in the initial activity stage of the catalyst, but also remained stable for one thousand hours with α,α-dimethylbenzyl alcohol conversion >99.72% and isopropylbenzene selectivity >99.88% in the 1000-hour reaction evaluation, as indicated that the catalyst performance did not undergo significant alteration. II. A method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol Petition 870220025896, dated 03 / 25 / 2022, pp. 78 / 106 59 / 76

[0258] The method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol of the present invention results in isopropylbenzene from a hydrocarbon feedstock comprising α,α-dimethylbenzyl alcohol and hydrogen via a first catalyst bed and a second catalyst bed in series, preferably by the liquid-phase thermal cycle process. Relevant examples and comparative examples are listed below, which, however, cannot be interpreted as a limitation of the present invention. Example T 1. Catalyst production a. Production of the catalyst for the first catalyst bed

[0259] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 450°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2'. b. Production of the catalyst for the second catalyst bed

[0260] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid-nickel nitrate solution containing 3.0 g of palladium and 0.3 g of nickel, dried at 110°C for 8 hours and calcined at 550°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was Petition 870220025896, dated 03 / 25 / 2022, pp. 79 / 106 60 / 76 reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The specific components of the catalyst are shown in Table 2'. 2. Catalyst evaluation

[0261] The hydrogenation operation of the hydrocarbon material comprising α,α-dimethylbenzyl alcohol in Table 1 was carried out continuously. The material passed first through the first catalyst bed and then through the second catalyst bed. The catalyst loading volume ratio of the two catalyst beds was 4:1. The operating conditions of the two reactors were as follows: The first catalyst bed: Reaction temperature: 150°C Reaction pressure: 1.5 MPa Space velocity of volume of fresh raw material oil: 2 h-1 Relationship of the liquid phase thermal cycle: 4 Hydrogen / fresh oil ratio of the raw material by volume: 400 The second catalyst bed: Reaction temperature: 170°C Reaction pressure: 1.3 MPa Hydrogen / fresh oil ratio of the raw material by volume: 200

[0262] The average results of the 200-hour assessment are shown in Table 3'. Example 2' 1. Catalyst production Petition 870220025896, dated 03 / 25 / 2022, pp. 80 / 106 61 / 76 a. Production of the catalyst for the first catalyst bed

[0263] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 450°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2'. b. Production of the catalyst for the second catalyst bed

[0264] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid-nickel nitrate-magnesium nitrate solution containing 3.0 g of palladium, 0.2 g of nickel and 0.1 g of magnesium, dried at 110°C for 8 hours and calcined at 550°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a temperature of 300°C to produce a palladium-based catalyst. The specific components of the catalyst are shown in Table 2'. 2. Catalyst evaluation

[0265] The hydrogenation operation of the hydrocarbon material comprising α,α-dimethylbenzyl alcohol in Table 1 was carried out continuously. The material passed first through the first catalyst bed and then through the second catalyst bed. The catalyst loading volume ratio of the two catalyst beds was 4:1. The operating conditions Petition 870220025896, dated 03 / 25 / 2022, pp. 81 / 106 62 / 76 of the two reactors were as follows: First catalyst bed: Reaction temperature: 150°C Reaction pressure: 1.5 MPa Space velocity of fresh raw material oil: 2 h⁻¹ Relationship of the liquid phase thermal cycle: 4 Hydrogen / fresh oil ratio of the raw material by volume: 400 Second catalyst bed: Reaction temperature: 170°C Reaction pressure: 1.3 MPa Hydrogen / fresh oil ratio by volume: 100

[0266] The average results of the 200-hour assessment are shown in Table 3'. Example 3' 1. Catalyst production a. Production of the catalyst for the first catalyst bed

[0267] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 450°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2'. b. Production of the catalyst for the second catalyst bed Petition 870220025896, dated 03 / 25 / 2022, pp. 82 / 106 63 / 76

[0268] 1 L of the supporting catalyst was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 0.3 g of Cu, dried at 110°C for 8 hours and calcined at 550°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The specific components of the catalyst are shown in Table 2'. 2. Catalyst evaluation

[0269] The hydrogenation operation of the hydrocarbon material comprising α,α-dimethylbenzyl alcohol in Table 1 was carried out continuously. The material from which the heavy components were removed passed first through the first catalyst bed and then through the second catalyst bed. The catalyst loading volume ratio of the two catalyst beds was 4:1. The operating conditions of the two reactors were as follows: First catalyst bed: Reaction temperature: 150°C Reaction pressure: 1.5 MPa Space velocity of fresh raw material oil: 2 h⁻¹ Relationship of the liquid phase thermal cycle: 4 Hydrogen / fresh oil ratio of the raw material by volume: 400 The second catalyst bed: Reaction temperature: 170°C Petition 870220025896, dated 03 / 25 / 2022, pp. 83 / 106 64 / 76 Reaction pressure: 1.3 MPa Hydrogen / fresh oil ratio of the raw material by volume: 100

[0270] The average results of the 200-hour assessment are shown in Table 3'. Example 4'

[0271] The process from Example 2 was repeated, except in the production of the second catalyst:

[0272] 1 L of alumina was mixed with 600 ml of aqueous phosphoric acid solution containing 60 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support.

[0273] 1 L of the above support was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium catalyst precursor based on an oxidized state.

[0274] The palladium-based catalyst precursor above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 35°C to produce a palladium-based catalyst precursor in a reduced state.

[0275] 1 L of the palladium-based catalyst precursor above in a reduced state was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur and dried at 110°C to obtain a catalyst. The main components of the catalyst and the average results of the 200-hour evaluation are shown in Table 2' and Table 3' respectively. Example 5' Petition 870220025896, dated 03 / 25 / 2022, pp. 84 / 106 65 / 76

[0276] The process from Example 2 was repeated, except that in the production of the catalyst in the second step, specifically:

[0277] 1 L of alumina was mixed with 600 ml of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0278] 1 L of the above catalyst support containing P was mixed with 600 g of aqueous silica gel solution having a mass concentration of 5% SiO2, dried and calcined at 500°C to obtain a support containing P / SiO2.

[0279] 1 L of the above support containing P / S1O2 was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor in an oxidized state.

[0280] The palladium-based catalyst precursor above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 35°C to produce a palladium-based catalyst precursor in a reduced state.

[0281] 1 L of the palladium-based catalyst precursor above in a reduced state was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst and the average results of the 200-hour evaluation are shown in Table 2' and Table 3' respectively. Example 6'

[0282] The process of Example 5' was repeated, except that in the production of the catalyst in the second step, specifically: Petition 870220025896, dated 03 / 25 / 2022, pages 85 / 106 66 / 76

[0283] 1 L of alumina was mixed with 600 ml of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0284] 1 L of the above support containing P was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor in an oxidized state.

[0285] The palladium-based catalyst precursor above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 35°C to produce a palladium-based catalyst precursor in a reduced state.

[0286] 1 L of the palladium-based catalyst precursor above in a reduced state was impregnated with 550 g of tert-nonyl polysulfide cyclohexane solution containing 0.1 g of sulfur to obtain a palladium-based catalyst. The main components of the catalyst and the average results of the 200-hour evaluation are shown in Table 2' and Table 3' respectively. Example 7'

[0287] The process from Example 5' was repeated, except that in the production of the catalyst in the second step, specifically:

[0288] 1 L of alumina was mixed with 600 ml of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0289] 1 L of the above support containing P was mixed with 2000 g of aqueous chloropalladic acid-copper nitrate solution. Petition 870220025896, dated 03 / 25 / 2022, pp. 86 / 106 67 / 76 containing 3.0 g of palladium and 1.0 g of copper, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor in an oxidized state.

[0290] The palladium-based catalyst precursor above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 35°C to produce a palladium-based catalyst.

[0291] The main components of the catalyst and the average results of the 200-hour evaluation are shown in Table 2' and Table 3' respectively. Example 8'

[0292] The process of Example 5' was repeated, except that in the production of the catalyst in the second step, specifically:

[0293] 1 L of alumina was mixed with 600 g of aqueous phosphoric acid solution containing 27 g of P, dried at 110°C for 8 hours and calcined at 400°C for 4 hours to produce a catalyst support containing P.

[0294] 1 L of the above support containing P was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 500°C for 4 hours to produce a palladium-based catalyst precursor in an oxidized state.

[0295] The palladium-based catalyst precursor above in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours-1 for 4 hours at a reduction temperature of 35°C to produce a palladium-based catalyst. The main components of the catalyst and the average results of the 200-hour evaluation are shown in Table 2' and Table 3' respectively. Petition 870220025896, dated 03 / 25 / 2022, pp. 87 / 106 68 / 76 Comparative Example 1 1. Catalyst production

[0296] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid-nickel nitrate solution containing 3.0 g of palladium and 0.3 g of nickel, dried at 110°C for 8 hours and calcined at 550°C for 4 hours to produce a palladium-based catalyst precursor solution I in an oxidized state. The above palladium-based catalyst precursor solution I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2'. 2. Catalyst evaluation

[0297] The hydrogenation operation of the hydrocarbon material comprising α,α-dimethylbenzyl alcohol in Table 1 was carried out continuously. The material from which the heavy components were removed passed through only one catalyst bed. The catalyst loading of one catalyst bed was the same as that of two catalyst beds when employed. The specific operating conditions were as follows: Reaction temperature: 150°C; Reaction pressure: 1.50 MPa; Space velocity of fresh raw material oil volume: 2 h⁻¹ Relationship of the liquid phase thermal cycle: 4 Hydrogen / fresh oil ratio of the raw material by volume: 400

[0298] The average results of the 200-hour assessment are shown in Table 3'. Petition 870220025896, dated 03 / 25 / 2022, pp. 88 / 106 69 / 76 Comparative Example 2' 1. Catalyst production

[0299] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 450°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2'. 2. Catalyst evaluation

[0300] The hydrogenation operation of the hydrocarbon material comprising α,α-dimethylbenzyl alcohol in Table 1 was carried out continuously. The material from which the heavy components were removed passed through only one catalyst bed. The catalyst loading of one catalyst bed was the same as that of two catalyst beds when employed. The specific operating conditions were as follows: Reaction temperature: 150°C Reaction pressure: 1.50 MPa Space velocity of volume of fresh raw material oil: 2h-1 Relationship of the liquid phase thermal cycle: 4 Hydrogen / fresh oil ratio of the raw material by volume: 400 The average results of the 200-hour assessment are shown in Table 3'. Comparative Example 3' Petition 870220025896, dated 03 / 25 / 2022, pp. 89 / 106 70 / 76 1. Catalyst production a. Production of the catalyst for the first catalyst bed

[0301] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid solution containing 3.0 g of palladium, dried at 110°C for 8 hours and calcined at 450°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2'. b. Production of the catalyst for the second catalyst bed

[0302] 1 L of supporting alumina was mixed with 2000 g of aqueous chloropalladic acid-nickel nitrate solution containing 3.0 g of palladium and 0.3 g of nickel, dried at 110°C for 8 hours and calcined at 550°C for 4 hours to produce a palladium-based catalyst precursor I in an oxidized state. The above palladium-based catalyst precursor I in an oxidized state was reduced with hydrogen having a volume space velocity of 100 hours⁻¹ for 4 hours at a reduction temperature of 300°C to produce a palladium-based catalyst. The main components of the catalyst are shown in Table 2'. 2. Catalyst evaluation

[0303] The hydrogenation operation of the hydrocarbon material comprising α,α-dimethylbenzyl alcohol in Table 1 was carried out continuously. The material passed first through the first catalyst bed and then through the second catalyst bed. The catalyst loading volume ratio of the two catalyst beds was 1:4. The operating conditions Petition 870220025896, dated 03 / 25 / 2022, pp. 90 / 106 71 / 76 of the two reactors were as follows: The first catalyst bed: Reaction temperature: 150°C Reaction pressure: 1.50 MPa Space velocity of volume of fresh raw material oil: 2h'1 Relationship of the liquid phase thermal cycle: 4 Hydrogen / fresh oil ratio of the raw material by volume: 400 The second catalyst bed: Reaction temperature: 170°C Reaction pressure: 1.3 MPa Hydrogen / fresh oil ratio of the raw material by volume: 400

[0304] The average results of the 200-hour assessment are shown in Table 3'. Comparative Example 4'

[0305] The catalyst production in Example 1' was repeated, except in the catalyst evaluation:

[0306] The hydrogenation operation of the hydrocarbon material comprising α,α-dimethylbenzyl alcohol in Table 1 was carried out continuously. The material passed first through the first catalyst bed and then through the second catalyst bed. The catalyst loading volume ratio of the two catalyst beds was 4:1. The operating conditions of the two reactors were as follows: The first catalyst bed: Reaction temperature: 150°C Reaction pressure: 1.50 MPa Spatial velocity of fresh oil volume Petition 870220025896, dated 03 / 25 / 2022, pp. 91 / 106 72 / 76 raw material: 2tr1 Relationship of the liquid phase thermal cycle: 0 Hydrogen / fresh oil ratio of the raw material by volume: 400 The second catalyst bed: Reaction temperature: 170°C Reaction pressure: 1.3 MPa Hydrogen / fresh oil ratio of raw material by volume: 200

[0307] The average results of the 200-hour assessment are shown in Table 3'. Table 2: Main components of the catalyst Item Number AI2O3 g / L Pd g / L Metal Auxiliary g / LP g / LS g / L SiO2 g / L Example T First-stage catalyst 568 2.87 0 0 0 0 Second-stage catalyst 556 2.79 Ni-0.34 0 0 0 Example 2' First-stage catalyst 554 2.78 0 0 0 0 Second-stage catalyst 556 2.83 Ni-0.24 / Mg-0.09 0 0 0 Example 3' First-stage catalyst 558 2.81 0 0 0 0 Second-stage catalyst 561 2.79 Cu-0.28 0 0 0 Example 4' First-stage catalyst 558 2.91 0 0 0 0 Second-stage catalyst 552 2.86 Cu-0.89 56.32 0.083 0 Petition 870220025896, dated 03 / 25 / 2022, pp. 92 / 106 73 / 76 Example 5' First-stage catalyst 558 2.82 0 0 0 0 Second-stage catalyst 552 2.78 Cu-0.90 25.23 0.080 26 Example 6' First-stage catalyst 558 2.82 0 0 0 0 Second-stage catalyst 552 2.78 Cu-0.90 25.23 0.080 0 Example 7' First-stage catalyst 558 2.82 0 0 0 0 Second-stage catalyst 552 2.78 Cu-0.90 25.23 0 0 Example 8' First-stage catalyst 554 2.78 0 0 0 0 Second-stage catalyst 554 2.78 0 25.23 0 0 Example Comparative T Catalyst of Single-stage catalyst 560 2.84 Ni-0.32 0 0 0 Example Compar active 2' Single-stage catalyst 563 2.76 0 0 0 0 Example Compar active 3' First-stage catalyst 551 2.77 0 0 0 0 Second-stage catalyst 548 2.84 Ni-0.33 0 0 0 Example Compar active 4' First-stage catalyst 568 2.87 0 0 0 0 Second-stage catalyst 556 2.79 Ni-0.34 0 0 0 Petition 870220025896, dated 03 / 25 / 2022, pp. 93 / 106 74 / 76 Table 3': Item Isopropylbenzene hydroperoxide content in hydrogenation product ppm Amethylstyrene content in hydrogenation product ppm Dimerized isopropylbenzene content ppm α,α-dimethylbenzyl alcohol content in hydrogenation product ppm Isopropylbenzene selectivity % Example T 0 12 86 186 99.82 Example 2' 0 8.6 67 146 99.87 Example 3' 0 5.8 78 85 99.83 Example 4' 0 3.2 51 54 99.92 Example 5' 0 2.5 48 32 99.95 Example 6' 0 4.8 58 68 99.90 Example 7' 0 5.1 62 71 99.88 Example 8' 0 5.3 66 75 99.86 Comparative Example T 18 350 412 46520 99.72 Comparative Example 2' 22 467 426 57368 99.64 Comparative Example 3' 0 12 245 4876 99.69 Comparative Example 4' 0 356 3250 123 99.12

[0308] Can be seen in Table 2' and Table 3': (1) According to the respective comparison between Comparative Examples T-2' and Example T, and Example 3', in which both Comparative Examples T-2' employed a single catalyst bed filled with the same amount of catalyst, it can be observed that the isopropylbenzene hydroperoxide content, the α-methylstyrene content, the dimerized isopropylbenzene content and the α,α-dimethylbenzyl alcohol content in the products of Comparative Examples T-2' were all higher than those in the examples, particularly the α,α-dimethylbenzyl alcohol content. Petition 870220025896, dated 03 / 25 / 2022, pp. 94 / 106 75 / 76 above indicates that the method according to the present invention can achieve a high conversion to α,α-dimethylbenzyl alcohol. (2) According to the comparison between Comparative Examples 3' and Example T, in which the catalyst loading in the first catalyst bed in Comparative Example 3' was lower than in the second catalyst bed, it can be observed that the isopropylbenzene dimerized content and the α,adimethylbenzyl alcohol content in the product of Comparative Examples 3' were significantly higher. (3) According to the comparison between Examples 5' and Example 3', when phosphorus, silica and sulfur were introduced into the second catalyst simultaneously, the content of isopropylbenzene hydroperoxide, the content of α-methylstyrene, the content of dimerized isopropylbenzene and the content of α,α-dimethylbenzyl alcohol in the product of Examples 5' were all lower than those of Example 3'. (4) According to the comparison between Examples 6' and Example 5', when only phosphorus and sulfur were introduced into the second catalyst, the content of isopropylbenzene hydroperoxide, the content of α-methylstyrene, the content of dimerized isopropylbenzene and the content of α,α-dimethylbenzyl alcohol in the product of Examples 6' were all higher than those of Example 5'. (5) According to the comparison between Example 7' and Example 5', when only phosphorus was introduced into the second catalyst, the content of isopropylbenzene hydroperoxide, the content of α-methylstyrene, the content of dimerized isopropylbenzene and the content of α-dimethylbenzyl alcohol in the product of Example 7' were all higher than those of Example 5'. (6) According to the comparison between Examples 8' and Example 7', when only phosphorus was introduced in the second Petition 870220025896, dated 03 / 25 / 2022, pp. 95 / 106 76 / 76 catalyst, the isopropylbenzene hydroperoxide content, the α-methylstyrene content, the dimerized isopropylbenzene content, and the α-dimethylbenzyl alcohol content in the product of Examples 8' were all higher than those of Example 7'. (7) According to the comparison between Comparative Example 4' and Example 1', in which the thermal cycle ratio of the liquid phase of the first catalyst bed under the reactor operating conditions of Comparative Examples 4' was 0, it can be seen that the content of dimerized isopropylbenzene in the product of Comparative Examples 4' was significantly higher and the isopropylbenzene selectivity was significantly reduced.

Claims

1. Catalyst for the production of isopropylbenzene from α,α-dimethylbenzyl alcohol, characterized in that it comprises a support and an active component supported on the support, wherein the support comprises a supporting substrate and an auxiliary modifying component supported on the supporting substrate, wherein the active component includes palladium metal and / or oxides thereof, the auxiliary modifying component includes phosphorus and / or oxides thereof, wherein the supporting substrate is not silica, and the auxiliary modifying component also includes silica, wherein the molar ratio of silicon to phosphorus based on the element is < 20.

2. Catalyst according to claim 1, characterized in that the content of palladium metal and / or oxides thereof in the catalyst is 0.01-5% by weight, preferably 0.05-1% by weight, based on the content of the element palladium and / or the metal palladium having a dispersion of 5-10%, preferably 6.5-8.5%.

3. Catalyst according to claim 2, characterized in that the active component further includes an active auxiliary metal and / or oxides thereof; preferably, the active auxiliary metal is at least one selected from the group consisting of copper metal, zinc metal, cobalt metal, tin metal, nickel metal and silver metal; preferably, the content of the active auxiliary metal and / or oxides thereof in the catalyst is 0.0001-0.2% by weight, more preferably 0.0007-0.2% by weight, based on the content of the auxiliary metal element therein.

4. Catalyst according to any of claims 1 to 3, characterized in that the content of the auxiliary modifying component in the catalyst is 0.2-20% by weight, preferably 1-15% by weight, based on the content of the phosphorus element.

5. Catalyst according to any one of claims 1 to 4, characterized in that the supporting substrate is at least one selected from the group consisting of alumina and activated carbon, and / or the supporting substrate has a pore size of 10-25 nm and a specific surface area of ​​50-180 m2 / g, 6. Catalyst according to any one of claims 1 to 5, characterized in that the catalyst further includes a cocatalyst; preferably, the cocatalyst is a sulfur-containing compound; more preferably, the sulfur-containing compound is derived from a sulfur-containing organic matter; even more preferably, the sulfur-containing organic matter is at least one selected from the group of tert-nonyl polysulfides, tert-butyl polysulfides, thiophenes and dimethyl disulfides etc.; the cocatalyst content in the catalyst is preferably > 0-1% by weight, more preferably > 0-0.8% by weight, wherein the amount of cocatalyst is based on the amount of effective elements in it, for example, the amount of the element sulfur.

7. Catalyst according to any one of claims 1 to 6, characterized in that the silica is derived from silica gel, and the silica content in the catalyst is preferably > 0-60% by weight, more preferably > 0-40% by weight.

8. Catalyst according to any one of claims 1 to 7, characterized in that the molar ratio of silicon to phosphorus based on the element is < 10, preferably < 4, wherein the content of the auxiliary modifying component phosphorus and / or oxides thereof in the catalyst is 0.2-20% by weight, preferably 115% by weight, more preferably 1-7% by weight, wherein the content of phosphorus and / or oxides thereof is based on the content of phosphorus element therein, and the silica content in the catalyst is > 0-60% by weight, preferably > 0-40% by weight, for example, > 0-20% by weight.

9. A method for producing the catalyst as defined in any one of claims 1 to 8, characterized in that it comprises the following steps: step 1: an aqueous solution of a phosphorus-containing compound is mixed with a supporting substrate, dried, and calcined to obtain a phosphorus-containing support; step 1': the phosphorus-containing support is mixed with an aqueous solution of silica gel, dried, and calcined to obtain a phosphorus-containing and silicon-containing support; step 2: the phosphorus-containing and silicon-containing support is added to a solution of a palladium-containing compound, dried, and calcined to obtain an oxidized catalyst precursor; step 3: the oxidized catalyst precursor is subjected to a reduction treatment to obtain a catalyst.

10. Production method according to claim 9, characterized in that the supporting substrate is at least one selected from the group consisting of alumina and activated carbon, and / or the palladium-containing compound is at least one selected from the group consisting of palladium chloride, palladium nitrate and chloropalladic acid, and / or the phosphorus-containing compound is at least one selected from the group consisting of phosphoric acid, potassium dihydrogen phosphate, phosphorous acid, calcium phosphate and ammonium hydrogen phosphate, etc., and / or Petition 870250002089, dated 10 / 01 / 2025, p.14 / 241 4 / 8 The solution in step 2 further comprises a compound containing an active auxiliary metal which is preferably at least one selected from the group consisting of active auxiliary metal chlorides, active auxiliary metal nitrate compounds and active auxiliary metal acetate compounds; more preferably, the active auxiliary metal is at least one selected from the group consisting of copper metal, zinc metal, cobalt metal, tin metal, nickel metal and silver metal.

11. Production method according to claim 9 or 10, characterized in that, in step 1, step 2, the calcination temperature is 400-700°C, preferably 400-500°C, and / or in step 3, a reduction treatment with hydrogen is carried out; preferably, the reduction temperature is 40-300°C, preferably 200-300°C, more preferably 250°C; the volumetric space velocity of hydrogen is 50-500h-1, preferably 80-150h-1.

12. Production method according to any one of claims 9 to 11, characterized in that the method further comprises step 4: step 4: the catalyst according to step 3 is added to a solution containing cocatalyst and dried to obtain an additional catalyst; preferably, the cocatalyst is a sulfur-containing compound; more preferably, the sulfur-containing compound is derived from a sulfur-containing organic matter; even more preferably, the sulfur-containing organic matter is at least one selected from the group of tert-nonyl polysulfides, tert-butyl polysulfides, thiophenes and dimethyl disulfides.

13. Production method in accordance with any of the Petition 870250002089, dated 10 / 01 / 2025, page.15 / 241 5 / 8 claims 9 to 12, characterized in that, based on 1 L of the supporting substrate, the amount of the palladium-containing compound is 0.06 g / L-30 g / L, preferably 0.5 g / L-10 g / L, based on the amount of palladium element therein, and / or the amount of the compound containing an active auxiliary metal is 0.0006 g / L-1.2 g / L, preferably 0.01 g / L-1.0 g / L, based on the amount of the active auxiliary metal element therein, and / or the amount of the phosphorus-containing compound is 2 g / L-100 g / L, preferably 5 g / L-80 g / L, based on the amount of phosphorus element therein, and / or the amount of the cocatalyst is 0.0001 g / L-3 g / L, preferably 0.01 g / L-1 g / L, more preferably 0.05 g / L-0.2 g / L, wherein the amount of cocatalyst is based on the amount of effective elements in it, such as sulfur, and / or the amount of silica gel is 6-300 g / L, preferably 20-200 g / L, wherein the amount of silica gel is based on the amount of silica in it.

14. Use of the catalyst as defined in any one of claims 1 to 8 or of the catalyst obtained by the method as defined in any one of claims 9 to 13, characterized in that it is used in the production of isopropylbenzene from α,α-dimethylbenzyl alcohol.

15. Method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol, characterized in that it is carried out in the presence of the catalyst as defined in any one of claims 1 to 8 or the catalyst obtained by the method as defined in any one of claims 9 to 13; wherein, more preferably, the production method comprises: bringing the raw material into contact with hydrogen to react in the presence of the catalyst to obtain isopropylbenzene, wherein the method preferably uses a liquid-phase thermal cycle process; more preferably, wherein the cycle ratio is 1-10, preferably 4-8.

16. Production method according to claim 15, characterized in that the raw material comprises a hydrocarbon material comprising α,α-dimethylbenzyl alcohol, wherein the hydrocarbon material optionally comprises isopropylbenzene, acetophenone, α-methylstyrene and dimerized isopropylbenzene, and optionally comprises isopropylbenzene hydroperoxide; preferably, the hydrocarbon material comprising α,α-dimethylbenzyl alcohol comprises an inert solvent, preferably isopropylbenzene and α,α-dimethylbenzyl alcohol.

17. Production method according to claim 16, characterized in that the pressure is 0.1-4.0 MPa, the temperature is 130-220°C, the hourly space velocity of the liquid is 1-20 h-1 and the molar ratio of hydrogen to α,α-dimethylbenzyl alcohol is > 4 in the production method; preferably, the pressure is 0.5-3.0 MPa, the temperature is 150-200°C, the hourly space velocity of the liquid is 4-15 h-1 and the molar ratio of hydrogen to α,α-dimethylbenzyl alcohol is > 5.

18. Method for producing isopropylbenzene from α,α-dimethylbenzyl alcohol, characterized in that it comprises obtaining isopropylbenzene from a hydrocarbon feedstock comprising α,α-dimethylbenzyl alcohol and hydrogen through a first catalyst bed and a second catalyst bed in series, preferably by a liquid-phase thermal cycle process; wherein the catalyst charge of the first catalyst bed is greater than or equal to that of the second catalyst bed; preferably, the ratio in Petition 870250002089, dated 10 / 01 / 2025, p.17 / 241 7 / 8 The catalyst loading volume of the first catalyst bed to the catalyst loading of the second catalyst bed is (1-6):1, preferably (2-4):1; the inlet temperature of the first catalyst bed is not higher than the inlet temperature of the second catalyst bed; preferably, the first catalyst bed has a reaction temperature of 130-190°C, a reaction pressure of 0.1-5MPa and a net hourly space velocity of 1.0-20h-1, and / or the second catalyst bed has a reaction temperature of 150-230°C, a reaction pressure of 0.1-5 MPa and a liquid phase volume space velocity of 2.0-10h-1, the liquid phase thermal cycle ratio of the first catalyst bed is preferably 1-10; the liquid phase thermal cycle ratio of the second catalyst bed is preferably 0-2.

19. Production method according to claim 18, characterized in that, in the first catalyst bed, the hydrogen to liquid phase volume ratio is 300-1000, preferably 400-800, and / or in the second catalyst bed, the hydrogen to liquid phase volume ratio is 100-800, preferably 200-400.

20. Production method according to claim 18 or 19, characterized in that the catalyst of the first catalyst bed comprises metallic Pd and / or oxides, and a support, and / or the catalyst of the second catalyst bed comprises metal Pd and / or oxides, a metal auxiliary and / or oxides thereof, and a support; preferably, the metal auxiliary is at least one selected from the group consisting of Fe, Co, Ni, Ca, Mg and Cu, more preferably at least one selected from the group consisting of Cu, Ni and Mg, or Petition 870250002089, dated 10 / 01 / 2025, page 18 / 241 8 / 8 the catalyst of the first catalyst bed and / or the catalyst of the second catalyst bed are the catalysts as defined in any one of claims 1 to 8.

21. Use of the method as defined in any one of claims 15 to 20, characterized in that it is in the production of propylene oxide.

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