A hydrogenolysis catalyst, its preparation method and application

Abstract

This invention discloses a hydrogenolysis catalyst, its preparation method, and its application. The catalyst comprises a support and an active component, the active component being distributed on the surface and interior of the support. Based on a total content of 100 wt% for the support and active component, the bulk active component content of the catalyst is 0.01–5 wt%, and the surface active component content is 0.005–3 wt%. The catalyst of this invention can be used to treat the hydrogenolysis products of α,α-dimethylbenzyl alcohol, especially the heavy components such as cumene. Specifically, the hydrogenolysis catalyst can hydrogenolyze cumene, which has a boiling point similar to that of the high-value-added byproduct acetophenone, to produce cumene with a lower boiling point, maximizing the retention of acetophenone. High-purity acetophenone can be obtained in subsequent distillation columns, effectively reducing the cost of later byproduct separation and possessing high industrial application value.

Description

Technical Field

[0001] This invention relates to hydrogenolysis catalysts, and more particularly to hydrogenolysis catalysts for treating hydrogenolysis products of α,α-dimethylbenzyl alcohol. Specifically, it relates to a hydrogenolysis catalyst, its preparation method, and its application. Background Technology

[0002] Propylene oxide (PO) is an important organic chemical intermediate, mainly used as a raw material for the production of polyurethane—polyether polyols. Currently, the main industrial processes for producing PO include the chlorohydrin process, the co-oxidation process (PO / styrene monomer process, PO / tert-butanol process, PO / methyl tert-butyl ether process), the cumene hydroperoxide process (CHP process), and the hydrogen peroxide oxidation process (HPPO process).

[0003] Sumitomo Chemicals of Japan has developed a new process for producing PO, which includes three steps: cumene oxidation, propylene epoxidation, and α,α-dimethylbenzyl alcohol hydrogenolysis. This process has no byproducts, causes no environmental pollution, requires less investment, and is an environmentally friendly clean production process. The process includes cumene oxidation, propylene epoxidation, and α,α-dimethylbenzyl alcohol hydrogenolysis (DMBA). Theoretically, this process only consumes propylene, air, and hydrogen, with cumene used as a recycled material. However, the cumene peroxides formed after cumene oxidation, such as cumene hydroperoxide (CHP) and dicumene peroxide (DCP), are unstable, chemically reactive, and easily trigger various side reactions (as shown in Figure 1).

[0004] Cumene consumption is a key indicator for evaluating the economic efficiency and advanced nature of the CHP process for producing PO. Figure 1 It is known that the CHP process for producing PO generates acetophenone and other heavy components such as cumene, increasing the consumption of cumene during the process. These heavy components are eventually enriched in the bottom of the cumene recovery tower in the cumene recovery unit along with the feed material. Currently, there is no catalyst available to process these heavy components. Summary of the Invention

[0005] To overcome the problems existing in the prior art, the present invention provides a hydrogenolysis catalyst, its preparation method and application. The hydrogenolysis catalyst can be used to treat the hydrogenolysis products of α,α-dimethylbenzyl alcohol, especially the heavy components such as cumene. Specifically, the hydrogenolysis catalyst can hydrogenoly decompose cumene, which has a boiling point similar to that of the high-value-added byproduct acetophenone, to produce cumene with a lower boiling point, thus maximizing the retention of acetophenone. High-purity byproduct acetophenone can be obtained in subsequent distillation columns, effectively reducing the cost of subsequent byproduct separation and possessing high industrial application value.

[0006] One objective of this invention is to provide a hydrogenolysis catalyst, the catalyst comprising a support and an active component, the active component being distributed on the surface and interior of the support, wherein, based on a total content of 100 wt% of the support and the active component, the content of the bulk active component of the catalyst is 0.01–5 wt%, the content of the surface active component of the catalyst is 0.005–3 wt%, and preferably the content of the bulk active component is greater than the content of the surface active component.

[0007] In this invention, the active components are distributed not only on the surface of the support but also within the support. The bulk active component content refers to the total content of active components in the catalyst, and the surface active component content refers to the content of active components on the surface of the support. In the prior art, catalysts prepared by ordinary impregnation methods generally have active metals dispersed on the surface of the support or substrate. The interaction between the metal and the support or substrate is weak, and the metals mostly exist in a free state in the catalyst. At higher reaction temperatures, they are prone to migration and growth, resulting in a decrease in catalyst activity. The one-pot catalyst preparation technology provided in this process can embed the active metal into the support or substrate framework, improving the dispersion of the active metal while enhancing the interaction between the metal and the support or substrate, thereby improving the thermal stability of the catalyst.

[0008] In a preferred embodiment, the carrier is selected from at least one of metal oxides and activated carbon.

[0009] In a further preferred embodiment, the carrier is selected from at least one of alumina, silicon dioxide, activated carbon, titanium dioxide, zirconium oxide, and iron oxide, preferably silicon dioxide.

[0010] In a preferred embodiment, the active component is selected from noble metals, preferably palladium.

[0011] In a preferred embodiment, the catalyst may further optionally contain an auxiliary agent.

[0012] In a further preferred embodiment, the additive is selected from at least one of copper, iron, boron, phosphorus, and sulfur.

[0013] In a further preferred embodiment, the content of the adjuvant is 0 to 1500 ppm (e.g., 20 to 1500 ppm), preferably 0 to 200 ppm (e.g., 50 to 200 ppm), based on a total content of 100 wt% of the carrier and active component.

[0014] For example, the content of the auxiliary agent is 20 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, 1000 ppm or 1500 ppm, based on a total content of 100 wt% of the carrier and active component.

[0015] In a preferred embodiment, based on a total content of 100 wt% for the support and active components, the bulk active component content of the catalyst is 0.05-1 wt%, the surface active component content of the catalyst is 0.025-0.5 wt%, and preferably the bulk active component content is greater than the surface active component content.

[0016] For example, based on a total content of 100 wt% for the support and active components, the bulk active component content of the catalyst is 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt%.

[0017] In a preferred embodiment, the catalyst is prepared by impregnation, spraying, spin coating or deposition / precipitation, preferably by deposition / precipitation.

[0018] A second objective of this invention is to provide a method for preparing a hydrogenolysis catalyst, preferably used for preparing the hydrogenolysis catalyst described in one objective of this invention. The preparation method includes: adding a support precursor to a solution containing a nitrogen source, a carbon source, an active component precursor, and optionally an auxiliary agent precursor; performing post-treatment after reaction to obtain the hydrogenolysis catalyst.

[0019] The present invention uses a deposition precipitation method to prepare hydrogenolysis catalyst, which is completely different from the impregnation method disclosed in the prior art. The impregnation method of the prior art cannot provide any technical inspiration for the present invention.

[0020] In a preferred embodiment, the nitrogen source is selected from organic amine compounds.

[0021] In a further preferred embodiment, the nitrogen source is selected from one or more of ethylenediamine, aniline, oleylamine, urea, triethylamine, alkanolamines, and amino acids.

[0022] In a preferred embodiment, the carbon source is selected from hydroxyl-containing organic compounds.

[0023] In a further preferred embodiment, the carbon source is selected from one or more of glycerol, ethylene glycol, glucose, citric acid, xylitol, fructose, cellulose, polyvinyl alcohol, starch, and biomass.

[0024] Preferably, the carbon source and the nitrogen source are different substances.

[0025] In this invention, the nitrogen source and carbon source mainly play two roles: 1) structural template agents for the carrier, and 2) complexing noble metals (e.g., palladium).

[0026] In a preferred embodiment, the active component precursor is a water-soluble compound containing the active component.

[0027] In a further preferred embodiment, the active component precursor is selected from one or more of chloride, nitrate, acetate, sulfate and phosphate containing the active component.

[0028] In a preferred embodiment, the carrier precursor is selected from one or more of methyl orthosilicate, ethyl orthosilicate, trimethylethoxysilane, methyltriethylsilane, titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, zirconium oxychloride, zirconium nitrate, aluminum nitrate, aluminum isopropoxide, ferric nitrate, and sodium ferrate.

[0029] In a preferred embodiment, the auxiliary precursor is selected from at least one of copper and / or iron nitrates and / or carbonates, and organic and / or inorganic acids containing boron and / or phosphorus and / or sulfur, preferably from at least one of copper nitrate, basic copper carbonate, ferric nitrate, phosphoric acid, boric acid, and sulfuric acid.

[0030] In a preferred embodiment, the solvent is water.

[0031] In a preferred embodiment, the molar ratio of the carbon source to the nitrogen source is 1:(0.05-2), preferably 1:(0.1-1), and more preferably 1:(0.1-0.5).

[0032] For example, the molar ratio of the carbon source to the nitrogen source is 1:0.05, 1:0.08, 1:0.1, 1:0.12, 1:0.15, 1:0.18 or 1:0.2.

[0033] In a preferred embodiment, the mass ratio of the carbon source to the carrier precursor is 1:(0.1-20), preferably 1:(0.5-10).

[0034] For example, the mass ratio of the carbon source to the carrier precursor is 1:0.1, 1:0.5, 1:1, 1:2, 1:5, 1:8, 1:10, 1:12, 1:15, 1:18 or 1:20.

[0035] In a preferred embodiment, based on a total weight of 100 wt% of the active component precursor and the carrier precursor, the amount of the active component precursor is 0.01 to 5 wt%, preferably 0.005 to 1 wt%, wherein the weight of the active component precursor is based on the weight of the metal element, and the weight of the carrier precursor is based on the weight of its corresponding oxide.

[0036] For example, based on a total weight of 100 wt% for the active component precursor and the carrier precursor, the amount of the active component precursor is 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt%, wherein the weight of the active component precursor is based on the weight of the metal element, and the weight of the carrier precursor is based on the weight of its corresponding oxide.

[0037] In a preferred embodiment, the amount of the auxiliary agent precursor is 0-1500 ppm (e.g., 20-1500 ppm), preferably 0-200 ppm (e.g., 50-200 ppm), based on a total weight of 100 wt% of the active component precursor and the carrier precursor. The weight of the active component precursor is based on the weight of the metal element, the weight of the carrier precursor is based on the weight of its corresponding oxide, and the amount of the auxiliary agent precursor is based on the weight of the auxiliary element therein.

[0038] In a preferred embodiment, the reaction temperature is 80°C to 300°C and the time is 4 to 72 hours.

[0039] In a further preferred embodiment, the reaction temperature is 100℃~180℃ and the time is 8~24h.

[0040] In a preferred embodiment, when the carrier precursor is selected from at least one of methyl orthosilicate, ethyl orthosilicate, trimethylethoxysilane, methyltriethylsilane, tetrabutyl titanate, and isopropyl titanate, it is hydrolyzed before the reaction.

[0041] In a further preferred embodiment, the hydrolysis treatment is carried out at 20–70°C for 2–50 hours, preferably at 30–60°C for 15–30 hours.

[0042] For example, the temperature of the hydrolysis treatment is 20°C, 30°C, 40°C, 50°C, 60°C or 70°C, and the time of the hydrolysis treatment is 5h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 45h or 50h.

[0043] In a preferred embodiment, the preparation method includes:

[0044] (1) Mix the nitrogen source, the carbon source and the solvent to obtain solution A;

[0045] (2) Mix the active component precursor and the optional auxiliary agent precursor to obtain solution B;

[0046] It is preferable to proceed in the steps described above. Mixing in one pot may result in uneven mixing, which in turn may cause uneven dispersion of the carrier particles and the active phase.

[0047] (3) Mix the solution A and the solution B, and slowly add the carrier precursor to it to obtain the hydrogenolysis catalyst precursor through reaction;

[0048] In particular, the carrier precursor is preferably added slowly to ensure thorough mixing and prevent the formation of large particles.

[0049] (4) The hydrogenolysis catalyst precursor is post-treated to obtain the hydrogenolysis catalyst.

[0050] In a preferred embodiment, the post-processing includes washing, drying, and roasting.

[0051] In a further preferred embodiment, the drying temperature is 50–200°C, preferably 60–150°C, and the time is 4–24 h, preferably 8–15 h; and / or, the calcination temperature is 300–600°C, preferably 500–600°C, and the time is 4–12 h, preferably 4–8 h.

[0052] For example, the drying temperature is 50℃, 80℃, 100℃, 120℃, 140℃, 160℃, 180℃ or 200℃, and the time is 4h, 8h, 12h, 16h, 20h or 24h; the roasting temperature is 300℃, 400℃, 500℃ or 600℃, and the time is 4h, 4.5h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.

[0053] The third objective of this invention is to provide a hydrogenolysis catalyst obtained by the preparation method described in the second objective of this invention.

[0054] The fourth objective of this invention is to provide the application of the hydrogenolysis catalyst described in the first objective of this invention or the hydrogenolysis catalyst obtained by the preparation method described in the second objective of this invention in the treatment of α,α-dimethylbenzyl alcohol hydrogenolysis products, especially in the treatment of the material after the removal of cumene from the α,α-dimethylbenzyl alcohol hydrogenolysis products.

[0055] Preferably, the treatment of the α,α-dimethylbenzyl alcohol hydrogenolysis product using the hydrogenolysis catalyst includes: (A) recovery of cumene: the α,α-dimethylbenzyl alcohol hydrogenolysis product is subjected to distillation, cumene is recovered from the top of the column, and a liquid by-product is obtained from the bottom of the column; (B) hydrogenolysis treatment: the liquid by-product is hydrogenoly treated using the hydrogenolysis catalyst to obtain a hydrogenolysis product, the hydrogenolysis product is subjected to distillation, cumene is obtained from the top of the column, acetophenone is obtained from the bottom of the column, and other liquid by-products are collected from the side stream. Preferably, the α,α-dimethylbenzyl alcohol hydrogenolysis product is derived from the α,α-dimethylbenzyl alcohol hydrogenolysis product in the CHP process for preparing propylene oxide.

[0056] In this invention, cumene, which has a boiling point close to that of the high-value-added byproduct acetophenone, is preferentially hydrogenated to produce cumene with a lower boiling point, while retaining acetophenone to the greatest extent possible. High-purity byproduct acetophenone is then obtained in a subsequent distillation column, effectively reducing the cost of byproduct separation.

[0057] In this invention, the hydrogenolysis method can convert cumene in the hydrogenolysis product of α,α-dimethylbenzyl alcohol into isopropylbenzene without producing isopropylcyclohexane as a byproduct, and it does not affect acetophenone in the hydrogenolysis product of α,α-dimethylbenzyl alcohol.

[0058] The endpoints and any values ​​of the ranges disclosed in this invention are not limited to the precise ranges or values; these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In the following, various technical solutions can, in principle, be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0059] Compared with the prior art, the present invention has the following beneficial effects: the hydrogenolysis catalyst of the present invention can efficiently recover cumene from propylbenzene, reduce the cumene consumption in the CHP process for producing PO, reduce the cost of separating by-products in the later stage, and can efficiently recover the high-value-added by-product acetophenone, thus having high industrial application value. Attached Figure Description

[0060] Figure 1 The diagram shows the pyrolysis reaction of cumene peroxide and the formation of impurities such as acetophenone and methyl ethyl ketone. Detailed Implementation

[0061] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0062] It should also be noted that the various specific technical features described in the following embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the various possible combinations will not be described separately in this invention.

[0063] Furthermore, various embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention. The resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0064] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0065] In the examples: the titanium-containing silicon oxide catalyst in the epoxy process was prepared according to Example 2 of the published patent CN104437635B; the Pd / Al2O3 catalyst in the benzyl alcohol hydrogenolysis process can be used simultaneously for dehydration and hydrogenation processes, and was prepared according to Example 4 of the published patent CN104151129B.

[0066] The α,α-dimethylbenzyl alcohol hydrogenolysis products of the examples and comparative treatments were obtained as follows:

[0067] Cumene, washed with NaOH aqueous solution, and oxygen were introduced into an oxidation reactor for oxidation reaction. The temperature and pressure of the oxidation reaction were 90℃ and 300kPaG, respectively. The O2 content of the reaction tail gas was controlled to be less than 0.5%, and the reaction time was 0.5 hours, resulting in a stream containing cumene hydroperoxide (CHP).

[0068] The obtained stream containing cumene hydroperoxide (CHP) was reacted with propylene in the presence of a titanium-containing silicon oxide catalyst (TiSiO2) to produce a stream containing propylene oxide and α,α-dimethylbenzyl alcohol. The reaction temperature was 75°C, the reaction pressure was 5000 kPaG, the molar ratio of propylene to cumene hydroperoxide (CHP) was 8:1, and the weight hourly space velocity (WHSV) of cumene hydroperoxide (CHP) was 0.8 h⁻¹. -1 .

[0069] The stream flowing out of the epoxidation reactor is separated to obtain crude propylene oxide and a stream containing α,α-dimethylbenzyl alcohol. Excess propylene is recovered and recycled. The separated crude propylene oxide is further purified by distillation to obtain refined PO. Specifically, the stream flowing out of the epoxidation reactor is sequentially introduced into two distillation columns connected in series, column one and column two. Unreacted propylene and crude propylene oxide are separated sequentially from the top of each column. The conditions for distillation column one are: top temperature 50℃, pressure 1800 kPaG, and the conditions for distillation column two are: top temperature 45℃, pressure -50 kPaG.

[0070] A stream containing α,α-dimethylbenzyl alcohol was introduced into the benzyl alcohol hydrogenolysis process. First, a dehydration reaction occurred under the catalyst Pd / Al₂O₃ to obtain α-methylstyrene. The reaction temperature was 155℃, the reaction pressure was 2000 kPaG, and the weight hourly space velocity (WHSV) of α,α-dimethylbenzyl alcohol was 1.4 h⁻¹. -1 The resulting mixture of α-methylstyrene was then introduced into a hydrogenation process. Under the action of the hydrogenation catalyst Pd / Al2O3, α-methylstyrene reacted with hydrogen to produce cumene, which was then recycled back to the oxidation process. The hydrogenation reaction temperature was 155℃, the reaction pressure was 2000 kPaG, the molar ratio of hydrogen to α-methylstyrene was 8:1, and the weight hourly space velocity (WHSV) of α-methylstyrene was 1 h⁻¹. -1 The hydrogenolysis product is obtained through the above-described hydrogenolysis process of benzyl alcohol.

[0071] In the embodiments and comparative examples of the present invention:

[0072] cumene conversion rate = (cumene content in raw material - cumene content in product) / cumene content in raw material;

[0073] Cumene selectivity = 2.38 * (moles of cumene in the product + moles of AMS) / (cumene content in the raw material - cumene content in the product);

[0074] Acetophenone yield = mass of acetophenone per unit product / theoretical yield of acetophenone per unit raw material.

[0075]

Example 1

[0076] 11.9 g of citric acid and 1.9 g of ethylenediamine were weighed and dissolved in 140 mL of deionized water. The solution was stirred until clear to obtain solution A. 0.45 g of a 5 wt% palladium chloroacetic acid solution was weighed as solution B. Solution B was added to solution A and stirred evenly. Then, 14.5 g of tetraethyl orthosilicate was slowly added dropwise. The mixture was hydrolyzed at 45 °C for 24 h. The suspension was then transferred to a homogeneous reactor and reacted at 120 °C for 12 h. The material after the hydrothermal reaction was naturally cooled, filtered, washed, dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to obtain a Pd / SiO2 catalyst with a palladium content of 0.5 wt%. The palladium content on the catalyst surface was quantitatively analyzed by EDS energy dispersive spectroscopy, and the palladium content in the bulk catalyst was detected by inductively coupled plasma atomic emission spectrometry. The results are shown in Table 1.

[0077]

Example 2

[0078] 11.9 g of citric acid and 1.9 g of ethylenediamine were weighed and dissolved in 140 mL of deionized water. The solution was stirred until clear to obtain solution A. 0.09 g of a 5 wt% chloropalladium acid solution was weighed as solution B. Solution B was added to solution A and stirred evenly. Then, 14.5 g of tetraethyl orthosilicate was slowly added dropwise. The mixture was hydrolyzed at 45 °C for 24 h. The suspension was then transferred to a homogeneous reactor and reacted at 120 °C for 12 h. The material after the hydrothermal reaction was naturally cooled, filtered, washed, dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to obtain a Pd / SiO2 catalyst with a palladium content of 0.1 wt%. The palladium content on the catalyst surface was quantitatively analyzed by EDS energy dispersive spectroscopy, and the palladium content in the bulk catalyst was detected by inductively coupled plasma atomic emission spectrometry. The results are shown in Table 1.

[0079]

Example 3

[0080] 11.9 g of citric acid and 0.9 g of ethylenediamine were weighed and dissolved in 140 mL of deionized water. The solution was stirred until clear to obtain solution A. 0.09 g of a 5 wt% chloropalladium acid solution was weighed as solution B. Solution B was added to solution A and stirred until homogeneous. Then, 14.5 g of tetraethyl orthosilicate was slowly added dropwise. The mixture was hydrolyzed at 45 °C for 24 h. The suspension was then transferred to a homogeneous reactor and reacted at 120 °C for 12 h. The material after the hydrothermal reaction was naturally cooled, filtered, washed, dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to obtain a Pd / SiO2 catalyst with a palladium content of 0.1 wt%. The palladium content on the catalyst surface was quantitatively analyzed by EDS energy dispersive spectroscopy, and the palladium content in the bulk catalyst was detected by inductively coupled plasma atomic emission spectrometry. The results are shown in Table 1.

[0081]

Example 4

[0082] 11.9 g of glucose and 1 g of urea were weighed and dissolved in 140 mL of deionized water. The solution was stirred until clear to obtain solution A. 0.09 g of a 5 wt% palladium chloroacetic acid solution was weighed as solution B. Solution B was added to solution A and stirred evenly. Then, 14.5 g of tetraethyl orthosilicate was slowly added dropwise. The mixture was hydrolyzed at 45 °C for 24 h. The suspension was then transferred to a homogeneous reactor and reacted at 120 °C for 12 h. The material after the hydrothermal reaction was naturally cooled, filtered, washed, dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to obtain a Pd / SiO2 catalyst with a palladium content of 0.1 wt%. The palladium content on the catalyst surface was quantitatively analyzed by EDS energy dispersive spectroscopy, and the palladium content in the bulk catalyst was detected by inductively coupled plasma optical emission spectrometry. The results are shown in Table 1.

[0083]

Example 5

[0084] 11.9 g of citric acid and 1.9 g of ethylenediamine were weighed and dissolved in 140 mL of deionized water. The solution was stirred until clear to obtain solution A. 0.45 g of 5 wt% palladium chloroacetic acid solution and 0.45 g of 0.1% copper nitrate solution were weighed and mixed evenly to obtain solution B. Solution B was added to solution A and stirred evenly. Then, 14.5 g of tetraethyl orthosilicate was slowly added dropwise. The mixture was hydrolyzed at 45 °C for 24 h. The suspension was then transferred to a homogeneous reactor and reacted at 120 °C for 12 h. The hydrothermal reaction material was naturally cooled, filtered, washed, dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to obtain a Pd / SiO2 catalyst with a palladium content of 0.5 wt% and a copper content of 100 ppm. The palladium content on the catalyst surface was quantitatively analyzed by EDS energy dispersive spectroscopy, and the palladium content in the bulk catalyst was detected by inductively coupled plasma atomic emission spectrometry. The results are shown in Table 1.

[0085] Comparative Example 1

[0086] 0.45 g of a 5 wt% palladium ammonium solution was weighed and dissolved in 4.5 mL of deionized water. The solution was then added dropwise to 4.4 g of SiO2 support to fully wet the support and form a thin liquid film. The solution was allowed to stand for 6 h, dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to obtain a Pd / SiO2 catalyst with a palladium content of 0.5 wt%. The palladium content on the catalyst surface was obtained by EDS energy dispersive spectroscopy, and the palladium content in the bulk catalyst was obtained by inductively coupled plasma atomic emission spectrometry. The results are shown in Table 1.

[0087] Comparative Example 2

[0088] 0.45 g of 5 wt% palladium chloroacetic acid solution was weighed and dissolved in 4.5 mL of deionized water. The solution was then added dropwise to 4.4 g of SiO2 support to fully wet the support and form a thin liquid film. The solution was allowed to stand for 6 h, dried at 110 °C for 12 h, and calcined at 550 °C for 4 h to obtain a Pd / SiO2 catalyst with a palladium content of 0.5 wt%. The palladium content on the catalyst surface was obtained by EDS energy dispersive spectroscopy, and the palladium content in the bulk catalyst was obtained by inductively coupled plasma atomic emission spectrometry. The results are shown in Table 1.

[0089] Comparative Example 3

[0090] Repeat the process of Example 1, except that ethylenediamine is replaced with an equimolar amount of citric acid, while other conditions remain unchanged.

[0091] In this Example 3, there is a problem with palladium loss.

[0092] Comparative Example 4

[0093] Repeat the process of Example 1, except that citric acid is replaced with an equimolar amount of ethylenediamine, while other conditions remain unchanged.

[0094] In this Example 4, there is a problem with palladium loss.

[0095] Table 1:

[0096] Theoretical Pd content (%) Surface Pd content (%) Bulk palladium content (%) Example 1 0.50 0.36 0.49 Example 2 0.10 0.05 0.10 Example 3 0.10 0.07 0.10 Example 4 0.10 0.04 0.09 Example 5 0.50 0.36 0.50 Comparative Example 1 0.50 0.48 0.49 Comparative Example 2 0.50 0.51 0.50 Comparative Example 3 0.50 0.16 0.35 Comparative Example 4 0.50 0.12 0.36

[0097] [Experimental Example 1] Catalyst Evaluation

[0098] The hydrogenolysis product of α,α-dimethylbenzyl alcohol was subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process. The bottom product (i.e., liquid phase by-product) contained cumene and acetophenone, with the content of cumene being 14.5 wt% and the content of acetophenone being 54.6 wt%.

[0099] Hydrogenolysis of liquid phase byproducts: The hydrogenolysis is carried out in a fixed bed using the catalyst prepared in Example 1, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0100] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0101] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0102] [Experimental Example 2] Catalyst Evaluation

[0103] The hydrogenolysis product of α,α-dimethylbenzyl alcohol was subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process. The bottom product (i.e., liquid phase by-product) contained cumene and acetophenone, with the content of cumene being 14.5 wt% and the content of acetophenone being 54.6 wt%.

[0104] Hydrogenolysis of liquid phase byproducts: The hydrogenolysis is carried out in a fixed bed using the catalyst prepared in Example 2, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0105] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0106] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0107] [Experimental Example 3] Catalyst Evaluation

[0108] The hydrogenolysis product of α,α-dimethylbenzyl alcohol was subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process. The bottom product (i.e., liquid phase by-product) contained cumene and acetophenone, with the content of cumene being 14.5 wt% and the content of acetophenone being 54.6 wt%.

[0109] Hydrogenolysis of liquid phase byproducts: The hydrogenolysis is carried out in a fixed bed using the catalyst prepared in Example 3, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0110] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0111] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0112] [Experimental Example 4] Catalyst Evaluation

[0113] The hydrogenolysis product of α,α-dimethylbenzyl alcohol was subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process. The bottom product (i.e., liquid phase by-product) contained cumene and acetophenone, with the content of cumene being 14.5 wt% and the content of acetophenone being 54.6 wt%.

[0114] Hydrogenolysis of liquid phase byproducts: The hydrogenolysis is carried out in a fixed bed using the catalyst prepared in Example 4, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0115] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0116] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0117] [Experimental Example 5] Catalyst Evaluation

[0118] The hydrogenolysis product of α,α-dimethylbenzyl alcohol was subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process. The bottom product (i.e., liquid phase by-product) contained cumene and acetophenone, with the content of cumene being 14.5 wt% and the content of acetophenone being 54.6 wt%.

[0119] Hydrogenolysis of liquid phase byproducts: The hydrogenolysis is carried out in a fixed bed using the catalyst prepared in Example 5, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0120] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0121] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0122]

Comparative Experiment Example 1

[0123] The hydrogenolysis products of α,α-dimethylbenzyl alcohol were subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process, and the material at the bottom of the column was subjected to hydrogenolysis.

[0124] The hydrogenolysis process was carried out in a fixed bed using the catalyst prepared in Comparative Example 1, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0125] After hydrogenolysis, the material is subjected to distillation at a top temperature of 80℃ and a bottom temperature of 160℃. The vaporous cumene at the top is recycled back to the oxidation process, while the bottom material yields high-value-added acetophenone. Side-collected material is discharged externally. The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0126]

Comparative Experiment Example 2

[0127] The hydrogenolysis products of α,α-dimethylbenzyl alcohol were subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process, and the material at the bottom of the column was subjected to hydrogenolysis.

[0128] The hydrogenolysis process was carried out in a fixed bed using the catalyst prepared in Comparative Example 2, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0129] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0130] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0131]

Comparative Experiment Example 3

[0132] The hydrogenolysis products of α,α-dimethylbenzyl alcohol were subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process, and the material at the bottom of the column was subjected to hydrogenolysis.

[0133] The hydrogenolysis process was carried out in a fixed bed using the catalyst prepared in Comparative Example 3, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0134] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0135] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0136]

Comparative Experiment Example 4

[0137] The hydrogenolysis products of α,α-dimethylbenzyl alcohol were subjected to distillation at a top temperature of 80°C and a bottom temperature of 160°C. The vapor phase of cumene at the top of the column was recycled back to the cumene oxidation process, and the material at the bottom of the column was subjected to hydrogenolysis.

[0138] The hydrogenolysis process was carried out in a fixed bed using the catalyst prepared in Comparative Example 4, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0139] After hydrogenolysis, the material is subjected to distillation. The top temperature of the column is 80℃ and the bottom temperature is 160℃. The gaseous cumene at the top of the column is recycled back to the oxidation process, and the material at the bottom of the column is used to obtain high-value-added acetophenone. The side-collected material is discharged externally.

[0140] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0141] Table 2:

[0142] And cumene conversion rate (%) Cumene selectivity (%) Acetophenone yield (%) Experimental Example 1 98.4 99.6 95.6 Experiment Example 2 98.6 99.5 95.7 Experimental Example 3 98.5 99.7 94.9 Experiment Example 4 98.3 99.5 95.3 Experimental Example 5 98.7 99.8 97.1 Comparative Experiment Example 1 90.1 99.1 39.5 Comparative Experiment Example 2 78.9 99.2 40.6 Comparative Experiment Example 3 75.8 99.4 93.5 Comparative Experiment Example 4 76.1 99.3 92.7

[0143] The present invention has been described in detail above with reference to specific embodiments and exemplary examples; however, these descriptions should not be construed as limiting the present invention. Those skilled in the art will understand that various equivalent substitutions, modifications, or improvements can be made to the technical solutions and embodiments of the present invention without departing from the spirit and scope of the invention, and all such modifications and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the appended claims.

Claims

1. A method of making a hydrogenolysis catalyst, the method comprising: (1) Mix the nitrogen source, carbon source and solvent to obtain solution A; (2) Mix the active component precursor and optional auxiliary agent precursor to obtain solution B; the active component is palladium; (3) Mix solution A and solution B, add the support precursor thereto, and react to obtain hydrogenolysis catalyst precursor; (4) The hydrogenolysis catalyst precursor is post-treated to obtain the hydrogenolysis catalyst; the nitrogen source is selected from organic amine compounds, the carbon source is selected from organic compounds containing hydroxyl groups, and the molar ratio of the carbon source to the nitrogen source is 1:(0.05~2).

2. The preparation method according to claim 1, characterized in that, The nitrogen source is selected from one or more of ethylenediamine, aniline, oleylamine, urea, triethylamine, alkanolamines, and amino acids.

3. The preparation method according to claim 1, characterized in that, The carbon source is selected from one or more of glycerol, ethylene glycol, glucose, citric acid, xylitol, fructose, cellulose, polyvinyl alcohol, starch, and biomass.

4. The preparation method according to claim 1, characterized in that, The active component precursor is a water-soluble compound containing the active component; and / or, The carrier precursor is selected from one or more of methyl orthosilicate, tetraethyl orthosilicate, trimethylethoxysilane, methyltriethylsilane, titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, zirconium oxychloride, zirconium nitrate, aluminum nitrate, aluminum isopropoxide, and ferric nitrate; and / or, The precursor of the adjuvant is selected from at least one of copper and / or iron nitrates and / or carbonates, and organic and / or inorganic acids containing boron and / or phosphorus and / or sulfur.

5. The preparation method according to claim 1, characterized in that, The active component precursor is selected from one or more of the chloride, nitrate, acetate, sulfate, and phosphate salts containing the active component; and / or, The precursor of the auxiliary agent is selected from at least one of copper nitrate, basic copper carbonate, ferric nitrate, phosphoric acid, boric acid, and sulfuric acid.

6. The preparation method according to claim 1, characterized in that, The mass ratio of the carbon source to the carrier precursor is 1:(0.1~20).

7. The preparation method according to claim 1, characterized in that, The molar ratio of the carbon source to the nitrogen source is 1:(0.1~1); and / or, The mass ratio of the carbon source to the carrier precursor is 1:(0.5~10).

8. The preparation method according to claim 1, characterized in that, Based on a total weight of 100 wt% for the active component precursor and the support precursor, the amount of the active component precursor is 0.01~5 wt%, wherein the weight of the active component precursor is based on the weight of the metal element therein, and the weight of the support precursor is based on the weight of its corresponding oxide; and / or, Based on a total weight of 100wt% for the active component precursor and the carrier precursor, the amount of the auxiliary agent precursor is 0~1500ppm, wherein the weight of the active component precursor is based on the weight of the metal element therein, the weight of the carrier precursor is based on the weight of its corresponding oxide, and the amount of the auxiliary agent precursor is based on the weight of the auxiliary agent element therein.

9. The preparation method according to claim 1, characterized in that, Based on a total weight of 100 wt% for the active component precursor and the support precursor, the amount of the active component precursor is 0.005~1 wt%, wherein the weight of the active component precursor is based on the weight of the metal element therein, and the weight of the support precursor is based on the weight of its corresponding oxide; and / or, Based on a total weight of 100wt% for the active component precursor and the carrier precursor, the amount of the auxiliary agent precursor is 0~200ppm, wherein the weight of the active component precursor is based on the weight of the metal element therein, the weight of the carrier precursor is based on the weight of its corresponding oxide, and the amount of the auxiliary agent precursor is based on the weight of the auxiliary agent element therein.

10. The preparation method according to claim 1, characterized in that, The reaction temperature is 80℃~300℃; and / or, The reaction time is 4 to 72 hours.

11. The preparation method according to claim 1, characterized in that, The reaction temperature is 100℃~180℃; and / or, The reaction time is 8-24 hours.

12. The method of any one of claims 1 to 11, wherein the method is performed in a single step. The post-processing includes washing, drying, and roasting.

13. The preparation method according to claim 12, characterized in that, The drying temperature is 50~200℃ and the time is 4~24h; and / or the calcination temperature is 300~600℃ and the time is 4~12h.

14. A hydrogenolysis catalyst obtained by the preparation method according to any one of claims 1 to 13.

15. The use of the hydrogenolysis catalyst obtained by the preparation method according to any one of claims 1 to 13 in the treatment of hydrogenolysis products of α,α-dimethylbenzyl alcohol.

16. The application according to claim 15, characterized in that, Used to process the material after removing cumene from the hydrogenolysis product of α,α-dimethylbenzyl alcohol.

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