A method, system and use thereof for processing alpha,alpha-dimethylbenzyl alcohol hydrogenolysis products

Abstract

The application discloses a kind of processing alpha, alpha-dimethyl benzyl alcohol hydrogenolysis product method, system and its application, the method includes: (1) recovery alpha, alpha-dimethyl benzyl alcohol hydrogenolysis product in isopropyl benzene, and obtain liquid phase by-product;(2) sequentially carry out hydrogenolysis treatment and product separation treatment to the liquid phase by-product.In step (1), recovery alpha, alpha-dimethyl benzyl alcohol hydrogenolysis product in isopropyl benzene is recovered by rectification, isopropyl benzene is recovered in tower top, and liquid phase by-product is obtained in tower pot;In step (2), the product separation treatment is carried out by rectification.The system includes rectification unit I, hydrogenolysis unit and rectification unit II connected in sequence, the material outlet I of the rectification tower I, the hydrogenolysis unit and the feed inlet II of the rectification tower II are connected in sequence.The method or system of the application can efficiently recover isopropyl benzene and isopropyl benzene, reduce the unit consumption of isopropyl benzene in the process of preparing PO by CHP method, and improve the technical advancement.

Description

Technical Field

[0001] This invention relates to the treatment of α,α-dimethylbenzyl alcohol hydrogenolysis products, and more particularly to a method, system, and application for treating α,α-dimethylbenzyl alcohol hydrogenolysis products. Background Technology

[0002] Propylene oxide (PO) is an important organic chemical intermediate, mainly used in the production of polyurethane raw materials—polyether polyols. Currently, industrial PO production processes mainly include the chlorohydrin process, co-oxidation process (PO / styrene monomer process, PO / tert-butanol process, PO / methyl tert-butyl ether process), cumene hydroperoxide process (CHP process), and hydrogen peroxide oxidation process (HPPO process). Before 2007, global PO production technology was mainly based on the chlorohydrin process and co-oxidation process, accounting for approximately 97% of PO production capacity. With increasing emphasis on environmental protection, optimization and adjustment of chemical product structure, and successful development of new technologies, PO production technology has undergone significant changes. Adopting new green PO production processes without co-products, such as the CHP process, will be the future development direction for PO synthesis and a priority technology route for new PO plants.

[0003] In 1998, Sumitomo Chemical Co., Ltd. successfully developed a novel CHP process for producing PO. This technology mainly includes processes such as cumene oxidation, propylene epoxidation, and α,α-dimethylbenzyl alcohol hydrogenolysis (DMBA). Theoretically, this process consumes only 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 prone to triggering 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 per unit volume during the process. These heavy components are ultimately enriched in the bottom of the cumene recovery tower in the cumene recovery unit along with the feed material. Figure 2 ).

[0005] In existing technologies, this tar is treated as waste liquid, which wastes resources. There are few technical solutions for reusing the by-products of α,α-dimethylbenzyl alcohol hydrogenolysis, especially for recovering the high-value-added by-product acetophenone and for adding value to cumene to make up for the consumption of cumene. Summary of the Invention

[0006] In order to overcome the problems in the prior art, the present application provides a method for treating α,α-dimethylbenzyl alcohol hydrogenolysis product, a system and application thereof. In the method for treating α,α-dimethylbenzyl alcohol hydrogenolysis product, cumene can be efficiently recovered to isopropylbenzene, the isopropylbenzene consumption in the CHP method for preparing PO is reduced, the technical advancement is improved, meanwhile, in the α,α-dimethylbenzyl alcohol hydrogenolysis product treatment method, cumene with a boiling point close to that of high-value byproduct acetophenone is preferentially hydrogenolyzed to isopropylbenzene with a lower boiling point, the acetophenone is maximally reserved, high-purity byproduct acetophenone can be obtained in the subsequent rectification tower, the late byproduct separation cost is effectively reduced, and the method has high industrial application value.

[0007] One of the objects of the present application is to provide a method for treating α,α-dimethylbenzyl alcohol hydrogenolysis product, comprising:

[0008] (1) recovering isopropylbenzene in the α,α-dimethylbenzyl alcohol hydrogenolysis product to obtain isopropylbenzene and liquid-phase byproducts;

[0009] (2) sequentially performing hydrogenolysis treatment and product separation treatment on the liquid-phase byproducts.

[0010] In the present application, cumene with a boiling point close to that of high-value byproduct acetophenone is preferentially hydrogenolyzed to isopropylbenzene with a lower boiling point, and the acetophenone in the α,α-dimethylbenzyl alcohol hydrogenolysis product is largely reserved, so that high-purity byproduct acetophenone is obtained in the subsequent separation treatment, and the byproduct separation cost is effectively reduced.

[0011] Preferably, the α,α-dimethylbenzyl alcohol hydrogenolysis product is the α,α-dimethylbenzyl alcohol hydrogenolysis product from the CHP method for preparing propylene oxide.

[0012] In a preferred embodiment, in step (1), the isopropylbenzene in the α,α-dimethylbenzyl alcohol hydrogenolysis product is recovered by distillation (in a rectification tower), wherein isopropylbenzene is obtained at the top of the tower, and liquid-phase byproducts are obtained at the bottom of the tower.

[0013] In a further preferred embodiment, in step (1), the distillation treatment is performed under the following conditions: the top temperature is 50-120℃, and the bottom temperature is 130-200℃.

[0014] In a still further preferred embodiment, in step (1), the distillation treatment is performed under the following conditions: the top temperature is 75-100℃, and the bottom temperature is 145-170℃.

[0015] For example, in step (1), the conditions of the rectification treatment are: the overhead temperature is 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C or 120°C, and the bottom temperature is 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 200°C.

[0016] In step (1), isopropylbenzene is recovered at the overhead, and other by-products including cumene and isopropylbenzene are mainly in the liquid phase by-products at the bottom of the column.

[0017] In a preferred embodiment, in step (1), the liquid phase by-products contain cumene and acetophenone, wherein the weight content of cumene is 5wt%-50wt%, and the weight content of acetophenone is 40wt%-80wt%.

[0018] In a further preferred embodiment, in step (1), the weight content of cumene is 10wt%-30wt%, and the weight content of acetophenone is 45wt%-65wt%.

[0019] For example, in step (1), the weight content of cumene is 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or 50wt%, and the weight content of acetophenone is 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt% or 80wt%.

[0020] In step (1), cumene and acetophenone are recovered after being concentrated with other impurities, and enter the hydrogenolysis treatment in step (2), in which isopropylbenzene can be recovered, the isopropylbenzene consumption in the process of preparing PO by CHO method can be reduced, high value-added by-product acetophenone can be recovered, and the process economy can be increased.

[0021] In a preferred embodiment, in step (2), the temperature of the hydrogenolysis treatment is 190-350°C; and / or, the pressure of the hydrogenolysis treatment is 0.1-10MPA.

[0022] In a further preferred embodiment, in step (2), the temperature of the hydrogenolysis treatment is 225-260°C; and / or, the pressure of the hydrogenolysis treatment is 0.3-2MPA.

[0023] For example, the temperature of the hydrogenolysis treatment is 190°C, 200°C, 230°C, 250°C, 280°C, 300°C, 330°C, or 350°C; and / or, the pressure of the hydrogenolysis treatment is 0.1 MPA, 0.5 MPA, 1 MPA, 2 MPA, 3 MPA, 4 MPA, 5 MPA, 6 MPA, 7 MPA, 8 MPA, 9 MPA, or 10 MPA.

[0024] In a preferred embodiment, in step (2), the product separation treatment is performed by distillation.

[0025] In a further preferred embodiment, the distillation treatment is performed under the conditions of a column top temperature of 50-120°C and a column bottom temperature of 130-200°C.

[0026] For example, in step (2), the product separation treatment is performed by distillation under the conditions of a column top temperature of 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C and a column bottom temperature of 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, or 200°C.

[0027] In a preferred embodiment, the hydrogenolysis treatment in step (2) is performed in the presence of a catalyst, which comprises a support and an active component, which is distributed on the surface and optionally in the interior of the support, wherein the bulk active component content of the catalyst is greater than or equal to the surface active component content (preferably the bulk active component content is greater than the surface active component content) based on 100 wt% of the total content of the support and the active component; preferably, the bulk active component content of the catalyst is 0.01-5 wt% and the surface active component content of the catalyst is 0.005-3 wt%.

[0028] In a further preferred embodiment, the support is selected from at least one of a metal oxide, activated carbon; and / or, the active component is selected from a noble metal.

[0029] In a further preferred embodiment, the support is selected from at least one of alumina, silica, activated carbon, titania, zirconia, iron oxide, preferably silica; and / or, the active component is palladium.

[0030] In a preferred embodiment, the bulk active component content of the catalyst is greater than or equal to the surface active component content (preferably the bulk active component content is greater than the surface active component content) based on 100 wt% of the total content of the support and the active component; preferably, the bulk active component content of the catalyst is 0.05-1 wt% and the surface active component content of the catalyst is 0.025-0.5 wt%.

[0031] For example, 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% based on the total content of the carrier and active component being 100 wt%; and the surface active component content of the catalyst is 0.025 wt%, 0.05 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt% or 0.5 wt%.

[0032] In a preferred embodiment, the catalyst further optionally contains an auxiliary agent (i.e. the catalyst comprises a carrier, an active component and optionally an auxiliary agent).

[0033] In a further preferred embodiment, the auxiliary agent is selected from at least one of copper, iron, boron, phosphorus, sulfur.

[0034] In a still further preferred embodiment, the content of the auxiliary agent is 0-1500 ppm (e.g. 20-1500 ppm), preferably 0-200 ppm (e.g. 50-200 ppm) based on the total content of the carrier and active component being 100 wt%.

[0035] 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 the total content of the carrier and active component being 100 wt%.

[0036] In a preferred embodiment, the method for preparing the catalyst comprises adding a carrier precursor to a solution containing a nitrogen source, a carbon source, a precursor of an active component and optionally a precursor of an auxiliary agent, and after reaction, performing post-treatment to obtain the hydrogenolysis catalyst.

[0037] In a further preferred embodiment, the nitrogen source is selected from organic amine compounds; and / or, the carbon source is selected from organic compounds containing hydroxyl groups.

[0038] In a still further preferred embodiment, the nitrogen source is selected from one or more of ethylenediamine, aniline, oleylamine, urea, triethylamine, alcohol amine compounds and amino acids; and / or, the carbon source is selected from one or more of glycerol, ethylene glycol, glucose, citric acid, xylitol, fructose, cellulose, polyvinyl alcohol, starch and biomass.

[0039] Preferably, the carbon source and the nitrogen source are different substances.

[0040] In the present application, the nitrogen source and the carbon source mainly play two roles, 1) a structural template of the carrier, 2) complexing noble metals (e.g. palladium).

[0041] In a preferred embodiment, the active component precursor is a water-soluble compound containing active component, preferably, the active component precursor is selected from one or more of chlorides, nitrates, acetates, sulfates and phosphates containing active component.

[0042] In a preferred embodiment, the carrier precursor is selected from one or more of tetramethylorthosilicate, tetraethylorthosilicate, trimethylethoxysilane, methyltriethysilane, titanium tetrachloride, tetrabutyl titanate, isopropyl titanate, zirconium oxychloride, zirconium nitrate, aluminum nitrate, aluminum isopropoxide, ferric nitrate, sodium ferrate.

[0043] In a preferred embodiment, the assistant precursor is selected from at least one of copper nitrate, basic copper carbonate, ferric nitrate, phosphoric acid, boric acid, sulfuric acid.

[0044] In a preferred embodiment, the solvent is water.

[0045] In the present application, the hydrogenolysis treatment of step (2) is carried out in a fixed bed.

[0046] 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), more preferably 1:(0.1-0.5).

[0047] 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.

[0048] 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.

[0049] 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).

[0050] 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.

[0051] In a preferred embodiment, the amount of the active component precursor is 0.01-5wt%, preferably 0.005-1wt%, based on 100wt% of the total weight of the active component precursor and the carrier precursor, 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.

[0052] For example, the active component precursor is used in an amount of 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%, based on 100 wt% of the total weight of the active component precursor and the carrier precursor, wherein the weight of the active component precursor is based on the weight of the metal element thereof, and the weight of the carrier precursor is based on the weight of the corresponding oxide thereof.

[0053] In a preferred embodiment, the additive precursor is used in an amount of 0-1500 ppm (e.g. 20-1500 ppm), preferably 0-200 ppm (e.g. 50-200 ppm), based on 100 wt% of the total weight of the active component precursor and the carrier precursor, wherein the weight of the active component precursor is based on the weight of the metal element thereof, and the weight of the carrier precursor is based on the weight of the corresponding oxide thereof, and the amount of the additive precursor is based on the weight of the additive element thereof.

[0054] In a preferred embodiment, the reaction is carried out at a temperature of 80-300 °C for a time period of 4-72 h.

[0055] In a further preferred embodiment, the reaction is carried out at a temperature of 100-180 °C for a time period of 8-24 h.

[0056] In a preferred embodiment, when the carrier precursor is selected from at least one of tetramethyl orthosilicate, tetraethyl orthosilicate, trimethylethoxysilane, methyltriethylsilane, tetrabutyl titanate, isopropyl titanate, a hydrolysis treatment is carried out prior to the reaction.

[0057] In a further preferred embodiment, the hydrolysis treatment is carried out at a temperature of 20-70 °C for a time period of 5-50 h, preferably at a temperature of 30-60 °C for a time period of 15-30 h.

[0058] 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 period of the hydrolysis treatment is 5 h, 10 h, 15 h, 20 h, 25 h, 30 h, 35 h, 40 h, 45 h or 50 h.

[0059] In a preferred embodiment, the preparation method comprises:

[0060] (A) mixing the nitrogen source, the carbon source and the solvent to obtain solution A;

[0061] (B) mixing the active component precursor and optionally the additive precursor to obtain solution B;

[0062] (C) mixing the solution A and the solution B, (slowly) adding a carrier precursor thereto, and obtaining a hydrogenolysis catalyst precursor by reaction;

[0063] wherein, preferably, the carrier precursor is (slowly) added thereto for sufficient mixing and to prevent the occurrence of large particles.

[0064] (D) post-treating the hydrogenolysis catalyst precursor to obtain the hydrogenolysis catalyst.

[0065] In a preferred embodiment, the post-treatment comprises washing, drying and calcination.

[0066] In a further preferred embodiment, the drying is at a temperature of 50-200°C, preferably 60-150°C, for a time of 4-24h, preferably 8-15h; and / or, the calcination is at a temperature of 300-600°C, preferably 500-600°C, for a time of 4-12h, preferably 4-8h.

[0067] For example, the drying is at a temperature of 50°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C or 200°C, for a time of 4h, 8h, 12h, 16h, 20h or 24h; and / or, the calcination is at a temperature of 300°C, 400°C, 500°C or 600°C, for a time of 4h, 4.5h, 5h, 6h, 7h, 8h, 9h, 10h, 11h or 12h.

[0068] In the present application, no special separation and purification is required for the liquid phase by-product after recovery of cumene, the method of the present application allows the liquid phase by-product to contain other impurities in addition to cumene, such as acetophenone / phenol, etc., while, by reasonably controlling the hydrogenolysis at high temperature in step (2), no isopropylcyclohexane by-product is produced, and by controlling the overhead temperature and the bottom temperature of the rectification treatment in step (2) within the range defined in the present application, no other impurities are mixed into the overhead gas phase, and thus the overhead gas phase contains only cumene, and the bottom contains only acetophenone, a high value-added product. Therefore, the method of the present application is relatively simple and does not require pre-removal of impurities.

[0069] The second object of the present application is to provide a system for treating the hydrogenolysis product of α,α-dimethylbenzyl alcohol, preferably for carrying out the method of the first object of the present application, which comprises a rectification unit I, a hydrogenolysis unit and a rectification unit II connected in sequence.

[0070] In a preferred embodiment, the feed of the rectification unit I is the hydrogenolysis product of α,α-dimethylbenzyl alcohol, in particular the hydrogenolysis product of α,α-dimethylbenzyl alcohol from the process for preparing propylene oxide by CHP method.

[0071] In a preferred embodiment, the rectification unit I is a rectification column I; and / or, the rectification unit II is a rectification column II.

[0072] In a further preferred embodiment, the rectification column I is provided with a feed inlet I, an overhead outlet I and a column bottom outlet I; and / or, the rectification column II is provided with a feed inlet II, an overhead outlet II, a column bottom outlet II and a side draw outlet.

[0073] In a still further preferred embodiment, the column bottom outlet I of the rectification column I, the hydrogenolysis unit and the feed inlet II of the rectification column II are connected in sequence.

[0074] In a preferred embodiment, the processing conditions of the rectification column I are: the overhead temperature is 50-120℃, and the column bottom temperature is 130-200℃.

[0075] In a further preferred embodiment, the processing conditions of the rectification column I are: the overhead temperature is 75-100℃, and the column bottom temperature is 145-170℃.

[0076] In a preferred embodiment, the hydrogenolysis unit is a hydrogenolysis reactor, in which the hydrogenolysis catalyst of the present application is loaded.

[0077] In a preferred embodiment, the processing conditions of the rectification column II are: the overhead temperature is 50-120℃, and the column bottom temperature is 130-200℃.

[0078] In a further preferred embodiment, the processing conditions of the rectification column II are: the overhead temperature is 75-100℃, and the column bottom temperature is 145-170℃.

[0079] The third object of the present application is to provide the use of the method of the first object of the present application or the system of the second object of the present application in the preparation of propylene oxide, especially in the CHP method for the preparation of propylene oxide.

[0080] The fourth object of the present application is to provide a method for the preparation of propylene oxide, comprising an isopropylbenzene oxidation process, a propylene epoxidation process, an α,α-dimethylbenzyl alcohol hydrogenolysis process and a process for treating the hydrogenolysis product of α,α-dimethylbenzyl alcohol, wherein the process for treating the hydrogenolysis product of α,α-dimethylbenzyl alcohol is carried out by the method of the first object of the present application or the system of the second object of the present application.

[0081] Preferably, the method comprises the following steps:

[0082] (a) an isopropylbenzene oxidation process: isopropylbenzene is subjected to an oxidation reaction in the presence of an oxygen-containing gas to obtain a cumene hydroperoxide;

[0083] (b) Propylene epoxidation process: In the presence of a catalyst, cumene hydroperoxide reacts with propylene to give a mixture of propylene oxide and α,α-dimethylbenzyl alcohol, which are then separated to give propylene oxide and α,α-dimethylbenzyl alcohol respectively.

[0084] (c) Hydrogenolysis of α,α-dimethylbenzyl alcohol: In the presence of a catalyst, α,α-dimethylbenzyl alcohol reacts with hydrogen to obtain hydrogenolysis products;

[0085] (d) The hydrogenolysis product is processed using the method described in one objective of the present invention or the system described in another objective of the present invention, wherein the obtained cumene is recycled back to the cumene oxidation process, and the obtained acetophenone is used as a high-value-added byproduct.

[0086] The reaction conditions and catalysts used in the cumene oxidation process, propylene epoxidation process, and α,α-dimethylbenzyl alcohol hydrogenolysis process are all carried out using existing technologies and are not specifically limited in this regard.

[0087] 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.

[0088] Compared with the prior art, the present invention has the following beneficial effects:

[0089] (1) The method for treating the hydrogenolysis product of α,α-dimethylbenzyl alcohol described in this invention can efficiently recover cumene to cumene, reduce the consumption of cumene in the process of producing PO by CHP, reduce the cost of separating by-products in the later stage, and efficiently recover the high-value-added by-product acetophenone, which has high industrial application value.

[0090] (2) The method for treating the hydrogenolysis products of α,α-dimethylbenzyl alcohol described in this invention does not require the addition of a hydrogenation reactor and its hydrogenation catalyst to the existing process equipment, which effectively reduces the investment cost;

[0091] (3) The method for processing the hydrogenolysis product of α,α-dimethylbenzyl alcohol described in this invention can efficiently recover cumene to cumene, reduce the consumption of cumene in the process of producing PO by CHP, and reduce the cost of separating by-products in the later stage, which has high industrial application value. Attached Figure Description

[0092] Figure 1The figure shows the thermal decomposition reaction of cumene hydroperoxide and the formation of cumyl and acetophenone impurities.

[0093] Figure 2 The figure shows the process of PO production by CHP method in the prior art.

[0094] Figure 3 The figure shows the process of PO production by CHP method in the prior art. DETAILED DESCRIPTION

[0095] The following specific embodiments of the present application will be described in detail, it is necessary to point out that the following examples are only used to further illustrate the present application, can not be understood as limiting the scope of protection of the present application, the skilled in the art according to the content of the present application to make some non-essential improvements and adjustment of the present application still belongs to the scope of protection of the present application.

[0096] In addition, it should be noted that the various specific technical features described in the following detailed description, in the case of no contradiction, can be combined by any suitable way. In order to avoid unnecessary repetition, the present application does not describe the various possible combinations.

[0097] In addition, the various embodiments of the present application can also be combined arbitrarily, as long as it does not deviate from the idea of the present application, thus forming a technical solution which belongs to the original disclosure of the present specification, and also falls within the scope of protection of the present application.

[0098] The raw materials used in the examples and comparative examples, if not specifically limited, are disclosed in the prior art, such as can be directly purchased or prepared according to the preparation method disclosed in the prior art.

[0099] In the examples: the titanium-containing silicon oxide catalyst in the epoxidation process is prepared according to Example 2 of the published patent CN104437635B; the catalyst Pd / Al2O3 in the hydrogenolysis of benzyl alcohol can be used simultaneously in the dehydration and hydrogenation processes, and is prepared according to Example 4 of the published patent CN104151129B.

[0100] The hydrogenolysis product of α,α-dimethylbenzyl alcohol treated in the examples is obtained as follows:

[0101] The cumene washed with aqueous NaOH solution and oxygen are introduced into the oxidation reactor for oxidation reaction, the temperature and pressure of the oxidation reaction are 90℃ and 300kPaG respectively, the O2 content of the tail gas is controlled to be less than 0.5%, the reaction time is 0.5 hours, and a stream containing cumene hydroperoxide (CHP) is obtained.

[0102] The stream containing cumene hydroperoxide (CHP) obtained above is reacted with propylene in the presence of a titanium-containing silicon oxide compound catalyst TiSiO2 to produce a stream containing propylene oxide and α,α-dimethylbenzyl alcohol. The reaction temperature is 75°C, the reaction pressure is 5000 kPaG, the molar ratio of propylene to cumene hydroperoxide (CHP) is 8:1, the weight hourly space velocity of cumene hydroperoxide (CHP) is 0.8 h -1 .

[0103] The stream flowing out of the epoxidation reactor is separated to obtain a crude propylene oxide and a stream containing α,α-dimethylbenzyl alcohol, and the excess propylene is recovered and recycled. The crude propylene oxide obtained by separation is further rectified and purified to obtain a refined PO product. Specifically, the stream flowing out of the epoxidation reactor is introduced into two rectification columns, rectification column one and rectification column two, in sequence, and unreacted propylene and crude propylene oxide are separated from the top of the columns in sequence. The conditions of rectification column one are: the top temperature is 50°C, and the pressure is 1800 kPaG. The conditions of rectification column two are: the top temperature is 45°C, and the pressure is -50 kPaG.

[0104] The stream containing α,α-dimethylbenzyl alcohol is introduced into a benzyl alcohol hydrogenolysis process, and α-methylstyrene is obtained by dehydration in the presence of a catalyst Pd / Al2O3. The reaction temperature is 155°C, the reaction pressure is 2000 kPaG, and the weight hourly space velocity of α,α-dimethylbenzyl alcohol is 1.4 h -1 . The mixture of α-methylstyrene obtained is introduced into a hydrogenation process. In the presence of a hydrogenation catalyst Pd / Al2O3, α-methylstyrene reacts with hydrogen to produce cumene, which is recycled to the oxidation process. The hydrogenation reaction temperature is 155°C, the reaction pressure is 2000 kPaG, the molar ratio of hydrogen to α-methylstyrene is 8:1, and the weight hourly space velocity of α-methylstyrene is 1 h -1 . The hydrogenolysis product is obtained by the above benzyl alcohol hydrogenolysis process.

[0105] In the embodiments of the present application:

[0106] cumene conversion rate = (cumene content in the raw material - cumene content in the product) / cumene content in the raw material;

[0107] cumene selectivity = 2.38 * (mole number of cumene in the product + mole number of AMS) / (cumene content in the raw material - cumene content in the product);

[0108] acetophenone yield = mass of acetophenone in unit product / theoretical amount of acetophenone in unit raw material.

[0109]

Example 1

[0110] Take 12.5 g of glucose and 2.0 g of ethylenediamine, dissolve in 150 mL of deionized water, stir to dissolve until the solution is clear, to obtain solution A. Take 0.45 g of 5 wt% chloropalladic acid solution as solution B, add solution B to solution A, stir evenly, then slowly drop 14.5 g of tetraethyl orthosilicate, hydrolyze at 50℃ for 18 h, then transfer the suspension to a homogeneous reactor, react at 110℃ for 12 h, naturally cool the hydrothermal reaction material, filter, wash, dry at 110℃ for 10 h, and calcine at 550℃ for 4.5 h, to obtain a Pd / SiO2 catalyst with a palladium content of 0.5 wt% (named C-1). The surface palladium content of the catalyst is quantitatively analyzed by EDS energy spectrum, and the bulk palladium content of the catalyst is detected by inductively coupled plasma spectroscopy. The results are shown in Table 1.

[0111] The hydrogenolysis product of α,α-dimethylbenzyl alcohol is subjected to rectification treatment, the overhead temperature is 80℃, the bottom temperature is 160℃, the overhead gas phase cumene is recycled back to the cumene oxidation process, and the bottom material (i.e. the liquid phase by-product) includes cumene and acetophenone, wherein the content of cumene is 14.5 wt% and the content of acetophenone is 54.6 wt%.

[0112] The liquid phase by-product is subjected to hydrogenolysis treatment: the hydrogenolysis treatment is carried out in a fixed bed, and the catalyst prepared in Example 1 is selected, the reaction temperature is 230℃, and the pressure is 0.5 MPa.

[0113] The material after hydrogenolysis treatment is subjected to rectification treatment, the overhead temperature is 80℃, the bottom temperature is 160℃, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material is obtained as high value-added acetophenone, and the side material is discharged.

[0114] The conversion of cumene and the yield of acetophenone are shown in Table 2.

[0115]

Example 2

[0116] Take 12.5 g of glucose and 2.0 g of ethylenediamine, dissolve in 150 mL of deionized water, stir to dissolve until the solution is clear, to obtain solution A. Take 0.45 g of 5 wt% chloropalladic acid solution as solution B, add solution B to solution A, stir evenly, then slowly drop 14.5 g of tetraethyl orthosilicate, hydrolyze at 50℃ for 18 h, then transfer the suspension to a homogeneous reactor, react at 110℃ for 12 h, naturally cool the hydrothermal reaction material, filter, wash, dry at 110℃ for 10 h, and calcine at 550℃ for 4.5 h, to obtain a Pd / SiO2 catalyst with a palladium content of 0.5 wt% (named C-1). The surface palladium content of the catalyst is quantitatively analyzed by EDS energy spectrum, and the bulk palladium content of the catalyst is detected by inductively coupled plasma spectroscopy. The results are shown in Table 1.

[0117] The hydrogenolysis product of the α,α-dimethylbenzyl alcohol is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the cumene oxidation process, and the bottom material (i.e. the liquid phase by-product) includes cumene and acetophenone, wherein the content of cumene is 14.5wt%, and the content of acetophenone is 54.6wt%.

[0118] The liquid phase by-product is subjected to hydrogenolysis treatment: the hydrogenolysis treatment is carried out in a fixed bed, the catalyst prepared in Example 2 is selected, the reaction temperature is 230°C, and the pressure is 0.5MPa.

[0119] The material after the hydrogenolysis treatment is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side material is discharged.

[0120] The conversion of cumene and the yield of acetophenone are shown in Table 2.

[0121]

Example 3

[0122] 12.5g of glucose and 1.0g of ethylenediamine are weighed and dissolved in 150mL of deionized water, stirred and dissolved until the solution is clear, to obtain solution A. 0.32g of a 5wt% concentration of chloropalladic acid solution is weighed as solution B, and solution B is added to solution A, stirred uniformly, and then 14.5g of tetraethyl orthosilicate is slowly dropped, hydrolyzed at 50°C for 18h, and then the suspension is transferred to a homogeneous reactor, reacted at 110°C for 12h, the material after the hydrothermal reaction is naturally cooled, filtered, washed, dried at 110°C for 10h, and calcined at 550°C for 4.5h, to obtain a Pd / SiO2 catalyst with a palladium content of 0.5wt% (named C-3), and a Pd / SiO2 catalyst with a palladium content of 0.35wt% (named C-4). The surface palladium content of the catalyst is obtained by EDS energy spectrum quantitative analysis, and the bulk palladium content of the catalyst is obtained by inductively coupled plasma spectrometry, and the results are shown in Table 1.

[0123] The hydrogenolysis product of the α,α-dimethylbenzyl alcohol is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the cumene oxidation process, and the bottom material (i.e. the liquid phase by-product) includes cumene and acetophenone, wherein the content of cumene is 14.5wt%, and the content of acetophenone is 54.6wt%.

[0124] The liquid phase by-product is subjected to hydrogenolysis treatment: the hydrogenolysis treatment is carried out in a fixed bed, the catalyst prepared in Example 3 is selected, the reaction temperature is 230°C, and the pressure is 0.5MPa.

[0125] The hydrogenolysis treated material is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side-drawn material is discharged.

[0126] The conversion of cumene and the yield of acetophenone are shown in Table 2.

[0127]

Example 4

[0128] 11.9g of citric acid and 1g of urea are weighed and dissolved in 140mL of deionized water, and stirred and dissolved until the solution is clear to obtain solution A. 0.09g of a 5wt% chloropalladic acid solution is weighed as solution B, and solution B is added to solution A and stirred uniformly, and then 14.5g of tetraethyl orthosilicate is slowly dropped, hydrolyzed at 50°C for 18h, and then the suspension is transferred to a homogeneous reactor, and reacted at 110°C for 12h. The hydrothermally reacted material is naturally cooled, filtered, washed, dried at 110°C for 10h, and calcined at 550°C for 4.5h to obtain a Pd / SiO2 catalyst with a palladium content of 0.1wt% (named C-4). The surface palladium content of the catalyst is obtained by EDS energy spectrum quantitative analysis, and the bulk palladium content of the catalyst is obtained by inductively coupled plasma spectrometry, and the results are shown in Table 1.

[0129] The hydrogenolysis treated material is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side-drawn material is discharged.

[0130] The hydrogenolysis treated material is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side-drawn material is discharged.

[0131] The hydrogenolysis treated material is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side-drawn material is discharged.

[0132] The conversion of cumene and the yield of acetophenone are shown in Table 2.

[0133]

Example 5

[0134] The hydrogenolysis treated material is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side-drawn material is discharged.

[0135] The hydrogenolysis treatment was carried out in a fixed bed using the catalyst C-1 prepared in Example 1, at a reaction temperature of 250°C and a pressure of 0.5 MPa.

[0136] The material after the hydrogenolysis treatment was subjected to rectification treatment, with a top temperature of 80°C and a bottom temperature of 160°C. The isopropylbenzene in the gas phase at the top was recycled back to the oxidation process, and the material at the bottom was obtained as high-value-added acetophenone, which was discharged from the side of the column.

[0137] The conversion of cumene and the yield of acetophenone are shown in Table 2.

[0138]

Example 6

[0139] The material after the hydrogenolysis treatment was subjected to rectification treatment, with a top temperature of 80°C and a bottom temperature of 160°C. The isopropylbenzene in the gas phase at the top was recycled back to the oxidation process, and the material at the bottom was obtained as high-value-added acetophenone, which was discharged from the side of the column.

[0140] The hydrogenolysis treatment was carried out in a fixed bed using the catalyst C-1 prepared in Example 1, at a reaction temperature of 230°C and a pressure of 1.0 MPa.

[0141] The material after the hydrogenolysis treatment was subjected to rectification treatment, with a top temperature of 80°C and a bottom temperature of 160°C. The isopropylbenzene in the gas phase at the top was recycled back to the oxidation process, and the material at the bottom was obtained as high-value-added acetophenone, which was discharged from the side of the column. The conversion of cumene and the yield of acetophenone are shown in Table 2.

[0142]

Example 7

[0143] A solution A was prepared by dissolving 12.5 g of glucose and 2.0 g of ethylenediamine in 150 mL of deionized water and stirring until the solution was clear. A solution B was prepared by uniformly mixing 0.45 g of a chloropalladic acid solution with a concentration of 5 wt% and 0.68 g of a copper nitrate solution with a concentration of 0.1%. The solution B was added to the solution A, and then 14.5 g of tetraethyl orthosilicate was slowly added dropwise. The mixture was hydrolyzed at 50°C for 18 h, and then the suspension was transferred to a homogeneous reactor and reacted at 110°C for 12 h. The material after the hydrothermal reaction was naturally cooled, filtered, washed, dried at 110°C for 10 h, and calcined at 550°C for 4.5 h to obtain a Pd / SiO2 catalyst (named as C-5) with a palladium content of 0.5 wt% and a copper content of 150 ppm. The surface palladium content of the catalyst was quantitatively analyzed by EDS spectroscopy, and the bulk palladium content of the catalyst was detected by inductively coupled plasma spectroscopy. The results are shown in Table 1.

[0144] The hydrogenolysis product of the α,α-dimethylbenzyl alcohol is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the cumene oxidation process, and the bottom material (i.e. the liquid phase by-product) includes cumene and acetophenone, wherein the content of cumene is 14.5wt%, and the content of acetophenone is 54.6wt%.

[0145] The liquid phase by-product is subjected to hydrogenolysis treatment: the hydrogenolysis treatment is carried out in a fixed bed, and catalyst C-5 prepared in this example 7 is selected, the reaction temperature is 230°C, and the pressure is 0.5MPa.

[0146] The material after the hydrogenolysis treatment is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side-drawn material is discharged.

[0147] The conversion result of cumene and the yield of acetophenone are shown in Table 2.

[0148]

Example 8

[0149] 0.45g of a 5wt% chloropalladic acid solution is dissolved in 2.0mL of deionized water, and is added dropwise to 4.4g of an alumina carrier, the carrier is fully wetted and a thin liquid film is formed, and is left to stand for 4h, is dried at 110°C for 10h, and is calcined at 550°C for 4.5h, to obtain a Pd / Al2O3 catalyst (named as C-6) with a palladium content of 0.5wt%, the surface palladium content of the catalyst is obtained by EDS energy spectrum quantitative analysis, and the bulk palladium content of the catalyst is obtained by inductively coupled plasma spectrometry, and the results are shown in Table 1.

[0150] The hydrogenolysis product of the α,α-dimethylbenzyl alcohol is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the cumene oxidation process, and the bottom material is subjected to hydrogenolysis treatment;

[0151] The hydrogenolysis treatment is carried out in a fixed bed, and the catalyst prepared in this example 8 is selected, the reaction temperature is 230°C, and the pressure is 0.5MPa.

[0152] The material after the hydrogenolysis treatment is subjected to rectification treatment, the overhead temperature is 80°C, the bottom temperature is 160°C, the overhead gas phase cumene is recycled back to the oxidation process, and the bottom material obtains high value-added acetophenone, and the side-drawn material is discharged.

[0153] The conversion result of cumene and the yield of acetophenone are shown in Table 2.

[0154]

Example 9

[0155] A 0.09 g sample of a 5 wt% palladium chloride solution was dissolved in 2.0 mL of deionized water and added dropwise to 4.4 g of an alumina carrier. The carrier was thoroughly wetted and a thin liquid film was formed. The mixture was allowed to stand for 4 h, dried at 110°C for 10 h, and calcined at 550°C for 4.5 h to obtain a Pd / Al2O3 catalyst (designated C-7) having a palladium content of 0.1 wt%. The surface palladium content of the catalyst was determined by EDS energy spectrum quantitative analysis, and the bulk palladium content of the catalyst was determined by inductively coupled plasma spectrometry. The results are shown in Table 1.

[0156] The hydrogenolysis product was subjected to distillation treatment, the overhead temperature was 80°C, the bottom temperature was 160°C, the overhead gas phase cumene was recycled to the cumene oxidation process, and the bottom material was subjected to hydrogenolysis treatment;

[0157] The hydrogenolysis treatment was carried out in a fixed bed using the catalyst prepared in this example 10, the reaction temperature was 230°C, and the pressure was 0.5 MPa.

[0158] The hydrogenolysis product was subjected to distillation treatment, the overhead temperature was 80°C, the bottom temperature was 160°C, the overhead gas phase cumene was recycled to the cumene oxidation process, and the bottom material was subjected to hydrogenolysis treatment;

[0159] The conversion of cumene and the yield of acetophenone are shown in Table 2.

[0160]

Example 10

[0161] A 0.45 g sample of a 5 wt% palladium ammonium solution was dissolved in 4.5 mL of deionized water and added dropwise to 4.4 g of a SiO2 carrier. The carrier was thoroughly wetted and a thin liquid film was formed. The mixture was allowed to stand for 6 h, dried at 110°C for 10 h, and calcined at 550°C for 4.5 h to obtain a Pd / SiO2 catalyst (designated C-8) having a palladium content of 0.5 wt%. The surface palladium content of the catalyst was determined by EDS energy spectrum quantitative analysis, and the bulk palladium content of the catalyst was determined by inductively coupled plasma spectrometry. The results are shown in Table 1.

[0162] The hydrogenolysis product was subjected to distillation treatment, the overhead temperature was 80°C, the bottom temperature was 160°C, the overhead gas phase cumene was recycled to the cumene oxidation process, and the bottom material was subjected to hydrogenolysis treatment;

[0163] The hydrogenolysis treatment was carried out in a fixed bed using the catalyst prepared in this example 10, the reaction temperature was 230°C, and the pressure was 0.5 MPa.

[0164] The hydrogenolysis product was subjected to distillation treatment, the overhead temperature was 80°C, the bottom temperature was 160°C, the overhead gas phase cumene was recycled to the cumene oxidation process, and the bottom material was subjected to hydrogenolysis treatment;

[0165] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0166]

Example 11

[0167] 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 4 h, dried at 110 °C for 10 h, and calcined at 550 °C for 4.5 h to obtain a Pd / SiO2 catalyst (named C-9) 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 optical emission spectrometry. The results are shown in Table 1.

[0168] 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.

[0169] 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.

[0170] 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.

[0171] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0172]

Example 12

[0173] The process of Example 1 was repeated, except that an equimolar amount of glucose was used to replace ethylenediamine in the preparation of the catalyst, while other conditions remained unchanged. The resulting catalyst was named C-10.

[0174] 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.

[0175] The hydrogenolysis process was carried out in a fixed bed using the catalyst prepared in Example 12, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0176] 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.

[0177] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0178]

Example 13

[0179] The process of Example 1 was repeated, except that equimolar amount of ethylenediamine was used to replace glucose in the preparation of catalyst, and other conditions were unchanged. The catalyst obtained was named as C-11.

[0180] The hydrogenolysis product of α,α-dimethylbenzyl alcohol was subjected to rectification treatment, with the top temperature being 80°C and the bottom temperature being 160°C. The gaseous cumene at the top was recycled back to the cumene oxidation process, and the bottom material was subjected to hydrogenolysis treatment.

[0181] The hydrogenolysis treatment was carried out in a fixed bed, using the catalyst prepared in this example 13, at a reaction temperature of 230°C and a pressure of 0.5 MPa.

[0182] The material after hydrogenolysis treatment was subjected to rectification treatment, with the top temperature being 80°C and the bottom temperature being 160°C. The gaseous cumene at the top was recycled back to the oxidation process, and the bottom material was obtained as high value-added acetophenone, and the side material was discharged.

[0183] The conversion results of cumene and the yield of acetophenone are shown in Table 2.

[0184] Table 1:

[0185] Catalyst Theoretical Pd content (%) Surface Pd content (%) Bulk Pd content (%) C-1 0.50 0.37 0.50 C-2 0.10 00.06 0.11 C-3 0.10 0.08 0.10 C-4 0.10 0.04 0.10 C-5 0.50 0.34 0.49 C-6 0.50 0.49 0.49 C-7 0.10 0.11 0.10 C-8 0.50 0.50 0.50 C-9 0.50 0.50 0.51 C-10 0.50 0.14 0.36 C-11 0.50 0.11 0.35

[0186] Note: Theoretically, the surface palladium content should not be higher than the bulk palladium content, but if the surface palladium content is higher than the bulk palladium content, it may be due to detection error.

[0187] Table 2:

[0188]

[0189]

[0190] The present application has been described in detail with reference to specific embodiments and illustrative examples, but these are not to be construed as limiting the present application. Those skilled in the art understand that various equivalent substitutions, modifications or improvements can be made to the technical solutions and embodiments of the present application without departing from the spirit and scope of the present application, and these all fall within the scope of the present application. The scope of protection of the present application is subject to the appended claims.

Claims

1. A method for treating the hydrogenolysis products of α,α-dimethylbenzyl alcohol, comprising: (1) Recover cumene from the hydrogenolysis product of α,α-dimethylbenzyl alcohol to obtain cumene and liquid phase byproduct, wherein the liquid phase byproduct contains cumene and acetophenone; (2) The liquid phase by-products are subjected to hydrogenolysis and product separation treatment in sequence; The hydrogenolysis treatment in step (2) is carried out in the presence of a catalyst, which includes a support, an active component and optional additives. The support is selected from at least one of metal oxides and activated carbon. The active component is selected from noble metals. The active component is distributed on the surface and inside the support. The bulk active component of the catalyst is greater than or equal to the content of the surface active component.

2. The method according to claim 1, characterized in that, In step (1), isopropylbenzene in the hydrogenolysis product of α,α-dimethylbenzyl alcohol is recovered by distillation, wherein isopropylbenzene is obtained at the top of the column and liquid phase byproduct is obtained at the bottom of the column.

3. The method according to claim 2, characterized in that, The conditions for the distillation process are: top temperature of 50~120℃ and bottom temperature of 130~200℃.

4. The method according to claim 1, characterized in that, In the liquid phase byproduct described in step (1), the weight content of cumene is 5wt%~50wt%, and the weight content of acetophenone is 40wt%-80wt%.

5. The method according to claim 1, characterized in that, In step (2), the temperature of the hydrogenolysis treatment is 190~350℃; and / or, the pressure of the hydrogenolysis treatment is 0.1~10MPA.

6. The method according to claim 1, characterized in that, Based on a total content of 100 wt% for the support and active components, the bulk active component content of the catalyst is 0.01~5 wt%, and the surface active component content of the catalyst is 0.005~3 wt%; and / or, The content of the auxiliary agent is 0~1500 ppm, based on a total content of 100wt% of the carrier and active components.

7. The method according to claim 1, characterized in that, Based on a total content of 100 wt% for the support and active components, the bulk active component content of the catalyst is 0.01~5 wt%, and the surface active component content of the catalyst is 0.005~3 wt%; and / or, The content of the auxiliary agent is 0~200 ppm, based on a total content of 100 wt% of the carrier and active components.

8. The method according to claim 5, characterized in that, The carrier is selected from at least one of alumina, silica, activated carbon, titanium dioxide, zirconium oxide, and iron oxide; and / or, The active component is palladium; and / or, The additive is selected from at least one of copper, iron, boron, phosphorus, and sulfur.

9. The method according to any one of claims 1 to 8, characterized in that, In step (2), the product is separated by distillation.

10. The method according to claim 9, characterized in that, The conditions for the distillation process are: top temperature of 50~120℃ and bottom temperature of 130~200℃.

11. The use of the method according to any one of claims 1 to 10 in the preparation of propylene oxide.

12. The application according to claim 11, characterized in that, Application in the preparation of propylene oxide using the CHP method.

13. A method for preparing propylene oxide, comprising an isopropylbenzene oxidation process, a propylene epoxidation process, an α,α-dimethylbenzyl alcohol hydrogenolysis process, and a process for treating the α,α-dimethylbenzyl alcohol hydrogenolysis products, wherein, The process for treating the hydrogenolysis product of α,α-dimethylbenzyl alcohol is carried out using the method described in any one of claims 1 to 10.

14. The method according to claim 13, characterized in that, The method includes the following steps: (a) Oxidation process of cumene: Cumene undergoes an oxidation reaction in the presence of oxygen-containing gas to produce cumene hydrogen peroxide; (b) Propylene epoxidation process: In the presence of a catalyst, cumene hydroperoxide reacts with propylene to give a mixture of propylene oxide and α,α-dimethylbenzyl alcohol. After product separation, propylene oxide and α,α-dimethylbenzyl alcohol are obtained respectively. (c) Hydrogenolysis of α,α-dimethylbenzyl alcohol: In the presence of a catalyst, α,α-dimethylbenzyl alcohol reacts with hydrogen to obtain hydrogenolysis products; (d) The hydrogenolysis product is processed by the method according to any one of claims 1 to 10, wherein the obtained cumene is recycled back to the cumene oxidation process, and the obtained acetophenone is used as a high-value-added byproduct.

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