A method for synthesizing di-(2-hydroxy-2-propyl)benzene

Abstract

The invention discloses a method for synthesizing di-(2-hydroxy-2-propyl)benzene, which comprises subjecting aromatic hydroperoxide to hydrogen reduction reaction in an organic solvent in the presence of an organic polyphosphonic acid stabilizer and a hydrogenation catalyst. In the present invention, the organic polyphosphonic acid stabilizer and the hydrogenation catalyst are used in coordination to suppress the decomposition side reaction of the aromatic hydroperoxide, and the catalytic system of the present invention has the characteristics of high activity, high selectivity and high stability.

Description

Technical Field

[0001] The invention relates to an organic synthesis method, in particular to a synthesis method of di-(2-hydroxy-2-propyl)benzene. Background Art

[0002] Di-(2-hydroxyisopropyl)benzene (DC) is an important chemical intermediate raw material with molecular formula C 12 H 18 O2, molecular weight 194.28. As a tertiary alcohol, DC has relatively active chemical properties and can be dehydrated to generate olefins at higher temperatures (>120°C). DC itself can be polymerized, and can also react with tert-butyl hydroperoxide to generate various organic compounds. Based on these properties, DC is not only a stabilizer biphenol for the synthesis of polyolefins and polyurethanes, but also an important starting material for organic peroxide di(tert-butylperoxyisopropyl)benzene and aromatic diamines.

[0003] At present, the main production process of DC is the hydrogenation reduction process, that is, under a certain temperature and pressure, using palladium / alumina as a catalyst, diisopropylbenzene dihydroperoxide (DHP) and / or 2-hydroxy-2-propyl-isopropylbenzene hydroperoxide (HHP) are reduced to DC. However, the above reduction reactions will produce a certain amount of by-products, resulting in reduced raw material utilization and product selectivity.

[0004] The route for DHP reduction to generate DC includes the following reaction processes:

[0005] Main reaction:

[0006]

[0007] Side effects:

[0008]

[0009] The route for HHP reduction to generate DC includes the following reaction processes: Main reaction:

[0010]

[0011] Side effects:

[0012]

[0013] Patent EP0378165A2 provides an improved method for preparing aromatic alcohols in terms of catalysts, using a single Pt catalyst or a catalyst containing Pt and at least one element selected from Pb, Sn, Cu, As, Sb, In, Se, and Bi. This patent has the problems of low raw material concentration and low product purity due to excessive hydrogenation of aromatic rings in aromatic alcohols into alcohols with cyclohexane rings.

[0014] Patent JP1997194411A discloses a method for preparing high-purity bis(2-hydroxy-2-propyl)benzene by hydrogenation reduction using a methyl isobutyl ketone solution containing 2-hydroxy-2-propyl-cumene hydroperoxide as a main component in the presence of an alumina-supported palladium catalyst. The patent mentions that the water present in the raw material and the water produced by the reaction have the effects of covering the catalyst surface, promoting the coagulation of the catalyst and reducing its activity. Therefore, in order to maintain the activity of the catalyst, it is necessary to strictly control the water content in the raw material and the water content of the system during the reaction. There are problems such as harsh operating conditions, long reaction time and low raw material concentration. At the same time, the patent does not mention the problem of the catalyst life cycle.

[0015] Patent CN113880687A discloses a method for preparing di-(2-hydroxy-2-propyl)benzene by hydrogenation reduction using a mixture of 2-hydroxy-2-propyl-isopropylbenzene hydroperoxide and diisopropylbenzene dihydroperoxide as raw materials in the presence of a specific palladium catalyst. The catalyst needs to strictly control the particle size, dispersion and thickness of the Pd layer during the preparation process, otherwise the problem of poor activity or poor selectivity occurs. Therefore, the patent has the problems of harsh catalyst control conditions and unstable catalyst selectivity (such as the product selectivity ranges from 88% to 98%).

[0016] In summary, existing patents have problems such as harsh catalyst control conditions, easy catalyst deactivation, poor selectivity (such as excessive hydrogenation side reaction), harsh reaction operating conditions, low raw material concentration in the system, and low production efficiency. Summary of the invention

[0017] In order to solve the above technical problems, the present invention provides a method for synthesizing di-(2-hydroxy-2-propyl)benzene.

[0018] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0019] A method for synthesizing di-(2-hydroxy-2-propyl)benzene comprises the steps of subjecting aromatic hydroperoxide to hydrogen reduction reaction in an organic solvent in the presence of an organic polyphosphonic acid stabilizer and a hydrogenation catalyst.

[0020] The organic polyphosphonic acid stabilizer and the hydrogenation catalyst are used in coordination to inhibit the decomposition side reaction of the aromatic hydroperoxide, and the catalytic system of the present invention has the characteristics of high activity, high selectivity and high stability; at the same time, the reaction conditions of the present invention are mild, the reaction is easy to control, the reaction steps are few, the amount of three wastes generated is small, the process is clean and environmentally friendly, and is suitable for industrialization.

[0021] As a preferred embodiment of the present invention, the organic polyphosphonic acid stabilizer is selected from at least one of aminotrimethylenephosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid, preferably aminotrimethylenephosphonic acid and / or hydroxyethylidene diphosphonic acid, more preferably aminotrimethylenephosphonic acid.

[0022] As a preferred embodiment of the present invention, the amount of the organic polyphosphonic acid stabilizer is 50-500 ppm, preferably 100-400 ppm, more preferably 200-300 ppm, based on the weight of the aromatic hydroperoxide.

[0023] As a preferred embodiment of the present invention, the hydrogenation catalyst comprises an active component and a carrier; wherein the composition of the active component, based on the weight of the carrier, comprises:

[0024] NiO 1-10wt%, preferably 3-7wt%, more preferably 4-6wt%;

[0025] Ag2O 0.1-1wt%, preferably 0.3-0.7wt%, more preferably 0.4-0.6wt%;

[0026] Nb2O5 0.01-0.2wt%, preferably 0.05-0.15wt%, more preferably 0.08-0.1wt%.

[0027] As a preferred embodiment of the present invention, the carrier is selected from one of γ-alumina, magnesia, silicon dioxide, zirconium dioxide and activated carbon, preferably γ-alumina;

[0028] Preferably, the specific surface area of ​​the carrier is 100-600m 2 / g, preferably 200-500m 2 / g, more preferably 300-400m 2 / g; the average pore diameter is 10-100nm, preferably 30-80nm, more preferably 50-60nm.

[0029] The hydrogenation catalyst can be prepared by at least one of an impregnation method, a coprecipitation method, a deposition method, and an ion exchange method.

[0030] As an example of a feasible method for preparing the hydrogenation catalyst, for example, the conventional impregnation method is:

[0031] According to the designed component content, the carrier is immersed in an aqueous solution containing soluble nickel salt, silver salt and niobium salt, and after adsorption equilibrium is reached, it is dried and calcined to obtain the hydrogenation catalyst.

[0032] The nickel salt includes but is not limited to nickel nitrate and nickel sulfate, preferably nickel nitrate; the silver salt includes but is not limited to silver nitrate and silver sulfate, preferably silver nitrate; the niobium salt includes but is not limited to niobium nitrate and niobium sulfate, preferably niobium nitrate.

[0033] In the preparation method, the drying temperature is 100-200°C, preferably 120-180°C, more preferably 140-160°C; the drying time is 4-12h, preferably 4-10h, more preferably 6-8h; the roasting temperature is 300-600°C, preferably 350-550°C, more preferably 400-500°C; the roasting time is 2-8h, preferably 3-7h, more preferably 4-6h.

[0034] In addition, as is well known to those skilled in the art, the hydrogenation catalyst needs to be activated after being prepared to be active. The reaction conditions in the general activation method are, for example:

[0035] The reduction is carried out for 2-12 h, preferably 4-10 h, more preferably 6-8 h under the conditions of a hydrogen flow rate of 1-10 L / min / L·cat, preferably 3-7 L / min / L·cat, more preferably 5-6 L / min / L·cat, an absolute pressure of 1-4 MPa, preferably 1.5-3.5 MPa, more preferably 2-3 MPa, and an activation temperature of 200-400°C, preferably 240-360°C, more preferably 280-320°C.

[0036] However, it is worth noting that the above activation methods are only general examples of feasible solutions provided by the present invention and cannot be used as any limitation on the protection scope of the present invention.

[0037] As a preferred embodiment of the present invention, the aromatic hydroperoxide is selected from diisopropylbenzene hydroperoxide and / or 2-hydroxy-2-propyl-isopropylbenzene hydroperoxide, preferably 2-hydroxy-2-propyl-isopropylbenzene hydroperoxide.

[0038] As a preferred embodiment of the present invention, the raw material space velocity is 1-20L / h / L·cat, preferably 5-15L / h / L·cat, more preferably 8-12L / h / L·cat, based on the space velocity of the mixed solution consisting of the aromatic hydroperoxide and the organic solvent, wherein the mass concentration of the aromatic hydroperoxide in the mixed solution is 1-30wt%, more preferably 5-25wt%, and further preferably 10-20wt%.

[0039] As a preferred embodiment of the present invention, the organic solvent is at least one of methyl ethyl ketone, methyl isobutyl ketone, methanol, isopropanol, cumene and diisopropylbenzene, preferably methyl ethyl ketone and / or methyl isobutyl ketone.

[0040] As a preferred embodiment of the present invention, the hydrogen feed amount is 1-6 times, preferably 2-5 times, and more preferably 3-4 times the theoretical molar amount of the aromatic hydroperoxide.

[0041] As a preferred embodiment of the present invention, the reaction temperature is 40-120°C, preferably 60-100°C, more preferably 70-90°C; the reaction absolute pressure is 1-4MPa, preferably 1.5-3.5MPa, more preferably 2-3Mpa.

[0042] The beneficial effects of the present invention are:

[0043] (1) A trace amount of organic polyphosphonic acid stabilizer in the hydrogenation catalytic system can effectively inhibit the decomposition side reaction of aromatic hydroperoxides, thereby greatly improving the utilization rate of raw materials;

[0044] (2) In the hydrogenation catalyst, the synergistic effect of the three components of NiO-Ag2O-Nb2O5 greatly improves the activity, selectivity and stability of the catalyst. The raw material conversion rate can reach 100%, the product selectivity can reach more than 98.0%, and the catalyst can operate continuously and stably for more than 1000 hours;

[0045] (3) The catalyst preparation process of the present invention is simple, can operate stably for a long time, is suitable for industrial production, and is applicable to a continuous fixed bed process. It has the advantages of simple process operation, low cost, less three wastes, green environmental protection and high production efficiency. DETAILED DESCRIPTION

[0046] The present invention is further described below by means of specific examples. The examples described in the present invention are only used to illustrate the present invention and do not limit the scope of the present invention.

[0047] Gas chromatograph: Shimadzu GC-2014 (FID) detector, SE-30 capillary column (φ0.30 mm×30 m), injection port 300°C, detector 270°C; heating program: 100°C, constant temperature for 5 min, then increased to 260°C at a rate of 20°C / min, and maintained for 10 min.

[0048] The reactor in the embodiment is a fixed bed reactor.

[0049] Diisopropylbenzene dihydroperoxide (DHP): content ≥ 99.5wt%, Wuhan Kemik Biopharmaceutical Technology Co., Ltd.;

[0050] 2-Hydroxy-2-propyl-cumene hydroperoxide (HHP): content ≥ 99.5wt%, Wuhan Kemik Biopharmaceutical Technology Co., Ltd.;

[0051] γ-Al2O3: Specific surface area is 300m 2 / g; average pore size is 80nm, Yangzhou Zhongtianli New Materials Co., Ltd.;

[0052] ZrO2: Specific surface area is 200m 2 / g; average pore size is 10nm, Yangzhou Zhongtianli New Materials Co., Ltd.;

[0053] Activated carbon: Specific surface area is 400m 2 / g; average pore diameter is 60nm, Jiangsu Qisheng Carbon Technology Co., Ltd.

[0054] The hydrogenation catalysts prepared in the following examples were uniformly activated by the following process and applied to synthesize DC:

[0055] In the fixed bed reactor, the hydrogen flow rate was adjusted to 1 L / min / L·cat, the absolute pressure was 4 MPa, the activation temperature was 200°C, and the activation time was 12 h.

[0056] [Example 1]

[0057] (1) Preparation of hydrogenation catalyst A

[0058] Weigh 100 g of the γ-Al2O3 carrier and add it to 100 ml of an aqueous solution containing 3.89 g of nickel nitrate hexahydrate, 1.47 g of anhydrous silver nitrate and 0.61 g of anhydrous niobium nitrate by an equal volume impregnation method. After adsorption equilibrium, dry it at 200°C for 2 h and calcine it at 300°C for 8 h to obtain catalyst A with a composition of 1wt% NiO-1wt% Ag2O-0.2wt% Nb2O5 / γ-Al2O3.

[0059] (2) Synthetic DC

[0060] The temperature in the fixed bed reactor filled with hydrogenation catalyst A was adjusted to 40°C and the absolute pressure was adjusted to 4 MPa. After the system was stable, hydrogen gas of 1 times the theoretical molar amount of HHP was introduced, and then a 10 wt% HHP methyl isobutyl ketone solution containing 50 ppm aminotrimethylenephosphonic acid relative to the weight of HHP was introduced. The raw material feed space velocity was 8 L / h / L·cat, and the reduction reaction was carried out under this condition.

[0061] After 10 hours of reaction, gas chromatography analysis showed that the HHP conversion rate was 100.0%, the selectivity of DC was 99.61%, the selectivity of PTA was 0.22%, the selectivity of DST was 0.15%, and the selectivity of CPA was 0.02%. After the catalyst was continuously operated for 1500 hours, the HHP conversion rate remained unchanged, the selectivity of DC was 99.33%, the selectivity of PTA was 0.4%, the selectivity of DST was 0.15%, and the selectivity of CPA was 0.12%, and the catalytic stability was good.

[0062] [Comparative Example 1]

[0063] The difference from Example 1 is that no anhydrous niobium nitrate is added when preparing the hydrogenation catalyst in step (1). The obtained hydrogenation catalyst A-1 is used to synthesize DC in the same manner as in Example 1, except that the catalyst prepared in this comparative example is used instead.

[0064] After 10 hours of reaction, gas chromatography analysis showed that the HHP conversion rate was 98.5%, the DC selectivity was 93.89%, the PTA selectivity was 0.34%, the DST selectivity was 0.55%, and the CPA selectivity was 5.22%. After the catalyst was continuously operated for 800 hours, the HHP conversion rate was 90.8%, the DC selectivity was 90.71%, the PTA selectivity was 0.65%, the DST selectivity was 1.52%, and the CPA selectivity was 7.12%.

[0065] [Comparative Example 2]

[0066] The difference from Example 1 is that no anhydrous silver nitrate is added when preparing the hydrogenation catalyst in step (1). The obtained hydrogenation catalyst A-2 is used to synthesize DC in the same manner as in Example 1, except that the catalyst prepared in this comparative example is substituted.

[0067] After 10 hours of reaction, the HHP conversion rate was 100%, the selectivity of DC was 94.83%, the selectivity of PTA was 0.31%, the selectivity of DST was 4.32%, and the selectivity of CPA was 0.54%. After the catalyst was continuously operated for 1000 hours, the HHP conversion rate was 95.2%, the selectivity of DC was 91.22%, the selectivity of PTA was 0.32%, the selectivity of DST was 7.65%, and the selectivity of CPA was 0.81%.

[0068] [Comparative Example 3]

[0069] The difference from Example 1 is that the HHP solution introduced in step (2) during the synthesis of DC does not contain aminotrimethylenephosphonic acid.

[0070] After 10 hours of reaction, gas chromatography analysis showed that the HHP conversion rate was 100.0%, the selectivity of DC was 92.88%, the selectivity of PTA was 6.83%, the selectivity of DST was 0.24%, and the selectivity of CPA was 0.05%. After the catalyst was continuously operated for 1500 hours, the HHP conversion rate remained unchanged, the selectivity of DC was 90.53%, the selectivity of PTA was 8.35%, the selectivity of DST was 0.74%, and the selectivity of CPA was 0.38%.

[0071] [Comparative Example 4]

[0072] The hydrogenation catalyst A-4 was prepared by referring to the method in Example 1 of patent CN113880687A, and DC was synthesized by the same method as Example 1 of the present invention, except that the catalyst prepared in this comparative example was replaced.

[0073] After 10 hours of reaction, the HHP conversion rate was 94.2%, the selectivity of DC was 86.88%, the selectivity of PTA was 1.83%, the selectivity of DST was 4.24%, and the selectivity of CPA was 7.05%. After the catalyst was continuously operated for 300 hours, the HHP conversion rate was 83.4%, the selectivity of DC was 78.25%, the selectivity of PTA was 4.63%, the selectivity of DST was 7.74%, and the selectivity of CPA was 9.38%.

[0074] [Example 2]

[0075] (1) Preparation of hydrogenation catalyst B

[0076] Weigh 100 g of activated carbon carrier and add it to 100 ml of aqueous solution containing 11.68 g of nickel nitrate hexahydrate, 1.03 g of anhydrous silver nitrate and 0.45 g of anhydrous niobium nitrate by equal volume impregnation method. After adsorption equilibrium, dry it at 180°C for 4 h and calcine it at 350°C for 7 h to obtain catalyst B with a composition of 3wt% NiO-0.7wt% Ag2O-0.15wt% Nb2O5 / activated carbon.

[0077] (2) Synthetic DC

[0078] The temperature in the fixed bed reactor filled with hydrogenation catalyst B was adjusted to 60°C and the absolute pressure was adjusted to 3.5 MPa. After the system was stable, hydrogen gas twice the theoretical molar amount of HHP was introduced, and then a 20 wt% HHP solution in methyl ethyl ketone containing 100 ppm aminotrimethylenephosphonic acid relative to the weight of HHP was introduced. The raw material feed space velocity was 12 L / h / L·cat, and the reduction reaction was carried out under this condition.

[0079] After 15 hours of reaction, gas chromatography analysis showed that the HHP conversion rate was 100.0%, the selectivity of DC was 99.19%, the selectivity of PTA was 0.31%, the selectivity of DST was 0.35%, and the selectivity of CPA was 0.15%. After the catalyst was continuously operated for 1300 hours, the HHP conversion rate remained unchanged, the selectivity of DC was 98.93%, the selectivity of PTA was 0.55%, the selectivity of DST was 0.34%, and the selectivity of CPA was 0.18%, and the catalytic stability was good.

[0080] [Example 3]

[0081] (1) Preparation of hydrogenation catalyst C

[0082] Weigh 100 g of ZrO2 carrier and add it to 100 ml of aqueous solution containing 15.57 g of nickel nitrate hexahydrate, 0.88 g of anhydrous silver nitrate and 0.3 g of anhydrous niobium nitrate by equal volume impregnation method. After adsorption equilibrium, dry it at 160°C for 6 h and calcine it at 400°C for 6 h to obtain catalyst C with a composition of 4wt% NiO-0.6wt% Ag2O-0.1wt% Nb2O5 / ZrO2.

[0083] (2) Synthetic DC

[0084] The temperature in the fixed bed reactor filled with hydrogenation catalyst C was adjusted to 70°C and the absolute pressure was 3 MPa. After the system was stable, hydrogen gas was introduced at 3 times the theoretical molar amount of DHP, and then a 30 wt% DHP methyl isobutyl ketone solution containing 200 ppm of ethylenediaminetetramethylenephosphonic acid relative to the weight of DHP was introduced. The raw material feed space velocity was 1 L / h / L·cat, and the reduction reaction was carried out under this condition.

[0085] After 12 hours of reaction, the DHP conversion rate was 100.0%, the selectivity of DC was 99.25%, the selectivity of resorcinol (RES) was 0.28%, the selectivity of DST was 0.42%, and the selectivity of CPA was 0.05%. After the catalyst was continuously operated for 1200 hours, the DHP conversion rate remained unchanged, the selectivity of DC was 98.77%, the selectivity of resorcinol (RES) was 0.38%, the selectivity of DST was 0.45%, and the selectivity of CPA was 0.4%, and the catalytic stability was good.

[0086] [Example 4]

[0087] (1) Preparation of hydrogenation catalyst D

[0088] 100 g of the γ-Al2O3 carrier was weighed and added to 100 ml of an aqueous solution containing 23.36 g of nickel nitrate hexahydrate, 0.59 g of anhydrous silver nitrate and 0.24 g of anhydrous niobium nitrate by an equal volume impregnation method. After adsorption equilibrium, the catalyst was dried at 140°C for 8 h and calcined at 500°C for 4 h to obtain catalyst D with a composition of 6wt% NiO-0.4wt% Ag2O-0.08wt% Nb2O5 / γ-Al2O3.

[0089] (2) Synthetic DC

[0090] The temperature in the fixed bed reactor filled with hydrogenation catalyst D was adjusted to 90°C and the absolute pressure was adjusted to 2.5 MPa. After the system was stable, hydrogen gas of 4 times the theoretical molar amount of HHP was introduced, and then a 5wt% HHP methyl isobutyl ketone solution containing 300ppm of hydroxyethylidene diphosphonic acid relative to the weight of HHP was introduced. The raw material feed space velocity was 5L / h / L·cat, and the reduction reaction was carried out under this condition.

[0091] After 13 hours of reaction, gas chromatography analysis showed that the HHP conversion rate was 100.0%, the selectivity of DC was 99.73%, the selectivity of PTA was 0.17%, the selectivity of DST was 0.07%, and the selectivity of CPA was 0.03%. After the catalyst was continuously operated for 1400 hours, the HHP conversion rate remained unchanged, the selectivity of DC was 99.46%, the selectivity of PTA was 0.22%, the selectivity of DST was 0.17%, and the selectivity of CPA was 0.15%, and the catalytic stability was good.

[0092] [Example 5]

[0093] (1) Preparation of hydrogenation catalyst E

[0094] Weigh 100 g of the γ-Al2O3 carrier and add it to 100 ml of an aqueous solution containing 27.25 g of nickel nitrate hexahydrate, 0.44 g of anhydrous silver nitrate and 0.15 g of anhydrous niobium nitrate by an equal volume impregnation method. After adsorption equilibrium, dry it at 120°C for 10 h and calcine it at 550°C for 3 h to obtain catalyst E with a composition of 7wt% NiO-0.3wt% Ag2O-0.05wt% Nb2O5 / γ-Al2O3.

[0095] (2) Synthetic DC

[0096] The temperature in the fixed bed reactor filled with hydrogenation catalyst E was adjusted to 100°C and the absolute pressure was adjusted to 2 MPa. After the system was stable, hydrogen gas of 5 times the theoretical molar amount of HHP was introduced, and then a 25wt% HHP methyl ethyl ketone solution containing 400ppm aminotrimethylenephosphonic acid relative to the weight of HHP was introduced. The raw material feed space velocity was 15L / h / L·cat, and the reduction reaction was carried out under this condition.

[0097] After 17 hours of reaction, gas chromatography analysis showed that the HHP conversion rate was 100.0%, the selectivity of DC was 99.81%, the selectivity of PTA was 0.04%, the selectivity of DST was 0.1%, and the selectivity of CPA was 0.05%. After the catalyst was continuously operated for 1600 hours, the HHP conversion rate remained unchanged, the selectivity of DC was 99.26%, the selectivity of PTA was 0.19%, the selectivity of DST was 0.3%, and the selectivity of CPA was 0.25%, and the catalytic stability was good.

[0098] [Example 6]

[0099] (1) Preparation of hydrogenation catalyst F

[0100] Weigh 100 g of the γ-Al2O3 carrier and add it to 100 ml of an aqueous solution containing 38.93 g of nickel nitrate hexahydrate, 0.15 g of anhydrous silver nitrate and 0.03 g of anhydrous niobium nitrate by an equal volume impregnation method. After adsorption equilibrium, dry it at 100°C for 12 h and calcine it at 600°C for 2 h to obtain catalyst F with a composition of 10wt% NiO-0.1wt% Ag2O-0.01wt% Nb2O5 / γ-Al2O3.

[0101] (2) Synthetic DC

[0102] The temperature in the fixed bed reactor filled with hydrogenation catalyst F was adjusted to 120°C and the absolute pressure was 1 MPa. After the system was stable, hydrogen gas of 6 times the theoretical molar amount of HHP was introduced, and then a 1wt% HHP methyl isobutyl ketone solution containing 500ppm aminotrimethylenephosphonic acid relative to the weight of HHP was introduced. The raw material feed space velocity was 20L / h / L·cat, and the reduction reaction was carried out under this condition.

[0103] After 20 hours of reaction, gas chromatography analysis showed that the HHP conversion rate was 100.0%, the selectivity of DC was 99.43%, the selectivity of PTA was 0.19%, the selectivity of DST was 0.17%, and the selectivity of CPA was 0.21%. After the catalyst was continuously operated for 1800 hours, the HHP conversion rate remained unchanged, the selectivity of DC was 99.32%, the selectivity of PTA was 0.28%, the selectivity of DST was 0.23%, and the selectivity of CPA was 0.17%, and the catalytic stability was good.

[0104] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this field can make several improvements and supplements without departing from the method of the present invention. These improvements and supplements should also be regarded as the scope of protection of the present invention.

Claims

1. A method for synthesizing di-(2-hydroxy-2-propyl)benzene, characterized in that: The method comprises subjecting an aromatic hydroperoxide to a hydrogen reduction reaction in an organic solvent in the presence of an organic polyphosphonic acid stabilizer and a hydrogenation catalyst; The organic polyphosphonic acid stabilizer is selected from at least one of aminotrimethylenephosphonic acid, hydroxyethylenediphosphonic acid, ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid; The hydrogenation catalyst comprises an active component and a carrier; wherein the composition of the active component, based on the weight of the carrier, comprises: NiO 1-10wt%, Ag2O 0.1-1wt%, Nb2O5 0.01-0.2wt%.

2. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 1, characterized in that: The organic polyphosphonic acid stabilizer is selected from aminotrimethylenephosphonic acid and / or hydroxyethylidene diphosphonic acid.

3. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 2, characterized in that: The organic polyphosphonic acid stabilizer is aminotrimethylenephosphonic acid.

4. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 1, characterized in that: The organic polyphosphonic acid stabilizer is used in an amount of 50-500 ppm based on the weight of the aromatic hydroperoxide.

5. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 4, characterized in that: The organic polyphosphonic acid stabilizer is used in an amount of 100-400 ppm based on the weight of the aromatic hydroperoxide.

6. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 4, characterized in that: The organic polyphosphonic acid stabilizer is used in an amount of 200-300 ppm based on the weight of the aromatic hydroperoxide.

7. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 1, characterized in that: The hydrogenation catalyst comprises an active component and a carrier; wherein the composition of the active component, based on the weight of the carrier, comprises: NiO 3-7wt%; Ag2O 0.3-0.7wt%; Nb2O5 0.05-0.15wt%.

8. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 1, characterized in that: The hydrogenation catalyst comprises an active component and a carrier; wherein the composition of the active component, based on the weight of the carrier, comprises: NiO 4-6wt%; Ag2O 0.4-0.6wt%; Nb2O5 0.08-0.1wt%.

9. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 7, characterized in that: The carrier is selected from one of γ-alumina, magnesia, silicon dioxide, zirconium dioxide and activated carbon.

10. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 9, characterized in that: The carrier is γ-alumina.

11. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 9, characterized in that: The specific surface area of ​​the carrier is 100-600m 2 / g; the average pore size is 10-100nm.

12. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 11, characterized in that: The specific surface area of ​​the carrier is 200-500m 2 / g; the average pore size is 30-80nm.

13. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 11, characterized in that: The specific surface area of ​​the carrier is 300-400m 2 / g; the average pore size is 50-60nm.

14. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to any one of claims 1 to 13, characterized in that: The aromatic hydroperoxide is selected from diisopropylbenzene hydroperoxide and / or 2-hydroxy-2-propyl-isopropylbenzene hydroperoxide.

15. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 14, characterized in that: The aromatic hydroperoxide is 2-hydroxy-2-propyl-cumene hydroperoxide.

16. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 14, characterized in that: The raw material space velocity is 1-20 L / h / L·cat, measured by the space velocity of a mixed solution consisting of aromatic hydroperoxide and an organic solvent, wherein the mass concentration of the aromatic hydroperoxide in the mixed solution is 1-30 wt%.

17. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 16, characterized in that: The raw material space velocity is 5-15 L / h / L·cat, measured by the space velocity of a mixed solution consisting of aromatic hydroperoxide and an organic solvent, wherein the mass concentration of the aromatic hydroperoxide in the mixed solution is 5-25 wt %.

18. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 16, characterized in that: The raw material space velocity is 8-12 L / h / L·cat, measured by the space velocity of a mixed solution consisting of aromatic hydroperoxide and an organic solvent, wherein the mass concentration of the aromatic hydroperoxide in the mixed solution is 10-20 wt%.

19. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to any one of claims 1 to 13, characterized in that: The organic solvent is at least one of methyl ethyl ketone, methyl isobutyl ketone, methanol, isopropanol, cumene and diisopropylbenzene.

20. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 19, characterized in that: The organic solvent is methyl ethyl ketone and / or methyl isobutyl ketone.

21. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to any one of claims 1 to 13, characterized in that: The amount of hydrogen fed is 1-6 times the theoretical molar amount of the aromatic hydroperoxide.

22. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 21, characterized in that: The amount of hydrogen fed is 2-5 times the theoretical molar amount of the aromatic hydroperoxide.

23. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 21, characterized in that: The amount of hydrogen fed is 3-4 times the theoretical molar amount of the aromatic hydroperoxide.

24. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to any one of claims 1 to 13, characterized in that: The reaction temperature is 40-120°C; the reaction absolute pressure is 1-4MPa.

25. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 24, characterized in that: The reaction temperature is 60-100°C; the reaction absolute pressure is 1.5-3.5MPa.

26. The method for synthesizing di-(2-hydroxy-2-propyl)benzene according to claim 24, characterized in that: The reaction temperature is 70-90°C; the reaction absolute pressure is 2-3Mpa.

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