A catalyst for the oxidation of 2-alkylanthracene to 2-alkylanthraquinone, its preparation and use

Abstract

A method for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene, characterized in that 2-alkylanthracene, a solvent and hydrogen peroxide are contacted in the presence of a catalyst and under an oxidizing reaction condition, the catalyst contains Hbeta molecular sieve modified by a lanthanide metal and an alkaline earth metal, and is obtained by the steps of acid treatment, lanthanide metal loading, ion exchange and calcination of Hbeta molecular sieve. The method has good selectivity, the catalyst is easy to separate and recycle, and the process is green and environmentally friendly.

Description

Technical Field

[0001] The present invention relates to a catalyst for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene, a preparation method and application thereof, and in particular to a catalyst containing a modified Hβ molecular sieve for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene, a preparation method and application of the catalyst in the 2-alkylanthracene oxidation reaction. Background Art

[0002] Hydrogen peroxide (H2O2) is a representative green basic chemical with both reducing and oxidizing properties. It produces only H2O and O2 after the reaction, without causing environmental pollution. Therefore, it is commonly used in many fields, including papermaking, textiles, metallurgy, and chemical synthesis. Currently, the main method for producing H2O2 is the anthraquinone process, which uses 2-alkylanthraquinone as the working carrier. 2-alkylanthraquinone is the core of the anthraquinone process and directly affects the quality and yield of H2O2.

[0003] Currently, the primary method for producing 2-alkylanthraquinones is the phthalic anhydride process. This process requires large amounts of aluminum trichloride and concentrated sulfuric acid, and produces significant amounts of waste acid, wastewater, and aluminum slag. These processes are not only highly corrosive but also cause significant environmental pollution, posing significant environmental challenges. In contrast, the one-step oxidation process for producing 2-alkylanthraquinones using 2-alkylanthracene as a raw material allows for cleaner production.

[0004] Zhang Yonghua (CN1231278A) disclosed a method for producing anthraquinone by oxidizing anthracene with oxygen in a mixed solvent of aromatic halogenated hydrocarbons and organic acids, using metal salts and bromides as catalysts. This method uses a large amount of organic acid as a solvent, which is corrosive to production equipment and does not meet the requirements of green production. Furthermore, anthracene has a low solubility in organic acids, making it unsuitable for large-scale industrial production.

[0005] Wang Weijian (CN106966884A) et al. proposed a method for preparing anthraquinone by catalyzing anthracene using a metal oxide complex. This method has high pressure and temperature and low safety.

[0006] CN111825512A discloses a method for oxidizing 2-alkylanthracene to produce 2-alkylanthraquinone. This method uses hydrogen chloride as a catalyst, achieving a product yield of 94.23%. However, hydrogen chloride is highly corrosive, and the resulting chlorine and hypochlorous acid react with the 2-alkylanthracene to form chlorinated products, hindering product separation. Furthermore, hydrogen chloride is soluble in water, hindering catalyst recovery and generating large amounts of chlorine-containing wastewater, creating environmental pressures. Summary of the Invention

[0007] Based on extensive experimental research, the inventors of this application discovered that by first treating an Hβ molecular sieve with an organic acid, then treating it twice with a lanthanide metal salt solution, then undergoing ion exchange with an alkaline earth metal salt solution, and finally calcining it, the resulting modified Hβ molecular sieve not only has significantly increased lanthanide and alkaline earth metal contents, but also improves the selectivity of 2-alkylanthraquinone when used as a catalyst in the oxidation of 2-alkylanthracene to produce 2-alkylanthraquinone. The 2-alkylanthraquinone is also more easily separated after the reaction compared to Hβ molecular sieves modified with metal oxide catalysts. Based on this, the present invention was developed.

[0008] Therefore, the present invention is based on the technical route of oxidizing 2-alkylanthracene to prepare 2-alkylanthraquinone. One purpose is to provide a catalyst for oxidizing 2-alkylanthracene to prepare 2-alkylanthraquinone that is different from the prior art; the second purpose is to provide a method suitable for preparing the catalyst for oxidizing 2-alkylanthracene to prepare 2-alkylanthraquinone of the present invention; the third purpose is to provide a method for oxidizing 2-alkylanthracene to prepare 2-alkylanthraquinone, which has good selectivity, easy separation and recycling of the catalyst, and a green and environmentally friendly process.

[0009] To achieve one of the objectives of the present invention, the present invention provides a catalyst for oxidizing 2-alkylanthracene to prepare 2-alkylanthraquinone, characterized in that the catalyst contains Hβ molecular sieve modified by lanthanide metal and alkaline earth metal.

[0010] The catalyst is characterized in that, based on the Hβ molecular sieve modified by lanthanide metals and alkaline earth metals, the lanthanide metal content, calculated as oxide, is 3-30% by weight, and the alkaline earth metal content is 0.1-10% by weight; preferably, the lanthanide metal content is 5-28% by weight, and the alkaline earth metal content is 0.5-9% by weight; more preferably, the lanthanide metal content is 9-25% by weight, and the alkaline earth metal content is 3-8% by weight.

[0011] The lanthanide metal is selected from at least one of lanthanum, cerium, praseodymium and neodymium, and the alkaline earth metal is selected from at least one of calcium, magnesium and barium; preferably, the lanthanide metal is lanthanum, and the alkaline earth metal is calcium.

[0012] In order to achieve the second object of the present invention, the present invention also provides a method for preparing a catalyst for oxidizing 2-alkylanthracene to prepare 2-alkylanthraquinone, characterized in that the method comprises the steps of acid treatment of Hβ molecular sieve, loading of lanthanide metal, ion exchange and calcination, wherein the ion exchange solution contains at least one alkaline earth metal compound.

[0013] The preparation method is characterized in that the acid treatment comprises: contacting the Hβ molecular sieve with an aqueous solution of an organic acid at a temperature of 20-80°C, a pressure of 0-0.3 MPa (absolute pressure), and a contact time of 2-24 hours; preferably, the temperature is 20-60°C, the pressure is 0-0.1 MPa, and the contact time is 2-18 hours.

[0014] The organic acid is at least one of acetic acid, oxalic acid, benzoic acid, and salicylic acid. Preferably, the organic acid is oxalic acid. The aqueous solution of the organic acid has a concentration of 0.1-2 mol·L -1 ; Preferably, the concentration is 0.1-1mol·L -1 ; The amount of the organic acid is 1-20ml / g molecular sieve; preferably, the amount of the organic acid is 1-10ml / g molecular sieve.

[0015] The preparation method is characterized in that after the acid treatment, the solid is washed with water to neutrality, dried, and then the solid is loaded with lanthanide metals.

[0016] The preparation method is characterized in that the lanthanide metal loading comprises: first contacting the acid-treated Hβ molecular sieve with a lanthanide metal salt solution, drying and calcining the first solid material obtained by the contact to obtain a second solid material, and then second contacting the second solid material with a lanthanide metal salt solution.

[0017] The lanthanide metal is selected from at least one of lanthanum, cerium, praseodymium and neodymium. Preferably, the lanthanide metal is lanthanum.

[0018] The lanthanide metal salt is selected from at least one of a lanthanide metal chloride, a lanthanide metal carbonate compound, and a lanthanide metal nitrate compound; preferably, the lanthanide metal salt is a lanthanide metal nitrate compound. The concentration of the lanthanide metal salt solution is 1-10 mol·L -1 , preferably, the concentration is 5-10 mol·L -1 The amount of the lanthanide metal salt solution used in the first contact is 5-200 ml / g molecular sieve, preferably, 20-100 ml / g molecular sieve; the amount of the lanthanide metal salt solution used in the second contact is 5-200 ml / g molecular sieve, preferably, 20-100 ml / g molecular sieve.

[0019] The conditions for the first contact are: contact temperature of 20-90°C, preferably 50-90°C; contact time of 1-24h, preferably 12-20h; pressure of 0-0.2MPa, preferably 0-0.1MPa; the conditions for the second contact are: contact temperature of 20-90°C, preferably 50-90°C; contact time of 1-24h, preferably 12-20h; pressure of 0-0.2MPa, preferably 0-0.1MPa.

[0020] In the preparation method, the solid after the lanthanide metal is loaded is washed with water to neutrality and dried, and then ion exchange is performed.

[0021] In the preparation method, the alkaline earth metal in the ion exchange solution is selected from at least one of calcium, magnesium, and barium, and the preferred alkaline earth metal is calcium. The ion exchange solution is selected from an alkaline earth metal salt solution, and preferably, the ion exchange solution is an alkaline earth metal nitrate compound solution. The concentration of the alkaline earth metal salt solution is 1-10 mol·L -1 Preferably, the concentration of the alkaline earth metal salt solution is 5-10 mol·L -1 The amount of the alkaline earth metal salt solution is 5-200 ml / g molecular sieve, preferably 20-100 ml / g molecular sieve.

[0022] The ion exchange conditions are as follows: contact temperature of 20-90°C, preferably 50-90°C, contact time of 1-24h, preferably 12-20h, and pressure of 0-0.2MPa, preferably 0-0.1MPa;

[0023] In the preparation method, after the ion exchange, the solid is washed with water to neutrality, dried, and roasted.

[0024] The catalyst for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene obtained by the above preparation method.

[0025] In order to achieve the third object of the present invention, the present invention further provides a method for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene, characterized in that the method is carried out in the presence of the above-mentioned catalyst or the catalyst obtained by the above-mentioned preparation method.

[0026] The method is characterized in that 2-alkylanthracene, the catalyst, a solvent, and hydrogen peroxide are contacted. The contact temperature is 30-100°C, preferably 55-95°C; the pressure is 0-0.2 MPa, preferably 0-0.1 MPa; and the reaction time is 1-24 hours, preferably 1-20 hours. The solvent is one or more of methanol, ethanol, ether, benzene, toluene, chloroform, acetone, carbon tetrachloride, mesitylene, and N,N-dimethylformamide; preferably, the solvent is one or more of methanol, toluene, carbon tetrachloride, mesitylene, and N,N-dimethylformamide.

[0027] The method is characterized in that the molar ratio of hydrogen peroxide to 2-alkylanthracene is (2-20):1, preferably (3-12):1; the amount of the catalyst is 0.001-0.1 g, preferably 0.005-0.07 g, per milliliter of solvent, and the catalyst is calculated as a molecular sieve; and the concentration of the 2-alkylanthracene is 0.01-1 g, preferably 0.02-0.3 g, per milliliter of solvent.

[0028] The method is characterized in that the structure of the 2-alkylanthracene is composed of anthracene and an alkyl substituent, and the alkyl substituent position is the β position of the anthracene ring.

[0029] The method is characterized in that the carbon number of the alkyl substituent is preferably 2 to 6. Preferably, the 2-alkylanthracene is one or more of 2-ethylanthracene, 2-n-propylanthracene, 2-isopropylanthracene, 2-n-butylanthracene, 2-tert-butylanthracene, 2-tert-amylanthracene, and 2-sec-amylanthracene. DETAILED DESCRIPTION

[0030] The following is a detailed description of the specific embodiments of the present invention. It should be understood that the embodiments described herein are only used to illustrate and explain the present invention and are not intended to limit the present invention.

[0031] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0032] The present invention provides a catalyst for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene, characterized in that the catalyst contains Hβ molecular sieve modified by lanthanide metal and alkaline earth metal.

[0033] Hβ molecular sieve refers to hydrogen-type β molecular sieve, which is commercially available.

[0034] The present invention provides a modified Hβ molecular sieve, which contains lanthanide metals and alkaline earth metals. Based on the total amount of the modified Hβ molecular sieve, the transition metal content is 3-30% by weight and the alkaline earth metal content is 0.1-10% by weight in terms of oxide.

[0035] In order to further improve the stability, catalytic activity and 2-alkylanthraquinone selectivity of the modified Hβ molecular sieve, based on the Hβ molecular sieve modified by lanthanide metals and alkaline earth metals, the lanthanide metal content is 3-30% by weight, and the alkaline earth metal content is 0.1-10% by weight, calculated as oxide; preferably, the lanthanide metal content is 5-28% by weight, and the alkaline earth metal content is 0.5-9% by weight; more preferably, the lanthanide metal content is 9-25% by weight, and the alkaline earth metal content is 3-8% by weight.

[0036] The lanthanide metal element can be selected from a wide range of species. Any lanthanide metal element commonly used in the art can be used in the present invention. The lanthanide metal element can be selected from at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Preferably, the lanthanide metal element is selected from at least one of lanthanum, cerium, praseodymium, and neodymium, with lanthanum being most preferred. The alkaline earth metal is selected from at least one of calcium, magnesium, and barium, with calcium being preferred.

[0037] The present invention also provides a method for preparing a catalyst for oxidizing 2-alkylanthracene to prepare 2-alkylanthraquinone, characterized in that the method comprises the steps of acid treatment of Hβ molecular sieve, loading of lanthanide metal, ion exchange and calcination, wherein the ion exchange solution contains at least one alkaline earth metal compound.

[0038] According to a preferred embodiment of the present invention, the acid treatment conditions include: contacting the Hβ molecular sieve with an aqueous solution of an organic acid, the heating method can be a water bath heating method, the temperature is 20-80°C, the pressure is 0-0.3 MPa (absolute pressure), and the contact time is 2-24 hours; preferably, the Hβ molecular sieve is contacted with the aqueous solution of the organic acid at a temperature of 20-60°C, a pressure of 0-0.1 MPa, and the contact time is 2-18 hours. The acid treatment can further expand the pore size of the Hβ molecular sieve, which is beneficial to increasing the loading capacity of the modified Hβ molecular sieve metal and reducing mass transfer and diffusion resistance.

[0039] According to the preparation method of the present invention, the Hβ molecular sieve is contacted with the organic acid aqueous solution by immersing the Hβ molecular sieve in the organic acid aqueous solution. To ensure more thorough contact, the contact is preferably carried out under stirring. The stirring rate during contact is not particularly limited in the present invention; for example, the stirring rate is 500-1500 rpm, preferably 800-1200 rpm.

[0040] According to the preparation method of the present invention, in the acid treatment, the organic acid is at least one of acetic acid, oxalic acid, benzoic acid, and salicylic acid. More preferably, the organic acid is oxalic acid.

[0041] According to the preparation method of the present invention, preferably, the concentration of the organic acid is 0.1-2 mol / L, and the dosage is 1-20 ml / g molecular sieve. More preferably, the concentration of the organic acid is 0.1-1 mol / L, and the dosage is 1-10 ml / g molecular sieve.

[0042] According to the preparation method of the present invention, preferably, after the acid treatment, the solid is washed with water until neutral, dried, and then loaded with lanthanide metals. The drying conditions are, for example, drying at 120° C. for 1-6 hours.

[0043] According to the preparation method of the present invention, the lanthanide metal loading conditions include: the lanthanide metal loading comprises: first contacting the acid-treated Hβ molecular sieve with a lanthanide metal salt solution, drying and calcining the resulting first solid material to obtain a second solid material, and then second contacting the second solid material with the lanthanide metal salt solution. The drying process is, for example, at 120°C for 1-2 hours, and the calcination is, for example, at 550°C for 1-12 hours. The lanthanide metal loading process is beneficial for increasing the lanthanide metal loading capacity on the modified Hβ molecular sieve, and when the modified Hβ molecular sieve is used in a 2-alkylanthracene oxidation reaction, it is beneficial for improving the reaction selectivity.

[0044] According to the preparation method of the present invention, preferably, the lanthanide metal is selected from at least one of lanthanum, cerium, praseodymium and neodymium, and more preferably, the lanthanide metal is lanthanum.

[0045] According to the preparation method of the present invention, the lanthanide metal salt is selected from at least one of a lanthanide metal chloride, a lanthanide metal carbonate compound, and a lanthanide metal nitrate compound; preferably, the lanthanide metal salt is a lanthanide metal nitrate compound. The concentration of the lanthanide metal salt solution is 1-10 mol / L, preferably 5-10 mol / L.

[0046] According to the preparation method of the present invention, the amount of the lanthanide metal salt solution in the first contact is 5-200 ml / g molecular sieve, preferably, the amount is 20-100 ml / g molecular sieve; the amount of the lanthanide metal salt solution in the second contact is 5-200 ml / g molecular sieve, preferably, the amount is 20-100 ml / g molecular sieve.

[0047] According to the present invention, the conditions for the first contact are: contact temperature of 20-90°C, preferably 50-90°C; contact time of 1-24h, preferably 12-20h; pressure of 0-0.2MPa, preferably 0-0.1MPa; the conditions for the second contact are: contact temperature of 20-90°C, preferably 50-90°C; contact time of 1-24h, preferably 12-20h; pressure of 0-0.2MPa, preferably 0-0.1MPa.

[0048] According to the preparation method of the present invention, the contacting method during the lanthanide metal loading is to immerse the solid Hβ molecular sieve material in the lanthanide metal salt solution. To ensure more thorough contacting, the contacting is preferably carried out under stirring conditions. The stirring rate during the contacting is not particularly limited in the present invention; for example, the stirring rate is 500-1500 rpm, preferably 800-1200 rpm.

[0049] According to the preparation method of the present invention, the solid after the lanthanide metal is loaded is washed with water to neutrality and dried, and then ion exchange is performed.

[0050] According to the preparation method of the present invention, the ion exchange conditions include: exchanging the metal-loaded Hβ molecular sieve with an alkaline earth metal salt solution. The alkaline earth metal in the ion exchange solution is selected from at least one of calcium, magnesium, and barium, preferably calcium. The ion exchange solution is selected from an alkaline earth metal salt solution, preferably an alkaline earth metal nitrate compound solution. Preferably, the concentration of the alkaline earth metal salt solution is 1-10 mol·L -1 , the dosage is 5-200ml (g-molecular sieve) -1 More preferably, the concentration of the alkaline earth metal salt solution is 5-10 mol·L -1 , the dosage is 20-100ml (g-molecular sieve) -1 .

[0051] According to the preparation method of the present invention, the conditions for the ion exchange are: a contact temperature of 20-90°C, preferably 50-90°C, a contact time of 1-24h, preferably 12-20h, and a pressure of 0-0.2MPa, preferably 0-0.1MPa. The ion exchange can be carried out under stirring conditions, for example. The stirring rate selection can refer to the above and will not be repeated here. After the ion exchange, the solid is washed with water until neutral, dried, and calcined. For example, it is dried at 120°C for 1-2h, and then the solid is calcined at 550°C for 1-12h.

[0052] The present invention further provides a catalyst for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene obtained by the preparation method.

[0053] The present invention further provides a method for oxidizing 2-alkylanthracene to produce 2-alkylanthraquinone, characterized in that the method is carried out in the presence of the aforementioned catalyst or the catalyst obtained by the aforementioned preparation method. Specifically, the aforementioned catalyst is used in the 2-alkylanthracene oxidation reaction. In the presence of the catalyst and under oxidation reaction conditions, 2-alkylanthracene, a solvent, and hydrogen peroxide are contacted.

[0054] According to the method of the present invention, the oxidation reaction conditions are: reaction temperature is 30-100° C., preferably 55-95° C.; pressure is 0-0.2 MPa, preferably 0-0.1 MPa; reaction time is 1-24 h, preferably 1-20 h.

[0055] According to the method of the present invention, the solvent is one or more of methanol, ethanol, ether, benzene, toluene, chloroform, acetone, carbon tetrachloride, mesitylene, and N,N-dimethylformamide; preferably, the solvent is one or more of methanol, toluene, carbon tetrachloride, mesitylene, and N,N-dimethylformamide.

[0056] According to the method of the present invention, the molar ratio of hydrogen peroxide to 2-alkylanthracene is (2-20):1, preferably (3-12):1; based on the volume of the solvent, the amount of modified Hβ molecular sieve is 0.001-0.1 (g-molecular sieve) ml -1 ; preferably 0.005-0.07 (g-molecular sieve) ml -1 Based on the volume of the solvent, the concentration of 2-alkylanthracene is 0.01-1g·ml -1 ; preferably 0.02-0.3g ml -1 .

[0057] According to the method of the present invention, the 2-alkylanthracene is composed of anthracene and an alkyl substituent, the alkyl substitution position is the β position of the anthracene ring, the carbon number of the alkyl group is preferably 2-6, and the more preferred 2-alkylanthracene is one or more of 2-ethylanthracene, 2-n-propylanthracene, 2-isopropylanthracene, 2-n-butylanthracene, 2-tert-butylanthracene, 2-tert-amylanthracene, and 2-sec-amylanthracene.

[0058] The modified Hβ molecular sieve provided by the present invention is used as a catalyst in the oxidation reaction of 2-alkylanthracene, achieving a 2-alkylanthracene conversion rate exceeding 53 mol% and a 2-alkylanthraquinone selectivity approaching 98 mol%. After the reaction, the catalyst can be separated and recycled using conventional liquid-solid separation methods. This method has high selectivity, easy catalyst separation and recycling, and an environmentally friendly process.

[0059] The present invention is further described below with reference to examples, but the present invention is not limited thereto.

[0060] In the following examples and comparative examples, the conversion rate and product selectivity of 2-alkylanthracene were calculated using a chromatographic analysis method.

[0061] The conversion rate of 2-alkylanthracene is X Ci-R-AN (mol%), the material selectivity calculated based on the conservation of substance amount is S Ci-R-AQ (mol %), the correction factor is f, and the chromatographic peak area is A.

[0062] Ci-R-AN represents 2-alkylanthracene, and Ci-R-AQ represents 2-alkylanthraquinone.

[0063] The conversion rate of 2-alkylanthracene is shown in formula (1):

[0064]

[0065] The selectivity of 2-alkylanthraquinone is shown in formula (2):

[0066]

[0067] Examples 1-28 illustrate the Hβ molecular sieve modified with lanthanide metals and alkaline earth metals and the modification method of the present invention.

[0068] Example 1

[0069] (1) Hβ molecular sieve was placed in contact with an aqueous oxalic acid solution at 20°C for 2 h, where the oxalic acid concentration was 0.1 mol·L -1 , the dosage is 1ml·(g-molecular sieve) -1 After the reaction, the solid was washed with water until neutral and dried at 120 °C for 2 h to obtain modified Hβ molecular sieve BZ1;

[0070] (2) The acid-treated Hβ molecular sieve BZ1 was mixed with 5 mol·L -1 The first contact is carried out at 50°C with a lanthanum nitrate solution, the amount of lanthanum nitrate used is 20 ml·(g-molecular sieve) -1 The contact time is 12h, the first solid material Z1 obtained by contact is dried at 120℃ for 2h, and then calcined at 550℃ for 2h to obtain the second solid material Z2. The second solid material Z2 is mixed with 5mol·L -1 The lanthanum nitrate solution was contacted for the second time at 50°C, and the amount of lanthanum nitrate used was 20 ml·(g-molecular sieve) -1 The contact time is 12 hours, and the third solid material Z3 obtained by contact is dried at 120° C. for 2 hours to obtain a modified Hβ molecular sieve BZ2;

[0071] (3) The metal-loaded modified Hβ molecular sieve BZ2 was mixed with 5 mol·L -1The calcium nitrate solution was ion exchanged at 50 ° C for 12 h, and the amount of calcium nitrate solution was 20 ml (g-molecular sieve) -1 The solid was then washed with water until neutral, dried at 120°C for 2h, and then calcined at 550°C for 2h to obtain modified Hβ molecular sieve B1.

[0072] Example 2

[0073] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the contact temperature of the Hβ molecular sieve and the oxalic acid aqueous solution is 40° C., and a modified Hβ molecular sieve B2 is obtained.

[0074] Example 3

[0075] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the contact temperature of the Hβ molecular sieve and the oxalic acid aqueous solution is 60° C., and a modified Hβ molecular sieve B3 is obtained.

[0076] Example 4

[0077] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the contact time between the Hβ molecular sieve and the oxalic acid aqueous solution is 10 hours, and a modified Hβ molecular sieve B4 is obtained.

[0078] Example 5

[0079] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the contact time between the Hβ molecular sieve and the oxalic acid aqueous solution is 18 hours, and a modified Hβ molecular sieve B5 is obtained.

[0080] Example 6

[0081] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the concentration of the oxalic acid aqueous solution in contact with the Hβ molecular sieve is 0.5 mol·L -1 , and the modified Hβ molecular sieve B6 was prepared.

[0082] Example 7

[0083] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the concentration of the oxalic acid aqueous solution in contact with the Hβ molecular sieve is 1 mol·L -1 , to obtain modified Hβ molecular sieve B7.

[0084] Example 8

[0085] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the amount of oxalic acid aqueous solution in contact with the Hβ molecular sieve is 5 ml·(g-molecular sieve) -1, and the modified Hβ molecular sieve B8 was prepared.

[0086] Example 9

[0087] Step (2) and step (3) are the same as those in Example 1. The difference is that in step (1), the amount of oxalic acid aqueous solution in contact with the Hβ molecular sieve is 10 ml·(g-molecular sieve) -1 , to obtain modified Hβ molecular sieve B9.

[0088] Example 10

[0089] Step (1) and step (3) are the same as those in Example 1. The difference is that in step (2), the temperature during the first contact and the second contact is 70°C, and the modified Hβ molecular sieve B is obtained. 10 .

[0090] Example 11

[0091] Step (1) and step (3) are the same as those in Example 1. The difference is that in step (2), the temperature during the first contact and the second contact is 90°C, and the modified Hβ molecular sieve B is obtained. 11 .

[0092] Example 12

[0093] Step (1) and step (3) are the same as those in Example 1. The difference is that in step (2), the time of the first contact and the time of the second contact are 16 hours respectively, and the modified Hβ molecular sieve B is obtained. 12 .

[0094] Example 13

[0095] Step (1) and step (3) are the same as those in Example 1. The difference is that in step (2), the time of the first contact and the second contact are 20 hours respectively, and the modified Hβ molecular sieve B is obtained. 13 .

[0096] Example 14

[0097] Step (1) and step (3) are the same as in Example 1. The difference is that in step (2), the concentration of the lanthanum nitrate solution used in the first contact and the second contact is 7 mol·L -1 , to obtain modified Hβ molecular sieve B 14 .

[0098] Example 15

[0099] Step (1) and step (3) are the same as in Example 1. The difference is that in step (2), the concentration of the lanthanum nitrate solution used in the first contact and the second contact is 10 mol·L -1 , to obtain modified Hβ molecular sieve B15 .

[0100] Example 16

[0101] Step (1) and step (3) are the same as in Example 1. The difference is that in step (2), the amount of lanthanum nitrate solution used in the first contact and the second contact is 60 ml·(g-molecular sieve) -1 , to obtain modified Hβ molecular sieve B 16 .

[0102] Example 17

[0103] Step (1) and step (3) are the same as in Example 1. The difference is that in step (2), the amount of lanthanum nitrate solution used in the first contact and the second contact is 100 ml·(g-molecular sieve) -1 , to obtain modified Hβ molecular sieve B 17 .

[0104] Example 18

[0105] Steps (1) and (2) are the same as those in Example 1. The difference is that in step (3), the reaction temperature of the modified Hβ molecular sieve BZ2 and the calcium nitrate solution is 70°C to obtain the modified Hβ molecular sieve B 18 .

[0106] Example 19

[0107] Steps (1) and (2) are the same as those in Example 1. The difference is that in step (3), the reaction temperature of the modified Hβ molecular sieve BZ2 and the calcium nitrate solution is 90°C to obtain the modified Hβ molecular sieve B 19 .

[0108] Example 20

[0109] Steps (1) and (2) are the same as those in Example 1. The difference is that in step (3), the modified Hβ molecular sieve BZ2 reacts with the calcium nitrate solution for 16 hours to obtain the modified Hβ molecular sieve BZ2. 20 .

[0110] Example 21

[0111] Steps (1) and (2) are the same as those in Example 1. The difference is that in step (3), the modified Hβ molecular sieve BZ2 reacts with the calcium nitrate solution for 20 hours to obtain the modified Hβ molecular sieve BZ2. 21 .

[0112] Example 22

[0113] Steps (1) and (2) are the same as in Example 1. The difference is that in step (3), the concentration of the calcium nitrate solution reacting with the modified Hβ zeolite BZ2 is 7 mol·L -1 , to obtain the modified Hβ zeolite B 22 .

[0114] Example 23

[0115] Steps (1) and (2) are the same as in Example 1. The difference is that in step (3), the concentration of the calcium nitrate solution reacting with the modified Hβ zeolite BZ2 is 10 mol·L -1 , to obtain the modified Hβ zeolite B 23 .

[0116] Example 24

[0117] Steps (1) and (2) are the same as in Example 1. The difference is that in step (3), the amount of the calcium nitrate solution reacting with the modified Hβ zeolite BZ2 is 60 ml·(g-zeolite) -1 , to obtain the modified Hβ zeolite B 24 .

[0118] Example 25

[0119] Steps (1) and (2) are the same as in Example 1. The difference is that in step (3), the amount of the calcium nitrate solution reacting with the modified Hβ zeolite BZ2 is 100 ml·(g-zeolite) -1 , to obtain the modified Hβ zeolite B 25 .

[0120] Example 26

[0121] Steps (1) and (3) are the same as in Example 1. The difference is that in step (2), the aqueous cerium nitrate solution is used to contact the Hβ zeolite treated with acid twice, to obtain the modified Hβ zeolite B 26 .

[0122] Example 27

[0123] Steps (1) and (2) are the same as in Example 1. The difference is that in step (3), the aqueous magnesium chloride solution is used to ion-exchange the modified Hβ zeolite loaded with metal, to obtain the modified Hβ zeolite B 27 .

[0124] Example 28

[0125] Steps (1) and (3) are the same as in Example 26. The difference is that in step (3), the aqueous magnesium chloride solution is used to ion-exchange the modified Hβ zeolite loaded with metal, to obtain the modified Hβ zeolite B 28.

[0126] Catalyst B1-B prepared in Examples 1-28 above 28 The composition is shown in Table 1.

[0127] Comparative Example 1

[0128] Steps (2) and (3) are the same as those in Example 1, except that in step (1), the Hβ molecular sieve is contacted with hydrochloric acid, and the Hβ molecular sieve is contacted with hydrochloric acid at 20°C for 2 h, wherein the hydrochloric acid concentration is 0.1 mol·L -1 , the dosage is 1ml·(g-molecular sieve) -1 , to obtain modified Hβ molecular sieve B d1 .

[0129] Comparative Example 2

[0130] Steps (1) and (3) are the same as those in Example 1, except that after step (1), step (2) is not performed and step (3) is performed directly to obtain modified Hβ molecular sieve B. d2 .

[0131] Comparative Example 3

[0132] Steps (1) and (3) are the same as those in Example 1, except that in step (2), the Hβ molecular sieve is only contacted with the lanthanum nitrate solution once. -1 The lanthanum nitrate solution was contacted at 50°C, and the amount of lanthanum nitrate used was 20 ml·(g-molecular sieve) -1 The contact time is 12h, and the solid material obtained by contact is dried at 120℃ for 2h to obtain modified Hβ molecular sieve BZ3, which is then obtained by step (3) to obtain modified Hβ molecular sieve B d3 .

[0133] Comparative Example 4

[0134] Steps (1) and (2) are the same as those in Example 1, except that in step (3), the modified Hβ molecular sieve BZ2 is not subjected to ion exchange with the calcium nitrate solution, but is directly calcined at 550°C for 2h to obtain the modified Hβ molecular sieve B d4 .

[0135] Comparative Example 5

[0136] No modification is performed on Hβ molecular sieve, which is denoted as B d5 .

[0137] Comparative catalyst B prepared in Comparative Examples 1-5 d1 -B d5 The composition is shown in Table 1.

[0138] Table 1

[0139] Metal content and content Alkali metal content(weight%) <![CDATA[B1]]> At, 9.1 Like, 3.0 <![CDATA[B2]]> At, 11.5 As, 4.2 [B3] At, 12.6 As, 7.3 <![CDATA[B4]]> At, 12.5 As, 4.3 [B5] At, 12.6 As, 7.6 <![CDATA[B6]]> At, 15.9 As, 4.8 <![CDATA[B7]]> At, 17.4 Like, 7.7 <![CDATA[B8]]> At, 16.3 As, 7.6 <![CDATA[B9]]> At, 17.1 Like, 7.7 B 10 ]]> At, 20.7 As, 3.1 <![CDATA[B 11 ]]> At, 23.0 As, 3.2 <![CDATA[B 12 ]]> At, 21.0 As, 3.1 <![CDATA[B 13 ]]> On, 23.4 As, 3.2 B 14 ]]> At, 19.8 As, 3.1 <![CDATA[B 15 ]]> At, 21.1 As, 3.1 <![CDATA[B 16 ]]> At, 14.5 As, 3.1 <![CDATA[B 17 ]]> At, 22.2 As, 3.2 B 18 ]]> At, 9.1 Like, 5.1 B 19 ]]> At, 9.1 As, 7.9 B 20 ]]> At, 9.0 As, 6.2 B 21 ]]> At, 9.1 Like, 8.0 <![CDATA[B 22 ]]> At, 9.0 As, 6.1 <![CDATA[B 23 ]]> At, 9.1 As, 7.6 B 24 ]]> At, 9.1 As, 6.3 <![CDATA[B 25 ]]> At, 9.2 Like, 7.5 B 26 ]]> What, 8.9 Like, 3.0 <![CDATA[B 27 ]]> At, 9.0 Mg, 2.8 <![CDATA[B 28 ]]> What, 8.8 Mg, 2.8 <![CDATA[B d1 ]]> At, 2.5 Like, 1.0 <![CDATA[B d2 ]]> At,0 As, 2.8 <![CDATA[B d3 ]]> At, 4.5 As, 2.9 <![CDATA[B d4 ]]> At, 9.1 Like, 0 <![CDATA[B d5 ]]> At,0 Like, 0

[0140] Examples 29-56 are used to illustrate the process for preparing 2-alkylanthraquinone by oxidation of 2-alkylanthracene according to the present application.

[0141] Example 29

[0142] Into a 500ml jacketed reactor, 15g of 2-alkylanthracene (18wt% 2-butylanthracene, 73wt% 2-pentylanthracene, 1wt% 2-hexylanthracene, 8wt% impurities, same below), 150ml of N,N-dimethylformamide solvent, 2.84g of modified Hβ zeolite B1 prepared in Example 1, heated in a water bath at 70°C, 33.5ml of hydrogen peroxide (35wt%) was added to the reaction system at a rate of 0.5ml / min by peristaltic pump. The reaction was stirred by a magnetic stirrer at a rate of 1000rpm, after the reaction, the catalyst was separated by simple liquid-solid filtration, then the reaction liquid was analyzed by chromatography. The results are shown in Table 2.

[0143] Examples 30-56

[0144] Examples 30-56 are the same as Example 29, except that the modified Hβ zeolite B1 is replaced by B2-B 28 , respectively. The results are shown in Tables 2-3.

[0145] Comparative Examples 6-10

[0146] Comparative Examples 6-10 are the same as Example 29, except that the modified Hβ zeolite B1 is replaced by B d1 -B d5 , respectively. The results are shown in Table 4.

[0147] Table 2

[0148]

[0149] Table 3

[0150]

[0151] Table 4

[0152]

[0153] Examples 57-66 are used to illustrate the process for preparing 2-alkylanthraquinone by oxidation of 2-alkylanthracene according to the present application.

[0154] Example 57

[0155] The same as Example 39, except that the amount of 2-alkylanthracene used is 20g.

[0156] Example 58

[0157] The same as Example 39, except that the amount of 2-alkylanthracene used is 25 g.

[0158] Example 59

[0159] Same as Example 39, except that the modified Hβ molecular sieve B 11 The dosage is 0.5g.

[0160] Example 60

[0161] Same as Example 39, except that the modified Hβ molecular sieve B 11 The dosage is 1.0g.

[0162] Example 61

[0163] Same as Example 39, except that the water bath heating temperature is 50°C.

[0164] Example 62

[0165] Same as Example 39, except that the water bath heating temperature is 90°C.

[0166] Example 63

[0167] The same as Example 39, except that the feed rate of hydrogen peroxide was 0.2 ml / min.

[0168] Example 64

[0169] The same as Example 39, except that the feed rate of hydrogen peroxide was 0.4 ml / min.

[0170] Example 65

[0171] The same as Example 39, except that the amount of hydrogen peroxide used is 5 ml.

[0172] Example 66

[0173] The same as Example 39, except that the amount of hydrogen peroxide used is 10 ml.

[0174] The reaction solutions of Examples 57-66 were subjected to chromatographic analysis. The results are shown in Table 5. Table 5 also lists the results of Example 39.

[0175] Table 5

[0176] example no X Ci-R-AN / %]]> <![CDATA[S Ci-R-AQ / %]]> 39 53.1 97.8 57 40.2 96.8 58 38.5 96.7 59 42.1 96.8 60 48.0 97.0 61 40.2 98.0 62 54.2 89.9 63 45.6 96.1 64 49.7 97.1 65 17.2 95.6 66 34.1 96.2

Claims

1. A method for preparing 2-alkylanthraquinone by oxidizing 2-alkylanthracene, comprising contacting 2-alkylanthracene, a solvent, and hydrogen peroxide in the presence of a catalyst and under oxidation reaction conditions, wherein: The catalyst contains Hβ molecular sieve modified by lanthanide metal and alkaline earth metal. Based on the Hβ molecular sieve modified by lanthanide metal and alkaline earth metal, the lanthanide metal content is 9-25% by weight and the alkaline earth metal content is 3-8% by weight in terms of oxide.

2. The method according to claim 1, characterized in that The contacting is carried out at a temperature of 30-100° C., a pressure of 0-0.2 MPa, and a time of 1-24 h.

3. The method according to claim 2, characterized in that The contacting is carried out at a temperature of 55-95° C., a pressure of 0-0.1 MPa and a time of 1-20 h.

4. The method according to claim 1, characterized in that The solvent is one or more of methanol, ethanol, ether, benzene, toluene, chloroform, acetone, carbon tetrachloride, mesitylene, and N,N-dimethylformamide.

5. The method according to claim 1, characterized in that The solvent is one or more of methanol, toluene, carbon tetrachloride, mesitylene, and N,N-dimethylformamide.

6. The method according to claim 1, characterized in that The molar ratio of hydrogen peroxide to 2-alkylanthracene is (2-20):1; the amount of the catalyst is 0.001-0.1 g per milliliter of solvent, and the catalyst is calculated as a molecular sieve; the concentration of the 2-alkylanthracene is 0.01-1 g per milliliter of solvent.

7. The method according to claim 1, characterized in that The molar ratio of hydrogen peroxide to 2-alkylanthracene is (3-12):1; the amount of the catalyst is 0.005-0.07 g per milliliter of solvent, and the catalyst is calculated as molecular sieve; the concentration of the 2-alkylanthracene is 0.02-0.3 g per milliliter of solvent.

8. The method according to claim 1, 6 or 7, characterized in that The structure of the 2-alkylanthracene is composed of anthracene and an alkyl substituent, and the alkyl substituent is located at the β position of the anthracene ring.

9. The method according to claim 8, characterized in that The carbon number of the alkyl substituent is 2-6.

10. The method according to claim 1, characterized in that The 2-alkylanthracene is one or more of 2-ethylanthracene, 2-n-propylanthracene, 2-isopropylanthracene, 2-n-butylanthracene, 2-tert-butylanthracene, 2-tert-amylanthracene, and 2-sec-amylanthracene.

11. The method according to claim 1, characterized in that The lanthanide metal is selected from at least one of lanthanum, cerium, praseodymium and neodymium, and the alkaline earth metal is selected from at least one of calcium, magnesium and barium.

12. The method according to claim 11, characterized in that The lanthanide metal is lanthanum, and the alkaline earth metal is calcium.

13. The method according to claim 1, characterized in that The catalyst is prepared by a method comprising the steps of acid-treating an Hβ molecular sieve, loading a lanthanide metal, ion-exchanging, and calcining the Hβ molecular sieve. The lanthanide metal loading comprises: first contacting the acid-treated Hβ molecular sieve with a lanthanide metal salt solution, drying and calcining the first solid material obtained by the contact to obtain a second solid material, and then second contacting the second solid material with a lanthanide metal salt solution. The ion exchange comprises exchanging a solution containing at least one alkaline earth metal compound.

14. The method according to claim 13, characterized in that The acid treatment step comprises: contacting the Hβ molecular sieve with an aqueous solution of an organic acid at a temperature of 20-80° C., a pressure of 0-0.3 MPa, and a contact time of 2-24 hours.

15. The method according to claim 14, characterized in that In the acid treatment step, the temperature is 20-60° C., the pressure is 0-0.1 MPa, and the contact time is 2-18 hours.

16. The method according to claim 14, characterized in that The organic acid is at least one of acetic acid, oxalic acid, benzoic acid and salicylic acid.

17. The method according to claim 16, characterized in that The organic acid is oxalic acid.

18. The method according to claim 14, characterized in that The aqueous solution of the organic acid has a concentration of 0.1-2 mol·L -1 .

19. The method according to claim 18, characterized in that The aqueous solution of the organic acid has a concentration of 0.1-1 mol·L -1 .

20. The method according to claim 14, characterized in that The dosage of the organic acid is 1-20 ml / g molecular sieve.

21. The method according to claim 20, characterized in that The dosage of the organic acid is 1-10 ml / g molecular sieve.

22. The method according to claim 13, characterized in that After the acid treatment step, the solid is washed with water until it is neutral, and then dried before the solid is loaded with lanthanide metals.

23. The method according to claim 13, characterized in that The lanthanide metal is selected from at least one of lanthanum, cerium, praseodymium and neodymium.

24. The method according to claim 13, characterized in that The lanthanide metal is lanthanum.

25. The method according to claim 13, characterized in that The lanthanide metal salt is selected from at least one of lanthanide metal chlorides, lanthanide metal carbonate compounds and lanthanide metal nitrate compounds.

26. The method according to claim 13, characterized in that The lanthanide metal salt is a nitrate compound of a lanthanide metal.

27. The method according to claim 13, characterized in that The concentration of the lanthanide metal salt solution is 1-10 mol / L.

28. The method according to claim 27, characterized in that The concentration of the lanthanide metal salt solution is 5-10 mol / L.

29. The method according to claim 13, characterized in that The amount of the lanthanide metal salt solution used in the first contact is 5-200 ml / g molecular sieve; the amount of the lanthanide metal salt solution used in the second contact is 5-200 ml / g molecular sieve.

30. The method according to claim 29, characterized in that The amount of the lanthanide metal salt solution used in the first contact is 20-100 ml / g molecular sieve; the amount of the lanthanide metal salt solution used in the second contact is 20-100 ml / g molecular sieve.

31. The method according to claim 13, wherein The conditions for the first contact are: contact temperature of 20-90°C, contact time of 1-24h, and pressure of 0-0.2MPa; the conditions for the second contact are: contact temperature of 20-90°C, contact time of 1-24h, and pressure of 0-0.2MPa.

32. The method according to claim 31, characterized in that The conditions for the first contact are: contact temperature of 50-90°C, contact time of 12-20h, and pressure of 0-0.1MPa; the conditions for the second contact are: contact temperature of 50-90°C, contact time of 12-20h, and pressure of 0-0.1MPa.

33. The method according to claim 13, wherein The solid after the lanthanide metal loading step is washed with water to neutrality and dried before being subjected to an ion exchange step.

34. The method according to claim 13, wherein In the ion exchange step, the alkaline earth metal in the exchange solution is selected from at least one of calcium, magnesium and barium.

35. The method according to claim 34, characterized in that In the ion exchange step, the alkaline earth metal in the exchange solution is calcium.

36. The method according to claim 34 or 35, characterized in that In the ion exchange step, the exchange solution is selected from alkaline earth metal salt solution.

37. The method according to claim 36, characterized in that In the ion exchange step, the exchange solution is a solution of a nitrate compound of an alkaline earth metal.

38. The method according to claim 36, characterized in that The concentration of the alkaline earth metal salt solution is 1-10 mol·L -1 .

39. The method according to claim 38, characterized in that The concentration of the alkaline earth metal salt solution is 5-10 mol·L -1 .

40. The method according to claim 36, characterized in that The amount of the alkaline earth metal salt solution used is 5-200 ml / g molecular sieve.

41. The method according to claim 40, characterized in that The amount of the alkaline earth metal salt solution used is 20-100 ml / g molecular sieve.

42. The method according to claim 13, wherein The conditions of the ion exchange step are: contact temperature of 20-90° C., contact time of 1-24 h, and pressure of 0-0.2 MPa.

43. The method according to claim 42, characterized in that The conditions of the ion exchange step are: contact temperature of 50-90° C., contact time of 12-20 h, and pressure of 0-0.1 MPa.

44. The method according to claim 13, wherein After the ion exchange step, the solid is washed with water until neutral, dried, and calcined.

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