Catalyst for synthesis of epoxybutane, preparation method of catalyst and synthesis method of epoxybutane

Abstract

The invention provides a catalyst for synthesis of epoxybutane, a preparation method of the catalyst and a synthesis method of epoxybutane, and belongs to the technical field of organic chemistry. The preparation method comprises the following steps: preparing an aluminum / magnesium / nickel layered metal oxide, depositing magnetic ferroferric oxide, compounding with phytic acid and beta-cyclodextrin, and impregnating with an impregnation liquid containing manganese salt and lanthanum salt to prepare the catalyst for synthesizing epoxybutane. The prepared catalyst is high in stability and catalytic activity, simple to prepare, easy to separate, high in repeated utilization rate, free of environmental pollution, green, efficient, low in cost and easy to realize industrial application.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemistry, and in particular to a catalyst for synthesizing butylene oxide and a preparation method thereof, and a method for synthesizing butylene oxide. Background Art

[0002] Butylene oxide (BO), also known as butylene oxide, is an organic synthesis raw material that can be used to manufacture organic synthesis intermediates and high molecular polymers, such as butanediol and butanolamine. Butanediol (CH3-CH2-CHOH-CH2OH) can be produced by hydrolysis of butylene oxide, which is the raw material for producing polymer plasticizers.

[0003] Butylene oxide can also replace acetone as a diluent for nitrocellulose lacquer with good performance. It can also be used as an antioxidant for chlorine-containing compounds, an anticorrosive agent for the production of vinyl chloride resin, a surfactant, a gasoline additive, etc. Butylene oxide is also a stabilizer for 1,1,1-trichloroethane (CH3-CCl3) and other chlorinated solvents.

[0004] The main production method of butylene oxide in industry still adopts the chlorohydrin process, that is, first chlorohydrinizing butene with hypochlorous acid and then epoxidizing it. However, when synthesizing butylene oxide by the chlorohydrin process, a large amount of Cl2 is consumed, the equipment is seriously corroded, and waste water and waste residue containing CaCl2 and organic chloride are produced during production, which causes great pollution to the environment. In addition, the production equipment is required to be built in a place with chlorine resources and sewage discharge conditions, and the production site requirements are relatively strict.

[0005] Due to pollution problems, the chlorohydrin method will inevitably be phased out. In recent years, the method of directly epoxidizing butene to produce butylene oxide under the action of a catalyst has attracted people's attention. In contrast, the direct epoxidation of butene omits the chlorohydrin step, thus simplifying the production process and, in particular, greatly reducing environmental pollution.

[0006] Chinese invention patent CN101085763B discloses a method for synthesizing 1,2-butylene oxide, wherein butylene oxide is synthesized from butene in one step. The whole process is simple and pollution-free, and the selectivity of butylene oxide is high. However, the price of the raw material butene is relatively expensive, and the purity of butene is required to be high, so the production cost of this method is relatively high. Summary of the invention

[0007] The invention aims to provide a catalyst for the synthesis of butylene oxide and a preparation method thereof, and a method for synthesizing butylene oxide, which improves the stability and catalytic activity of the prepared catalyst, is simple to prepare, and the prepared catalyst is easy to separate, has a high reuse rate, is environmentally friendly and efficient, has a low cost, and is easy to realize industrial application.

[0008] The technical solution of the present invention is achieved in this way:

[0009] The invention provides a method for preparing a catalyst for synthesizing butylene oxide. The method comprises the following steps: preparing aluminum / magnesium / nickel layered metal oxide, depositing magnetic ferroferric oxide, compounding with phytic acid and beta-cyclodextrin, and impregnating with an impregnation solution containing manganese salt and lanthanum salt to obtain the catalyst for synthesizing butylene oxide.

[0010] As a further improvement of the present invention, the following steps are included:

[0011] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: dissolving nickel nitrate, magnesium nitrate, aluminum nitrate and urea in water, heating and aging, filtering, washing and drying to obtain aluminum / magnesium / nickel layered metal oxide;

[0012] S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: adding aluminum / magnesium / nickel layered metal oxide to water, adding ferric chloride and ferrous chloride, adding ammonia water dropwise under inert gas protection, heating and stirring to react, filtering, washing, drying, and calcining to obtain magnetic aluminum / magnesium / nickel layered metal oxide;

[0013] S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: adding magnetic aluminum / magnesium / nickel layered metal oxide, phytic acid, β-cyclodextrin, and potassium dihydrogen phosphate to water, heating and stirring, hydrothermal reaction, adding the product to alkaline solution, stirring at room temperature, filtering, washing, and drying to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex;

[0014] S4. Preparation of an impregnation solution: dissolving a manganese salt and a lanthanum salt in water to obtain an impregnation solution;

[0015] S5. Preparation of a catalyst for the synthesis of butylene oxide: Add a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to the impregnation solution, impregnate overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

[0016] As a further improvement of the present invention, the molar ratio of nickel nitrate, magnesium nitrate, aluminum nitrate and urea in step S1 is 0.5-1.5:1-2:1:18-20, and the heating aging temperature is 120-140° C. and the time is 40-52 h.

[0017] As a further improvement of the present invention, the mass ratio of the aluminum / magnesium / nickel layered metal oxide, ferric chloride, ferrous chloride and ammonia water in step S2 is 10-12:3.24:1.26:3-5, the temperature of the heating and stirring reaction is 85-95°C, the time is 3-5h, and the calcination temperature is 450-550°C, and the time is 1-3h.

[0018] As a further improvement of the present invention, the mass ratio of the magnetic aluminum / magnesium / nickel layered metal oxide, phytic acid, β-cyclodextrin and potassium dihydrogen phosphate in step S3 is 10:1-3:3-5:0.2-0.4, the heating and stirring temperature is 90-110°C, the time is 0.5-1.5h, the hydrothermal reaction temperature is 145-155°C, the time is 8-10h, the alkali solution is 0.1-0.2mol / L NaOH or KOH solution, and the room temperature stirring time is 1-3h.

[0019] As a further improvement of the present invention, the manganese salt in step S4 is manganese chloride or manganese nitrate, the lanthanum salt is lanthanum nitrate, and the mass ratio of the manganese salt to the lanthanum salt is 10-15:1-2.

[0020] As a further improvement of the present invention, the mass ratio of the magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to the impregnation solution in step S5 is 1:3-5.

[0021] As a further improvement of the present invention, the present invention specifically comprises the following steps:

[0022] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 0.5-1.5 molar equivalents of nickel nitrate, 1-2 molar equivalents of magnesium nitrate, 1 molar equivalent of aluminum nitrate, and 18-20 molar equivalents of urea are dissolved in water, heated to 120-140° C., aged for 40-52 hours, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide;

[0023] S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: 10-12 parts by weight of aluminum / magnesium / nickel layered metal oxide is added to water, 3.24 parts by weight of ferric chloride and 1.26 parts by weight of ferrous chloride are added, 3-5 parts by weight of ammonia water are added dropwise under inert gas protection, heated to 85-95° C., stirred for reaction for 3-5 hours, filtered, washed, dried, and calcined at 450-550° C. for 1-3 hours to obtain a magnetic aluminum / magnesium / nickel layered metal oxide;

[0024] S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: 10 parts by weight of magnetic aluminum / magnesium / nickel layered metal oxide, 1-3 parts by weight of phytic acid, 3-5 parts by weight of β-cyclodextrin, and 0.2-0.4 parts by weight of potassium dihydrogen phosphate are added to water, heated to 90-110°C, stirred for 0.5-1.5h, and hydrothermally reacted at 145-155°C for 8-10h, the product is added to 0.1-0.2mol / L NaOH or KOH solution, stirred at room temperature for 1-3h, filtered, washed, and dried to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex;

[0025] S4. Preparation of an impregnation solution: 10-15 parts by weight of a manganese salt, 1-2 parts by weight of a lanthanum salt were dissolved in water to obtain an impregnation solution;

[0026] S5. Preparation of a catalyst for the synthesis of butylene oxide: Add 10 parts by weight of a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to 30-50 parts by weight of the impregnation solution, soak overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

[0027] The present invention further protects a catalyst for synthesizing butylene oxide obtained by the above preparation method.

[0028] The present invention further protects a method for synthesizing butylene oxide, comprising mixing low-carbon alcohol, hydrogen peroxide and 1-butene, reacting under the action of the above catalyst to obtain butylene oxide, separating the catalyst with a magnet, washing, drying and recycling.

[0029] As a further improvement of the present invention, the low-carbon alcohol is selected from at least one of methanol, ethanol, propylene glycol, glycerol, propanol, butanol, and 1,2-butanediol.

[0030] As a further improvement of the present invention, the concentration of the hydrogen peroxide is 15-20wt%.

[0031] As a further improvement of the present invention, the reaction temperature is 50-80°C, the reaction time is 40-70min, the reaction pressure is 1-2Mpa, the rotation speed is 300-700r / min, and the amount of the catalyst added is 0.1-0.15wt% of the total mass of the system.

[0032] The present invention has the following beneficial effects:

[0033] Aluminum / magnesium / nickel layered metal oxides have two-dimensional structural characteristics, such as a large specific surface area, exchangeability of anions and flexible interlayer space. The hydroxyl groups on the surface can promote the in-situ generation of magnetic ferroferric oxide materials. The multi-metal structure has a certain promoting effect on catalytic activity. It can then be coupled with β-cyclodextrin through phytic acid. Its surface has abundant hydroxyl, phosphate, carboxyl groups, etc., which can form hydrogen bonds with metal ions such as manganese and lanthanum, thereby greatly increasing the loading capacity of metal ions. At the same time, aluminum / magnesium / nickel layered metal oxides have abundant surface defect sites, thereby improving the catalytic activity of aluminum / magnesium / nickel layered metal oxides, improving the stability and catalytic activity of the prepared catalyst, and the preparation is simple. The prepared catalyst is easy to separate, has a high reuse rate, is environmentally friendly and efficient, has a low cost, and is easy to realize industrial application.

[0034] The catalyst in the present invention is coupled with beta-cyclodextrin, which is a type of cyclic structure formed by connecting multiple glucose units through glycosidic bonds, has a hydrophilic appearance and a hydrophobic inner cavity, and therefore has a strong molecular inclusion ability, can form a stable inclusion complex with the hydrophobic reaction molecule butene, improves the binding ability of the catalyst with the reaction substrate, promotes the in-situ reaction of the reactants, and reduces the reaction activation energy.

[0035] The manganese metal of the present invention greatly improves the catalytic activity of the catalyst under the synergistic catalytic effect of the lanthanum metal. The doping of the lanthanum metal enriches the electron density around the manganese metal, enhances the binding ability of the active center with butene, reduces the energy barrier of the reaction, and improves the catalytic reaction activity.

[0036] The synthetic method of butylene oxide of the present invention has the advantages of easy control of process, simple post-processing, good economic benefit, environmentally friendly process, high butene conversion rate, few reaction side reactions, high selectivity of butylene oxide, and broad application prospects. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] Example 1

[0039] This embodiment provides a method for preparing a catalyst for synthesizing butylene oxide, comprising the following steps:

[0040] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 0.5 mmol nickel nitrate, 1 mmol magnesium nitrate, 1 mmol aluminum nitrate, and 18 mmol urea were dissolved in 50 mL water, heated to 120° C., aged for 40 h, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide;

[0041] S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: 10 g of aluminum / magnesium / nickel layered metal oxide was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, 3 g of ammonia water was added dropwise under nitrogen protection, the mixture was heated to 85° C., stirred for reaction for 3 h, filtered, washed, dried, and calcined at 450° C. for 1 h to obtain magnetic aluminum / magnesium / nickel layered metal oxide;

[0042] S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: 10 g of magnetic aluminum / magnesium / nickel layered metal oxide, 1 g of phytic acid, 3 g of β-cyclodextrin, and 0.2 g of potassium dihydrogen phosphate were added to 200 mL of water, heated to 90°C, stirred for 0.5 h, and hydrothermally reacted at 145°C for 8 h. The product was added to 0.1 mmol / L NaOH solution, stirred at room temperature for 1 h, filtered, washed, and dried to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex;

[0043] S4. Preparation of the impregnation solution: 10 g of manganese chloride and 1 g of lanthanum nitrate were dissolved in 100 mL of water to obtain an impregnation solution;

[0044] S5. Preparation of a catalyst for the synthesis of butylene oxide: Add 10 g of a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to 30 g of the impregnation solution, soak overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

[0045] Example 2

[0046] This embodiment provides a method for preparing a catalyst for synthesizing butylene oxide, comprising the following steps:

[0047] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 1.5 mmol nickel nitrate, 2 mmol magnesium nitrate, 1 mmol aluminum nitrate, and 20 mmol urea were dissolved in 50 mL water, heated to 140° C., aged for 52 h, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide;

[0048] S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: 12 g of aluminum / magnesium / nickel layered metal oxide was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, 5 g of ammonia water was added dropwise under nitrogen protection, the mixture was heated to 95° C., stirred for reaction for 5 h, filtered, washed, dried, and calcined at 550° C. for 3 h to obtain magnetic aluminum / magnesium / nickel layered metal oxide;

[0049] S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: 10 g of magnetic aluminum / magnesium / nickel layered metal oxide, 3 g of phytic acid, 5 g of β-cyclodextrin, and 0.4 g of potassium dihydrogen phosphate were added to 200 mL of water, heated to 110° C., stirred for 1.5 h, and hydrothermally reacted at 155° C. for 10 h. The product was added to a 0.2 mmol / L KOH solution, stirred at room temperature for 3 h, filtered, washed, and dried to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex;

[0050] S4. Preparation of the impregnation solution: 15 g of manganese nitrate and 2 g of lanthanum nitrate were dissolved in 100 mL of water to obtain an impregnation solution;

[0051] S5. Preparation of a catalyst for the synthesis of butylene oxide: Add 10 g of a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to 50 g of the impregnation solution, soak overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

[0052] Example 3

[0053] This embodiment provides a method for preparing a catalyst for synthesizing butylene oxide, comprising the following steps:

[0054] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 1 mmol nickel nitrate, 1.5 mmol magnesium nitrate, 1 mmol aluminum nitrate, and 19 mmol urea were dissolved in 50 mL water, heated to 130° C., aged for 48 h, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide;

[0055] S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: 11 g of aluminum / magnesium / nickel layered metal oxide was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, 4 g of ammonia water was added dropwise under nitrogen protection, the mixture was heated to 90° C., stirred for 4 h, filtered, washed, dried, and calcined at 500° C. for 2 h to obtain magnetic aluminum / magnesium / nickel layered metal oxide;

[0056] S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: 10 g of magnetic aluminum / magnesium / nickel layered metal oxide, 2 g of phytic acid, 4 g of β-cyclodextrin, and 0.3 g of potassium dihydrogen phosphate were added to 200 mL of water, heated to 100 ° C, stirred for 1 h, and hydrothermally reacted at 150 ° C for 9 h. The product was added to 0.5 mmol / L NaOH solution, stirred at room temperature for 2 h, filtered, washed, and dried to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex;

[0057] S4. Preparation of the impregnation solution: 12 g of manganese chloride and 1.5 g of lanthanum nitrate were dissolved in 100 mL of water to obtain an impregnation solution;

[0058] S5. Preparation of a catalyst for the synthesis of butylene oxide: Add 10 g of a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to 40 g of the impregnation solution, soak overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

[0059] Comparative Example 1

[0060] Compared with Example 3, the difference is that step S2 is not performed.

[0061] The details are as follows:

[0062] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 1 mmol nickel nitrate, 1.5 mmol magnesium nitrate, 1 mmol aluminum nitrate, and 19 mmol urea were dissolved in 50 mL water, heated to 130° C., aged for 48 h, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide;

[0063] S2. Preparation of aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: 10 g of magnetic aluminum / magnesium / nickel layered metal oxide, 2 g of phytic acid, 4 g of β-cyclodextrin, and 0.3 g of potassium dihydrogen phosphate were added to 200 mL of water, heated to 100 ° C, stirred for 1 h, and hydrothermally reacted at 150 ° C for 9 h. The product was added to 0.5 mmol / L NaOH solution, stirred at room temperature for 2 h, filtered, washed, and dried to obtain an aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex;

[0064] S3. Preparation of the impregnation solution: 12 g of manganese chloride and 1.5 g of lanthanum nitrate were dissolved in 100 mL of water to obtain an impregnation solution;

[0065] S4. Preparation of a catalyst for the synthesis of butylene oxide: Add 10 g of an aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to 40 g of the impregnation solution, soak overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

[0066] Comparative Example 2

[0067] Compared with Example 3, the difference is that step S3 is not performed.

[0068] The details are as follows:

[0069] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 1 mmol nickel nitrate, 1.5 mmol magnesium nitrate, 1 mmol aluminum nitrate, and 19 mmol urea were dissolved in 50 mL water, heated to 130° C., aged for 48 h, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide;

[0070] S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: 11 g of aluminum / magnesium / nickel layered metal oxide was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, 4 g of ammonia water was added dropwise under nitrogen protection, the mixture was heated to 90° C., stirred for 4 h, filtered, washed, dried, and calcined at 500° C. for 2 h to obtain magnetic aluminum / magnesium / nickel layered metal oxide;

[0071] S3. Preparation of the impregnation solution: 12 g of manganese chloride and 1.5 g of lanthanum nitrate were dissolved in 100 mL of water to obtain an impregnation solution;

[0072] S4. Preparation of a catalyst for the synthesis of butylene oxide: Add 10 g of a magnetic aluminum / magnesium / nickel layered metal oxide to 40 g of an impregnation solution, soak overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

[0073] Comparative Example 3

[0074] Compared with Example 3, the difference is that lanthanum nitrate is not added in step S4.

[0075] The details are as follows:

[0076] S4. Preparation of impregnation solution: Dissolve 13.5 g of manganese chloride in 100 mL of water to prepare an impregnation solution.

[0077] Comparative Example 4

[0078] Compared with Example 3, the difference is that manganese chloride is not added in step S4.

[0079] The details are as follows:

[0080] S4. Preparation of impregnation solution: Dissolve 13.5 g of lanthanum nitrate in 100 mL of water to prepare an impregnation solution.

[0081] Comparative Example 5

[0082] Compared with Example 3, the difference is that steps S4 and S5 are not performed.

[0083] The details are as follows:

[0084] S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 1 mmol nickel nitrate, 1.5 mmol magnesium nitrate, 1 mmol aluminum nitrate, and 19 mmol urea were dissolved in 50 mL water, heated to 130° C., aged for 48 h, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide;

[0085] S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: 11 g of aluminum / magnesium / nickel layered metal oxide was added to 200 mL of water, 3.24 g of ferric chloride and 1.26 g of ferrous chloride were added, 4 g of ammonia water was added dropwise under nitrogen protection, the mixture was heated to 90° C., stirred for 4 h, filtered, washed, dried, and calcined at 500° C. for 2 h to obtain magnetic aluminum / magnesium / nickel layered metal oxide;

[0086] S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: Add 10g magnetic aluminum / magnesium / nickel layered metal oxide, 2g phytic acid, 4g β-cyclodextrin, and 0.3g potassium dihydrogen phosphate into 200mL water, heat to 100°C, stir for 1h, and hydrothermally react at 150°C for 9h. Add the product into 0.5mmol / L NaOH solution, stir at room temperature for 2h, filter, wash, and dry to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex, which is a catalyst for the synthesis of butylene oxide.

[0087] Test Example 1

[0088] The specific surface area and total pore volume of the catalysts for synthesizing butylene oxide prepared in Examples 1-3 and Comparative Examples 1-5 were measured using an H-Sorb X600 multi-station high-throughput gas adsorption instrument. The results are shown in Table 1.

[0089] Table 1

[0090] Group <![CDATA[Specific surface area (m 2 / g)]]> <![CDATA[Total pore volume (cm 3 / g)]]> Example 1 840.2 0.715 Example 2 843.9 0.717 Example 3 845.4 0.718 Comparative Example 1 804.2 0.678 Comparative Example 2 816.9 0.689 Comparative Example 3 833.4 0.712 Comparative Example 4 831.9 0.710 Comparative Example 5 826.8 0.704

[0091] It can be seen from the above table that the catalysts for synthesizing butylene oxide prepared in Examples 1-3 of the present invention have larger specific surface areas and larger total pore volumes.

[0092] Example 4

[0093] The present embodiment provides a method for synthesizing butylene oxide. 100 mL of low-carbon alcohol, 30 mL of 15 wt% hydrogen peroxide and 1-butene are mixed, the molar ratio of H2O2 to 1-butene is 1:1, the catalyst prepared in Example 1 is added, the amount of the catalyst added is 0.1 wt% of the total mass of the system, the reaction is stirred at 50° C. for 40 min, the reaction pressure is 1 MPa, the rotation speed is 300 r / min, butylene oxide is obtained, and the catalyst is separated by a magnet, washed, dried, and recycled.

[0094] Example 5

[0095] The present embodiment provides a method for synthesizing butylene oxide. 100 mL of low-carbon alcohol, 30 mL of 20 wt% hydrogen peroxide and 1-butene are mixed, the molar ratio of H2O2 to 1-butene is 1:1, the catalyst prepared in Example 2 is added, the amount of the catalyst added is 0.15 wt% of the total mass of the system, the reaction is stirred at 80° C. for 70 min, the reaction pressure is 2 MPa, the rotation speed is 700 r / min, butylene oxide is obtained, and the catalyst is separated by a magnet, washed, dried, and recycled.

[0096] Example 6

[0097] The present embodiment provides a method for synthesizing butylene oxide. 100 mL of low-carbon alcohol, 30 mL of 17 wt% hydrogen peroxide and 1-butene are mixed, the molar ratio of H2O2 to 1-butene is 1:1, the catalyst prepared in Example 3 is added, the amount of the catalyst added is 0.12 wt% of the total mass of the system, the reaction is stirred at 65°C for 55 min, the reaction pressure is 1.5 MPa, the rotation speed is 500 r / min, butylene oxide is obtained, and the catalyst is separated by a magnet, washed, dried, and recycled.

[0098] Comparative Example 6

[0099] Compared with Example 6, the difference is that the catalyst is prepared by Comparative Example 1.

[0100] Comparative Example 7

[0101] Compared with Example 6, the difference is that the catalyst is prepared by Comparative Example 2.

[0102] Comparative Example 8

[0103] Compared with Example 6, the difference is that the catalyst is prepared by Comparative Example 3.

[0104] Comparative Example 9

[0105] Compared with Example 6, the difference is that the catalyst is prepared from Comparative Example 4.

[0106] Comparative Example 10

[0107] Compared with Example 6, the difference is that the catalyst is prepared from Comparative Example 5.

[0108] Test Example 2

[0109] The reactions in Examples 4-6 and Comparative Examples 6-10 were evaluated and the results are shown in Table 2.

[0110] Table 2

[0111] Group Conversion rate of hydrogen peroxide (%) Selectivity of butylene oxide (%) Example 4 99.92 97.86 Example 5 99.95 97.95 Example 6 99.99 98.27 Comparative Example 6 98.25 95.81 Comparative Example 7 93.10 92.37 Comparative Example 8 94.85 93.11 Comparative Example 9 88.89 90.12 Comparative Example 10 82.47 81.19

[0112] It can be seen from the above table that the reaction raw material conversion rate and product selectivity in Examples 4-6 of the present invention are high.

[0113] Test Example 3

[0114] The catalyst in Example 6 was separated, and the experiment in Example 6 was repeated 10 times, and the reaction of the 10th time was evaluated. The results are shown in Table 3.

[0115] Table 3

[0116] Group Conversion rate of hydrogen peroxide (%) Selectivity of butylene oxide (%) 10th reaction 99.17 97.88

[0117] It can be seen from the above table that after the catalyst in Example 6 of the present invention is separated and washed, it still maintains good catalytic activity after multiple catalysis.

[0118] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a catalyst for the synthesis of butylene oxide, characterized in that: Aluminum / magnesium / nickel layered metal oxide is prepared. After magnetic ferroferric oxide is deposited, it is compounded with phytic acid and beta-cyclodextrin and impregnated with an impregnation solution containing manganese salt and lanthanum salt to obtain a catalyst for the synthesis of butylene oxide.

2. The preparation method according to claim 1, characterized in that: The following steps are involved: S1. Preparation of aluminum / magnesium / nickel layered metal oxide: dissolving nickel nitrate, magnesium nitrate, aluminum nitrate and urea in water, heating and aging, filtering, washing and drying to obtain aluminum / magnesium / nickel layered metal oxide; S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: adding aluminum / magnesium / nickel layered metal oxide to water, adding ferric chloride and ferrous chloride, adding ammonia water dropwise under inert gas protection, heating and stirring to react, filtering, washing, drying, and calcining to obtain magnetic aluminum / magnesium / nickel layered metal oxide; S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: adding magnetic aluminum / magnesium / nickel layered metal oxide, phytic acid, β-cyclodextrin, and potassium dihydrogen phosphate to water, heating and stirring, hydrothermal reaction, adding the product to alkaline solution, stirring at room temperature, filtering, washing, and drying to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex; S4. Preparation of an impregnation solution: dissolving a manganese salt and a lanthanum salt in water to obtain an impregnation solution; S5. Preparation of a catalyst for the synthesis of butylene oxide: Add a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to the impregnation solution, impregnate overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

3. The preparation method according to claim 2, characterized in that: In step S1, the molar ratio of nickel nitrate, magnesium nitrate, aluminum nitrate and urea is 0.5-1.5:1-2:1:18-20, and the heating aging temperature is 120-140° C. and the time is 40-52 hours.

4. The preparation method according to claim 2, characterized in that: The mass ratio of the aluminum / magnesium / nickel layered metal oxide, ferric chloride, ferrous chloride and ammonia water in step S2 is 10-12: 3.24:1.26:3-5, the temperature of the heating and stirring reaction is 85-95°C, the time is 3-5h, the temperature of the calcination is 450-550°C, the time is 1-3h.

5. The preparation method according to claim 2, characterized in that: In step S3, the mass ratio of the magnetic aluminum / magnesium / nickel layered metal oxide, phytic acid, β-cyclodextrin, and potassium dihydrogen phosphate is 10:1-3:3-5:0.2-0.4, the heating and stirring temperature is 90-110°C, the time is 0.5-1.5h, the hydrothermal reaction temperature is 145-155°C, the time is 8-10h, the alkali solution is 0.1-0.2mol / L NaOH or KOH solution, and the room temperature stirring time is 1-3h.

6. The preparation method according to claim 2, characterized in that: In step S4, the manganese salt is manganese chloride or manganese nitrate, the lanthanum salt is lanthanum nitrate, and the mass ratio of the manganese salt to the lanthanum salt is 10-15:1-2.

7. The preparation method according to claim 2, characterized in that: The mass ratio of the magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to the impregnation solution in step S5 is 1:3-5.

8. The preparation method according to claim 2, characterized in that: The specific steps include: S1. Preparation of aluminum / magnesium / nickel layered metal oxide: 0.5-1.5 molar equivalents of nickel nitrate, 1-2 molar equivalents of magnesium nitrate, 1 molar equivalent of aluminum nitrate, and 18-20 molar equivalents of urea are dissolved in water, heated to 120-140° C., aged for 40-52 hours, filtered, washed, and dried to obtain aluminum / magnesium / nickel layered metal oxide; S2. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide: 10-12 parts by weight of aluminum / magnesium / nickel layered metal oxide is added to water, 3.24 parts by weight of ferric chloride and 1.26 parts by weight of ferrous chloride are added, 3-5 parts by weight of ammonia water are added dropwise under inert gas protection, heated to 85-95° C., stirred for reaction for 3-5 hours, filtered, washed, dried, and calcined at 450-550° C. for 1-3 hours to obtain a magnetic aluminum / magnesium / nickel layered metal oxide; S3. Preparation of magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex: 10 parts by weight of magnetic aluminum / magnesium / nickel layered metal oxide, 1-3 parts by weight of phytic acid, 3-5 parts by weight of β-cyclodextrin, and 0.2-0.4 parts by weight of potassium dihydrogen phosphate are added to water, heated to 90-110°C, stirred for 0.5-1.5h, and hydrothermally reacted at 145-155°C for 8-10h, the product is added to 0.1-0.2mol / L NaOH or KOH solution, stirred at room temperature for 1-3h, filtered, washed, and dried to obtain a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex; S4. Preparation of an impregnation solution: 10-15 parts by weight of a manganese salt, 1-2 parts by weight of a lanthanum salt were dissolved in water to obtain an impregnation solution; S5. Preparation of a catalyst for the synthesis of butylene oxide: Add 10 parts by weight of a magnetic aluminum / magnesium / nickel layered metal oxide-β-cyclodextrin complex to 30-50 parts by weight of the impregnation solution, soak overnight, filter, wash, and dry to obtain a catalyst for the synthesis of butylene oxide.

9. A catalyst for the synthesis of butylene oxide obtained by the preparation method according to any one of claims 1 to 8.

10. A method for synthesizing butylene oxide, characterized in that: The low-carbon alcohol, hydrogen peroxide and 1-butene are mixed and reacted under the action of the catalyst described in claim 9 to obtain butylene oxide, and the catalyst is separated by a magnet, washed, dried and recycled.