Two-dimensional ruthenium polymer, preparation method thereof and method for catalyzing olefin air epoxidation reaction

Abstract

The invention discloses a two-dimensional ruthenium polymer and a preparation method thereof, and a catalyst olefin air epoxidation reaction method, the catalyst has a structure represented by a general formula (I): n-butene is used as a raw material, air or oxygen is used as an oxidant, the prepared two-dimensional ruthenium polymer is used as the catalyst, a solvent and a co-catalyst are added, the reaction temperature is controlled to be 80-160 DEG C, the reaction is carried out for 2-3 h, and the two-dimensional ruthenium polymer is obtained. The method has the advantages that the catalytic reaction is carried out under the conditions that the reaction temperature is 30-60 DEG C and the reaction pressure is 0.1-5.0 MPa, the epoxybutane can be prepared with high selectivity, the catalytic effect is good, and the process is simple; belongs to the technical field of catalysis.

Description

Technical Field

[0001] This invention relates to a two-dimensional ruthenium polymer, a method for preparing the two-dimensional ruthenium polymer, and a method for catalyzing the air epoxidation reaction of olefins; belonging to the field of catalysis. Background Technology

[0002] 1,2-Epoxybutane (BO), also known as butene oxide, is an important raw material for organic synthesis. It can be used to produce various products such as butanediol and butanolamine, and has broad application prospects. Its production routes mainly include the chlorohydrin process, the direct oxidation process, and the indirect oxidation process. The chlorohydrin process, a traditional method for preparing low-carbon epoxides, involves reacting butene with chlorine and water to produce chlorobutanol, which is then saponified with liquid alkali or lime milk to obtain epoxide. However, due to severe pollution, this method is facing elimination. The butene oxidation method, a direct oxidation process, uses butene as a raw material and cumene hydroperoxide as an oxidant, directly epoxidizing it to epoxide under the action of a silicon-titanium molecular sieve catalyst. While this method reduces environmental pollution, the product contains many impurities and has a boiling point close to that of epoxide, requiring complex refining processes and resulting in high investment and energy consumption. The peracetic acid method, an indirect oxidation process, involves two steps: first, acetaldehyde is oxidized to peracetic acid, which is then epoxidized with butene. Although this method produces no waste pollution, consumes less steam, and yields usable byproduct acetic acid, it has high operational requirements, a low safety factor, and is difficult to promote, thus limiting its development.

[0003] In the epoxidation reaction of butene, the catalyst plays a crucial role. Traditional catalysts suffer from problems such as low loading of active components, uneven dispersion, and easy loss, resulting in relatively low activity and selectivity, and poor stability. Chinese invention patent CN1151739A discloses a method for preparing 1,2-epoxybutane by catalytic hydrogenation of vinyl ethylene oxide. This method uses a palladium catalyst supported on barium sulfate, zirconium dioxide, or titanium dioxide, or a palladium catalyst supported on rhenium, for the hydrogenation reaction. However, this catalyst is a precious metal catalyst, which is expensive and not economically viable. Chinese patent CN103012320A discloses a method for producing epoxybutane, which uses ozone-containing gas as an oxidant to oxidize butene to prepare epoxybutane in the presence of a titanium-containing catalyst. However, this method has a low butene conversion rate, poor catalyst stability, and is prone to activity reduction.

[0004] Therefore, it can be seen that seeking a method for preparing epoxide that is highly atom-economical, green and pollution-free, has great development potential, and can be widely applied is of great practical significance. Summary of the Invention

[0005] In order to overcome the defects of the prior art, the present invention aims to provide a two-dimensional ruthenium polymer with specific structural features, which can effectively catalyze the air epoxidation reaction of olefins and has high activity and high selectivity.

[0006] The second objective of this invention is to provide a method for preparing the two-dimensional ruthenium polymer, which is simple in process, convenient in operation, and suitable for industrial production.

[0007] A third objective of this invention is to provide a method for the catalytic conversion of olefins into corresponding epoxides using two-dimensional ruthenium polymers. This method employs mild reaction conditions and can efficiently convert olefins into corresponding epoxides.

[0008] Therefore, the first technical solution provided by this invention is as follows:

[0009] A two-dimensional ruthenium polymer having a structure as shown in general formula (I):

[0010]

[0011] in:

[0012] In formula (I), M is selected from one of Ru, Pa, Ir, Au, Ag, Cu, Fe, Co, Ni, and Zn;

[0013] In formula (I), R is selected from one of isophthalaldehyde, terephthalaldehyde, 4,4-biphenyldicarboxaldehyde, 2',5'-dimethyl-[1,1':4',1'-terphenyl]-4,4'-dicarboxaldehyde, [1,1:4,1:4,1-tetraphenyl]-4,4-dicarboxaldehyde, and 1,3,5-benzenetricarboxaldehyde.

[0014] The second technical solution provided by this invention is a method for preparing the above-mentioned two-dimensional ruthenium polymer, which includes the following steps in sequence:

[0015] 1) 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin and metal compound were added to a reaction vessel. Solvent was added under anhydrous and oxygen-free N2 atmosphere. The reaction was carried out at 160-200℃ for 10-15 h. After cooling to room temperature, monomer and catalyst were added under N2 atmosphere. The reaction was carried out at 70-90℃ for 36-50 h. After cooling to room temperature, the mixture was filtered, the filter cake was washed and dried to obtain the product shown in general formula (I).

[0016] The mass ratio of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin, metal compound, monomer, and acetic acid is 200-400:10-200:10-200:1049-5245.

[0017] Furthermore, in the above-mentioned method for preparing the two-dimensional ruthenium polymer, the solvent is decahydronaphthalene, and the catalyst is acetic acid.

[0018] Furthermore, in the above-mentioned method for preparing the two-dimensional ruthenium polymer, the metal compound is Ru3(CO).12 One of the following: PaCl4, IrCl3, AuCl3, AgCl, CuCl2, FeCl3, CoCl2, NiCl2, ZnCl2.

[0019] Furthermore, in the above-mentioned method for preparing the two-dimensional ruthenium polymer, the monomer is isophthalaldehyde, terephthalaldehyde, 4,4-biphenyldialdehyde, or 2',5'-dimethyl-[1,1':4”-terphenyl]-4,4 ’ One of the following: -diformaldehyde (CAS No. 857412-04-5), [1,1:4,1:4,1-tetraphenyl]-4,4-diformaldehyde (CAS No.: 857412-06-7), and 1,3,5-benzenetriformaldehyde.

[0020] The present invention also provides a second technical solution using the two-dimensional ruthenium polymer as a catalyst for the air epoxidation reaction of olefins.

[0021] A method for olefin air epoxidation reaction, using n-butene as raw material, adding organic solvent and reducing agent, using air as oxidant, using the two-dimensional ruthenium polymer of claim 1 as catalyst, and carrying out the catalytic reaction under the conditions of reaction temperature of 80-160℃ and air pressure of 0.1-5.0MPa to obtain epoxide.

[0022] The ratio of n-butene, reducing agent, and two-dimensional ruthenium polymer is 0.1-100 mmol: 0.01-500 mmol: 0.1-100 mg.

[0023] Furthermore, in the above-mentioned method for the air epoxidation reaction of olefins, the reducing agent is one of cumene, ethylbenzene, toluene, cyclohexylbenzene, and adamantane.

[0024] Furthermore, in the above-mentioned method for olefin air epoxidation reaction, the organic solvent is one of acetonitrile, benzonitrile, ethanol, ethylbenzene, cyclohexylbenzene, ethyl acetate, propyl propionate, and methyl benzoate.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The technical solution provided by this invention involves adding a catalyst to a solvent and a reducing agent, allowing n-butene and air to undergo an epoxidation reaction under the action of the catalyst to produce epoxide. The purpose of adding the reducing agent is to allow the catalyst to abstract hydrogen atoms from the reducing agent, generating C free radicals, thereby activating oxygen molecules and producing low-concentration peroxides in situ, epoxidizing n-butene. Furthermore, metals also have a good activating effect on molecular oxygen, producing high-valence metal oxides, which assist the epoxidation reaction, resulting in high efficiency, high product selectivity, a simple process, and safety.

[0027] 2. The technical solution provided by this invention uses air as an oxidant, which avoids the serious equipment corrosion, environmental pollution and safety problems caused by peroxyacids, peroxides and other substances.

[0028] 3. The technical solution provided by this invention has a simple catalyst synthesis, requires a small amount of catalyst, and is recyclable and reusable. It has a simple process, low production cost, and is green and safe, and has good prospects for industrial application. Attached Figure Description

[0029] Figure 1 This is the infrared spectrum of a two-dimensional ruthenium polymer;

[0030] Figure 2 This is the XRD pattern of a two-dimensional ruthenium polymer;

[0031] Figure 3 This is a SEM image of a two-dimensional ruthenium polymer;

[0032] Figure 4 This is a TEM image of a two-dimensional ruthenium polymer;

[0033] Figure 5 This is the gas chromatogram of the product after the reaction in Example 3;

[0034] Figure 6 This is the gas chromatogram of the product after the reaction in Example 4;

[0035] Figure 7 This is the gas chromatogram of the product after the reaction in Example 11;

[0036] Figure 8 This is a gas chromatogram of the product after the reaction in Example 12. Detailed Implementation

[0037] The present invention will be further described below with reference to the embodiments, but the scope of protection of the present invention is not limited to the scope shown in the embodiments.

[0038] Example 1

[0039] This embodiment provides a two-dimensional ruthenium polymer having a structure as described in general formula (I):

[0040]

[0041] It is prepared through the following steps:

[0042] 200 mg of 5,10,15,20-tetra(4-aminophenyl)-21H,23H-porphyrin and 63 mg of dodecyltriruthenium carbonyl were added sequentially to a 25 mL Schlenk tube. 10 mL of decahydronaphthalene was added under an anhydrous and oxygen-free N2 atmosphere. The reaction was carried out at 180 °C for 12 h. After cooling to room temperature, 63 mg of 4,4'-biphenyldicarboxaldehyde and 1–5 mL of acetic acid were added under an N2 atmosphere. The reaction was carried out at 80 °C for 48 h. After cooling to room temperature, the mixture was filtered. The filter cake was washed three times with 20 mL of deionized water and ethanol, and then dried to obtain the solid product of general formula (I).

[0043] For the infrared spectrum of the two-dimensional ruthenium polymer, please refer to [reference needed]. Figure 1 ;pass Figure 1 It can be seen that 1600cm -1 The peaks on the left and right are C=N stretching vibration peaks, proving the successful synthesis of the catalyst. See the XRD pattern of the two-dimensional ruthenium polymer. Figure 2 ;pass Figure 2 The refined curves show a high degree of agreement with the experimental data, exhibiting relatively obvious "bulges" or broad peaks at low angles, indicating that the material possesses a certain degree of short-range order. See the SEM image of the two-dimensional ruthenium polymer for reference. Figure 3 ;pass Figure 3 It can be seen that the catalyst has a rough surface and a plate-like structure. See the TEM image of the two-dimensional ruthenium polymer. Figure 4 ;pass Figure 4 The metal is uniformly dispersed.

[0044] Example 2

[0045] In a high-pressure reactor, 5 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane (CAS: 281-23-2), 20 mL of acetonitrile solution, 8 mmol of n-butene, and 2 MPa of air. The mixture was stirred at 130 °C for 7 h, and the reaction was analyzed by gas chromatography. (See reference...) Figure 5 The butene conversion rate was 48%, and the selectivity for epoxide was 80%.

[0046] Example 3

[0047] In a high-pressure reactor, 10 mg of a covalent polymer catalyst (M1 = Ru) with general formula (I) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of n-butene, and 2 MPa of air. The mixture was stirred at 130 °C for 7 h, and the reaction was analyzed by gas chromatography. (See reference...) Figure 6 The butene conversion rate was 55%, and the selectivity for epoxide was 88%.

[0048] Example 4

[0049] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of n-butene and 2 MPa of air. The mixture was stirred at 130 °C for 8 h. Gas chromatography analysis showed that the butene conversion rate was 64% and the selectivity of epoxide was 82%.

[0050] Example 5

[0051] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of n-butene, and 2 MPa of air. The mixture was stirred at 130 °C for 10 h. Gas chromatography analysis showed that the butene conversion rate was 59% and the selectivity of epoxide was 81%.

[0052] Example 6

[0053] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of n-butene and 1 MPa of air. The mixture was stirred at 130 °C for 8 h. Gas chromatography analysis showed that the butene conversion rate was 40% and the selectivity of epoxide was 85%.

[0054] Example 7

[0055] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of n-butene, and 2.5 MPa of air. The mixture was stirred at 130 °C for 8 h. Gas chromatography analysis showed that the butene conversion rate was 65% and the selectivity for epoxide was 81%.

[0056] Example 8

[0057] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of n-butene, and 2.5 MPa of air. The mixture was stirred at 125 °C for 8 h. Gas chromatography analysis showed that the butene conversion rate was 55% and the selectivity for epoxide was 82%.

[0058] Example 9

[0059] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 4 mmol of n-butene and 2.5 MPa of air. The mixture was stirred at 125 °C for 8 h. Gas chromatography analysis showed that the butene conversion rate was 44% and the selectivity of epoxide was 85%.

[0060] Example 10

[0061] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 10 mmol of n-butene and 2.5 MPa of air. The mixture was stirred at 125 °C for 8 h. Gas chromatography analysis showed that the butene conversion rate was 50% and the selectivity for epoxide was 77%.

[0062] Example 11

[0063] In a high-pressure reactor, 10 mg of a covalent polymer catalyst (M1 = Ru) with general formula (I) was added sequentially, followed by 20 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, and then 8 mmol of n-butene and 2.5 MPa of air. The mixture was stirred at 125 °C for 8 h, and the reaction was analyzed by gas chromatography. (See reference...) Figure 7 The butene conversion rate was 84%, and the selectivity for epoxide was 80%.

[0064] Example 12

[0065] In a high-pressure reactor, 10 mg of a covalent polymer catalyst (M1 = Ru) with general formula (I) was added sequentially, followed by 5 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of butene, and 2.5 MPa of air. The mixture was stirred at 125 °C for 8 h, and the reaction was analyzed by gas chromatography. (See reference...) Figure 8 The butene conversion rate was 28%, and the selectivity for epoxide was 81%.

[0066] Example 13

[0067] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 30 mmol of adamantane as a reducing agent, 20 mL of acetonitrile solution, 8 mmol of butene, and 2.5 MPa of air. The mixture was stirred at 125 °C for 8 h. Gas chromatography analysis showed that the butene conversion rate was 69% and the selectivity for epoxide was 84%.

[0068] Comparative Example 1

[0069] In a high-pressure reactor, 10 mmol of reducing agent adamantane and 20 mL of acetonitrile solution were added sequentially, followed by the introduction of 8 mmol of butene and 2 MPa of air. The mixture was stirred for 7 h at 130 °C. Gas chromatography analysis showed that the butene conversion rate was 5% and the selectivity of epoxide was 60%.

[0070] Comparative Example 2

[0071] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru) was added sequentially, followed by 10 mmol of adamantane as a reducing agent, 20 mL of ethylbenzene solution and 2 MPa of air. 8 mmol of butene was then introduced, and the mixture was stirred at 130 °C for 7 h. Gas chromatography analysis showed that the butene conversion rate was 17% and the selectivity of epoxide was 54%.

[0072] Comparative Example 3

[0073] In a high-pressure reactor, 10 mg of a covalent polymer catalyst with general formula (I) (M1 = Ru), 20 mL of cyclohexylbenzene solution, and 8 mmol of butene were added sequentially. The mixture was stirred at 130 °C for 7 h. Gas chromatography analysis showed that the butene conversion rate was 12% and the selectivity of epoxide was 70%.

[0074] Comparative Example 4

[0075] In a high-pressure reactor, 10 mmol of adamantane, 20 mL of acetonitrile solution, and 8 mmol of butene were added sequentially. The mixture was stirred at 130 °C for 7 h. Gas chromatography analysis showed that the butene conversion rate was 5% and the selectivity of epoxide was 56%.

Claims

1. A two-dimensional ruthenium polymer, characterized by, Has the structure as shown in general formula (I): Wherein: M in formula (I) is selected from one of Ru, Pa, Ir, Au, Ag, Cu, Fe, Co, Ni, Zn; R in formula (I) is selected from one of p-phenylenediform, 4,4-biphenyldiform, 2',5'-dimethyl-[1,1':4',1'-triphenyl]-4,4'-diform, [1,1:4,1:4,1-Quaterphenyl]-4,4-diform, 1,3,5-benzene triform, p-phenylenediamine.

2. The method for preparing the two-dimensional ruthenium polymer of claim 1, characterized in that, In turn comprising the following steps: 1) 5,10,15,20-tetra (4-aminobenzene)-21H, 23H-porphyrin, metal compound is added to the Schlenk tube, under anhydrous and anaerobic, N2 atmosphere, solvent is added, and the reaction is carried out at 160-200 DEG C for 10-15 h, cooled to room temperature, continue to add monomer under N2 atmosphere, catalyst, reaction at 70-90 DEG C for 36-50 h, after cooling to room temperature, filter, filter cake is washed and dried to obtain the product shown in general formula (I). The mass ratio of the 5,10,15,20-tetra (4-aminobenzene)-21H, 23H-porphyrin, metal compound, monomer, acetic acid is 200-400:100-200:100-200:1049-5245.

3. The method for preparing a two-dimensional ruthenium polymer according to claim 2, characterized by, The solvent is decalin.

4. The method for preparing a two-dimensional ruthenium polymer according to claim 2, characterized by, The catalyst is acetic acid.

5. The method for preparing a two-dimensional ruthenium polymer according to claim 2, wherein The metal compound is one of Ru3(CO) 12 , PaCl4, IrCl3, AuCl3, AgCl, CuCl2, FeCl3, CoCl2, NiCl2, ZnCl2.

6. The method for preparing a two-dimensional ruthenium polymer according to claim 2, characterized by, The monomer is one of m-benzenediform, p-phenylenediform, 4,4-biphenyldiform, 2',5'-dimethyl-[1,1':4',1'-triphenyl]-4,4'-diform, [1,1:4,1:4,1-Quaterphenyl]-4,4-diform, 1,3,5-benzene triform.

7. The two-dimensional ruthenium polymer of claim 1 as a catalyst for olefin air epoxidation reaction.

8. A process for the olefin air epoxidation reaction, characterized by, With n-butene as raw material, organic solvent and reducing agent are added, air is used as oxidant, the two-dimensional ruthenium polymer of claim 1 is used as catalyst, and the catalytic reaction is carried out under the conditions of reaction temperature of 80-160 DEG C and air pressure of 0.1-5.0 MPa to obtain epoxy butane; The ratio of the n-butene, reducing agent, two-dimensional ruthenium polymer is 0.1-100 mmol:0.01-500 mmol:0.1-100 mg.

9. The method of olefin air epoxidation reaction according to claim 8, wherein, The reducing agent is one of cumene, ethylbenzene, toluene, cyclohexylbenzene, adamantane.

10. The method of olefin air epoxidation reaction according to claim 8, wherein, The organic solvent is one of acetonitrile, benzonitrile, ethanol, ethylbenzene, cyclohexylbenzene, ethyl acetate, propyl propionate, methyl benzoate.

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