Method for synthesizing vinyl acetate

[0026] [Example 1]

[0027] Preparation of carbonylation catalyst: Co containing 9.35gCo, 3.20gBe and 1.85gAu 2 (CO) 8 , BeCl 2 and NH 4 AuCl 4 ·2H 2 O is thoroughly mixed and dissolved in acetic acid with a concentration of 10wt% to obtain 400ml of immersion solution, and 1.0L of the specific surface is 170m 2 /g, spherical SiO with a pore volume of 0.97 and a diameter of 5.6 mm 2The carrier was immersed in the above-mentioned dipping solution, and dried at 100° C. for 2 hours to obtain the catalyst. The carbonylation catalyst was analyzed by ICP, and the Co content was 9.35 g/L, the Be content was 3.20 g/L, and the Au content was 1.85 g/L.

[0028] Synthesis of vinyl acetate:

[0029] Step (1): add 1.5mol acetic acid, 0.05mol carbonylation catalyst, 0.10mol methyl iodide and 0.45mol methyl acetate into the 500ml titanium material reaction kettle, discharge the air in the kettle with argon first and then pressurize to 2.0MPa, then Introduce carbon monoxide and hydrogen until the pressure is 8.2MPa, increase the stirring speed to 1200rpm, and heat up to the reaction temperature while stirring and heating, control the reaction temperature to be 176 ° C, the molar ratio of carbon monoxide and hydrogen is 2:1, and the reaction is stopped after 7.5 hours of continuous reaction. . The reaction kettle was lowered to room temperature, the product obtained by the reaction was washed three times with water, the organic matter entered the oil phase, and the solvent, ethyl acetate, acetaldehyde and other by-products were removed by rectification and purification to obtain ethylene diacetate.

[0030] Step (2): adding above-mentioned 20ml of ethylene diacetate, 30ml of acetic anhydride, and 0.01mol of benzenesulfonic acid into a rectification reaction tower with a volume of 150ml of reaction kettle, first discharge the air in the kettle with argon and pressurize to 0.35MPa, The stirring speed was increased to 600 rpm, and the temperature was raised to the reaction temperature while stirring and heating, and the reaction temperature was controlled to be 148° C., and the reaction was stopped after continuing the reaction for 45 min.

[0031] Product analysis: The reaction mixture obtained by the above reaction was cooled, decompressed and separated, and the liquid phase was analyzed by gas chromatography-mass spectrometry (GC-MASS).

[0032] The calculated yield of vinyl acetate is 58.25%, and the selectivity is 81.36%. For the convenience of description and comparison, the preparation conditions, reaction conditions, material feeding amount, yield and selectivity of the catalyst are listed in Table 1 respectively. and Table 2.

[0033] [Example 2]

[0034] Preparation of carbonylation catalyst: Co containing 9.35g Co, 3.20g Be and 1.85g Sb 2 (CO) 8 , BeCl 2 and Cl 3 Sb was thoroughly mixed and dissolved in acetic acid with a concentration of 10wt% to obtain 400ml of immersion solution, and 1.0L of the specific surface was 170m 2 /g, spherical SiO with a pore volume of 0.97 and a diameter of 5.6 mm 2 The carrier was immersed in the above-mentioned dipping solution, and dried at 100° C. for 2 hours to obtain the catalyst. The carbonylation catalyst was analyzed by ICP, and the Co content was 9.35 g/L, the Be content was 3.20 g/L, and the Sb content was 1.85 g/L.

[0035] Synthesis of vinyl acetate:

[0036] Step (1): add 1.5mol acetic acid, 0.05mol carbonylation catalyst, 0.10mol methyl iodide and 0.45mol methyl acetate into the 500ml titanium material reaction kettle, discharge the air in the kettle with argon first and then pressurize to 2.0MPa, then Introduce carbon monoxide and hydrogen until the pressure is 8.2MPa, increase the stirring speed to 1200rpm, and heat up to the reaction temperature while stirring and heating, control the reaction temperature to be 176 ° C, the molar ratio of carbon monoxide and hydrogen is 2:1, and the reaction is stopped after 7.5 hours of continuous reaction. . The reaction kettle was lowered to room temperature, the product obtained by the reaction was washed three times with water, the organic matter entered the oil phase, and the solvent, ethyl acetate, acetaldehyde and other by-products were removed by rectification and purification to obtain ethylene diacetate.

[0037] Step (2): adding above-mentioned 20ml of ethylene diacetate, 30ml of acetic anhydride, and 0.01mol of benzenesulfonic acid into a rectification reaction tower with a volume of 150ml of reaction kettle, first discharge the air in the kettle with argon and pressurize to 0.35MPa, The stirring speed was increased to 600 rpm, and the temperature was raised to the reaction temperature while stirring and heating, and the reaction temperature was controlled to be 148° C., and the reaction was stopped after continuing the reaction for 45 min.

[0038] Product analysis: The reaction mixture obtained by the above reaction was cooled, decompressed and separated, and the liquid phase was analyzed by gas chromatography-mass spectrometry (GC-MASS).

[0039] The calculated yield of vinyl acetate is 58.18%, and the selectivity is 81.49%. In order to facilitate the description and comparison, the preparation conditions, reaction conditions, material feed amount, vinyl acetate yield and selectivity of the catalyst are listed in Table 1 respectively. and Table 2.

[0049] [Example 3]

[0050] Preparation of carbonylation catalyst: Co(OAc) containing 7.00 g Co, 1.00 g Mg and 1.00 g Au 2 ·4H 2 O, MgSO 4 ·7H 2 O and HAuCl 4 Fully mixed and dissolved in pure water to obtain 400ml of immersion liquid, and the specific surface of 1.0L was 150m 2 /g, spherical Al with a pore volume of 0.90 and a diameter of 5.6 mm 2 O 3 The carrier was immersed in the above-mentioned dipping solution, and dried at 80° C. for 2 hours to obtain the catalyst. The carbonylation catalyst was analyzed by ICP, and the Co content was 7.00 g/L, the Mg content was 1.00 g/L, and the Au content was 1.00 g/L.

[0051] Synthesis of vinyl acetate:

[0052] Step (1): add 1.5mol acetic acid, 0.05mol carbonylation catalyst, 0.10mol methyl iodide and 0.45mol methyl acetate into the 500ml titanium material reaction kettle, first discharge the air in the kettle with argon and pressurize to 2.0MPa, then Feed carbon monoxide and hydrogen until the pressure is 8.2MPa, increase the stirring speed to 1200rpm, and heat up to the reaction temperature while stirring and heating, control the reaction temperature to be 176 ° C, and the molar ratio of carbon monoxide and hydrogen to be 2:1. After continuing the reaction for 7.5h, stop the reaction . The reaction kettle was lowered to room temperature, the product obtained by the reaction was washed three times with water, the organic matter entered the oil phase, and the solvent, ethyl acetate, acetaldehyde and other by-products were removed by rectification and purification to obtain ethylene diacetate.

[0053] Step (2): adding above-mentioned 20ml of ethylene diacetate, 30ml of acetic anhydride and 0.01mol of benzenesulfonic acid into a rectification reaction tower with a volume of 150ml reactor, first discharge the air in the kettle with argon and pressurize to 0.35MPa, The stirring speed was increased to 600 rpm, and the temperature was raised to the reaction temperature while stirring and heating, and the reaction temperature was controlled to be 148° C., and the reaction was stopped after continuing the reaction for 45 min.

[0054] Product analysis: The reaction mixture obtained by the above reaction was cooled, decompressed and separated, and the liquid phase was analyzed by gas chromatography-mass spectrometry (GC-MASS).

[0055] The calculated yield of vinyl acetate is 56.44%, and the selectivity is 80.87%. For the convenience of description and comparison, the preparation conditions, reaction conditions, material feeding amount, yield and selectivity of the catalyst are listed in Table 1 respectively. and Table 2.