Catalyst for preparing methylal and methyl formate through one-step selective oxidation of methanol

Abstract

The invention provides a catalyst for preparing methylal and methyl formate through one-step selective oxidation of methanol. The catalyst comprises the following raw material components in percentage by mass based on total mass of the raw material components of the catalyst: 10-20% of a vanadium source, 55-65% of a titanium source and 15-35% of sulfuric acid. The invention provides a catalyst for preparing methyl formate and methylal through one-step selective oxidation of methanol and a preparation method of the catalyst. The catalyst has a high methanol conversion rate, high product selectivity, long life and low-temperature fluctuation sensitivity, the product composition is easily controlled in industrial reaction, and subsequent separation is convenient.

Description

technical field

[0001] The invention relates to the field of catalysts, and specifically discloses a catalyst for preparing methylal and methyl formate by one-step selective oxidation of methanol. Background technique

[0002] Methanol is an important chemical basic raw material and clean liquid fuel, widely used in organic synthesis, fuel, medicine, pesticide, paint, automobile and national defense and other industries. In recent years, the scale of methanol production has been increasing day by day, but the demand for methanol has grown slowly, making methanol in a serious state of oversupply, and actively developing downstream products of methanol has become a top priority. Methanol mainly has the following downstream products: formaldehyde FA, methylal DMM, olefins, methyl tert-butyl ether MTBE, dimethyl carbonate DMC, dimethyl ether and esters, which include acrylates and Methyl formate MF. Among these downstream products, methylal and methyl formate have attracted mu...

Examples

Embodiment 1

[0046] 4.0g of vanadyl sulfate, 17.4g of titanium sulfate and 8.6g of sulfuric acid were dissolved in a three-necked flask containing 680ml of deionized water, dissolved under stirring, and 0.5g of activated carbon dispersant was added to obtain solution A; 40ml of ammonia (25%) was dissolved in Prepare solution B in 360ml deionized water. Place A under an ice-water bath and stir vigorously, and drop B into the mixture A at a speed of 110 r / min until the pH=9.0, and a slurry containing a yellow-brown precipitate is obtained. Continue to stir for 0.5h, then leave it to age for 2h, wash twice with 100ml of water to obtain a tan solid, dissolve the obtained tan solid in a solution of 15ml of water and 35ml of n-butanol, stir for 6h, and then suction filter to obtain filter cake C , C was dried at 110°C for 2h, and calcined at 400°C for 6h to obtain a catalyst for the selective oxidation of methanol to prepare methylal and methyl formate.

[0047] attached figure 1 As the XRD ch...

Embodiment 2

[0056] 4.2g of vanadyl sulfate, 17.4g of titanium sulfate and 8.6g of sulfuric acid were dissolved in a three-necked flask containing 680ml of deionized water, dissolved under stirring, and 1.0g of activated carbon dispersant was added to obtain solution A; 40ml of ammonia (28%) was dissolved in Prepare solution B in 360ml deionized water. Place A under an ice-water bath and stir vigorously, and drop B into the mixture A at a speed of 110 r / min until the pH=9.5, and a slurry containing a yellow-brown precipitate is obtained. Continue to stir for 0.5h, then leave it to age for 2h, wash twice with 100ml of water to obtain a tan solid, dissolve the obtained tan solid in a solution of 15ml of water and 35ml of n-butanol, stir for 6h, and then suction filter to obtain filter cake C , C was dried at 100°C for 2h, and calcined at 430°C for 6h to obtain a catalyst for the selective oxidation of methanol to prepare methylal and methyl formate.

[0057] The obtained catalyst was presse...

Embodiment 3

[0061] 3.5g of vanadyl sulfate, 17g of titanium sulfate and 6.3g of sulfuric acid were dissolved in a three-necked flask filled with 680ml of deionized water, dissolved under stirring, and 1.5g of active carbon dispersant was added to obtain solution A; 50ml of ammonia (18%) was dissolved in 450ml of deionized water was prepared as solution B. Place A under an ice-water bath and stir vigorously, and drop B into the mixture A at a speed of 130 r / min until the pH=9.3, and a slurry containing a yellow-brown precipitate is obtained. Continue to stir for 0.5h, then leave it to age for 2h, wash with 100ml of water for 3 times to obtain a tan solid, dissolve the obtained tan solid in a solution of 15ml of water and 35ml of Tween, stir for 7h, and then suction filter to obtain filter cake C. Dry C at 120°C for 2 hours, and roast at 400°C for 6 hours to obtain a catalyst for the selective oxidation of methanol to prepare methylal and methyl formate.

[0062] The prepared catalyst was ...

technical field

[0001] The invention relates to the field of catalysts, and specifically discloses a catalyst for preparing methylal and methyl formate by one-step selective oxidation of methanol. Background technique

[0002] Methanol is an important chemical basic raw material and clean liquid fuel, widely used in organic synthesis, fuel, medicine, pesticide, paint, automobile and national defense and other industries. In recent years, the scale of methanol production has been increasing day by day, but the demand for methanol has grown slowly, making methanol in a serious state of oversupply, and actively developing downstream products of methanol has become a top priority. Methanol mainly has the following downstream products: formaldehyde FA, methylal DMM, olefins, methyl tert-butyl ether MTBE, dimethyl carbonate DMC, dimethyl ether and esters, which include acrylates and Methyl formate MF. Among these downstream products, methylal and methyl formate have attracted mu...

Examples

Embodiment 1

[0046] 4.0g of vanadyl sulfate, 17.4g of titanium sulfate and 8.6g of sulfuric acid were dissolved in a three-necked flask containing 680ml of deionized water, dissolved under stirring, and 0.5g of activated carbon dispersant was added to obtain solution A; 40ml of ammonia (25%) was dissolved in Prepare solution B in 360ml deionized water. Place A under an ice-water bath and stir vigorously, and drop B into the mixture A at a speed of 110 r / min until the pH=9.0, and a slurry containing a yellow-brown precipitate is obtained. Continue to stir for 0.5h, then leave it to age for 2h, wash twice with 100ml of water to obtain a tan solid, dissolve the obtained tan solid in a solution of 15ml of water and 35ml of n-butanol, stir for 6h, and then suction filter to obtain filter cake C , C was dried at 110°C for 2h, and calcined at 400°C for 6h to obtain a catalyst for the selective oxidation of methanol to prepare methylal and methyl formate.

[0047] attached figure 1 As the XRD ch...

Embodiment 2

[0056] 4.2g of vanadyl sulfate, 17.4g of titanium sulfate and 8.6g of sulfuric acid were dissolved in a three-necked flask containing 680ml of deionized water, dissolved under stirring, and 1.0g of activated carbon dispersant was added to obtain solution A; 40ml of ammonia (28%) was dissolved in Prepare solution B in 360ml deionized water. Place A under an ice-water bath and stir vigorously, and drop B into the mixture A at a speed of 110 r / min until the pH=9.5, and a slurry containing a yellow-brown precipitate is obtained. Continue to stir for 0.5h, then leave it to age for 2h, wash twice with 100ml of water to obtain a tan solid, dissolve the obtained tan solid in a solution of 15ml of water and 35ml of n-butanol, stir for 6h, and then suction filter to obtain filter cake C , C was dried at 100°C for 2h, and calcined at 430°C for 6h to obtain a catalyst for the selective oxidation of methanol to prepare methylal and methyl formate.

[0057] The obtained catalyst was presse...

Embodiment 3

[0061] 3.5g of vanadyl sulfate, 17g of titanium sulfate and 6.3g of sulfuric acid were dissolved in a three-necked flask filled with 680ml of deionized water, dissolved under stirring, and 1.5g of active carbon dispersant was added to obtain solution A; 50ml of ammonia (18%) was dissolved in 450ml of deionized water was prepared as solution B. Place A under an ice-water bath and stir vigorously, and drop B into the mixture A at a speed of 130 r / min until the pH=9.3, and a slurry containing a yellow-brown precipitate is obtained. Continue to stir for 0.5h, then leave it to age for 2h, wash with 100ml of water for 3 times to obtain a tan solid, dissolve the obtained tan solid in a solution of 15ml of water and 35ml of Tween, stir for 7h, and then suction filter to obtain filter cake C. Dry C at 120°C for 2 hours, and roast at 400°C for 6 hours to obtain a catalyst for the selective oxidation of methanol to prepare methylal and methyl formate.

[0062] The prepared catalyst was ...

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