CN112642422A - Manganese-based catalyst for synthesizing methacrylonitrile and preparation and application thereof - Google Patents
Manganese-based catalyst for synthesizing methacrylonitrile and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of liquid-phase ammoniation oxidation, and discloses a manganese-based catalyst for synthesizing methacrylonitrile, and a preparation method and application thereof. Wherein the pure manganese oxide is obtained by the reaction of high-valence manganese salt and low-valence manganese salt, and a certain amount of alkaline compound is added in the synthesis process to modify the pure manganese oxide; the supported manganese oxide is obtained by depositing and precipitating a manganese oxide on a carrier and then calcining at high temperature. Under the existence of the manganese-based catalyst, methacrolein is taken as a substrate, no auxiliary agent is added in the atmosphere of oxygen and ammonia gas, and the yield of methacrylonitrile is up to 92%. Compared with the prior art, the reaction is carried out under the liquid phase condition, and the method has the advantages of mild reaction condition, simple operation, low cost, high product yield, environmental protection and the like.
Description
Technical Field
The invention belongs to the technical field of liquid-phase catalytic oxidation, relates to a manganese-based catalyst, and particularly relates to a manganese-based catalyst for synthesizing methacrylonitrile through liquid-phase ammoniation and oxidation, and a preparation method and application thereof.
Background
Methacrylonitrile is an important intermediate product in petrochemical industry. The methacrylate obtained by hydrolyzing and esterifying the methacrylonitrile is a valuable monomer of a high polymer, particularly the methyl methacrylate is an important raw material of high polymer chemistry, organic glass and other synthetic resin monomers, the methacrylamide prepared from the methacrylonitrile can be used as a strong water repellent and a comonomer, the methacrylonitrile can be homopolymerized or copolymerized with other monomers to prepare plastics or fibers, for example, the methacrylonitrile is a main monomer raw material of Polymethacrylimide (PMI) foam plastics, the specific strength and the specific modulus of the PMI foam plastics are the highest under the condition of the same density in a plurality of foam plastics, the PMI foam plastics also have excellent mechanical properties, the heat-resistant temperature reaches 240 ℃, the PMI foam plastics are easy to process and form, have good compatibility with various resins, and are ideal core materials of sandwich structure composite materials. The high-performance sandwich structure composite material prepared by taking the composite material as the core material is widely applied to the high-tech fields of aerospace, vehicles, ships and the like in the United states, Japan, Europe and the like.
As early as 1973, Sohoi, USA, used a process for preparing methacrylonitrile by ammoxidation of pure isobutylene for industrial production, but the process had more by-products, which resulted in complicated post-treatment process equipment, more investment and large energy consumption. Other synthesis processes, such as the process for preparing methacrylonitrile and butadiene by ammoxidation of mixed C4 olefins, have been published in foreign patents, and have remained in the pilot plant stage so far, and no industrial reports are found.
Disclosure of Invention
The method uses a process route for preparing methacrylonitrile by a two-step method, and in the first step, methacrolein is obtained by starting from isobutene and carrying out catalytic oxidation; the second step relates to the invention, namely, methacrolein is subjected to catalytic ammoxidation under liquid phase conditions to obtain methacrylonitrile. The total yield of the two-step method can reach 80 percent, side reactions are less, process equipment is simple, energy consumption is less, and the method has industrial production prospect, and the invention provides the preparation method and the application of the manganese-based catalyst required by the second step of the process. Compared with the prior art, the process has the advantages of simple operation, low cost, high product yield, environmental protection and the like.
The invention is mainly realized by the following technical scheme:
a manganese-based catalyst for the synthesis of methacrylonitrile, characterized in that said manganese-based catalyst comprises a simple manganese oxide or a supported manganese oxide. Wherein the pure manganese oxide is obtained by the reaction of high-valence manganese salt and low-valence manganese salt, and a certain amount of alkaline compound is added in the synthesis process to modify the pure manganese oxide; the supported manganese oxide is obtained by depositing and precipitating a manganese oxide on a carrier and then calcining at high temperature. The manganese-based catalyst is used for the reaction of synthesizing methacrylonitrile by ammonification and oxidation of methacrolein.
The manganese-based catalyst for synthesizing methacrylonitrile is characterized by comprising the following preparation steps:
preparing pure manganese oxide: weighing a certain amount of potassium permanganate, adding the potassium permanganate into water, stirring and dissolving at room temperature to obtain a potassium permanganate aqueous solution; weighing a certain amount of manganese nitrate, adding the manganese nitrate into water, stirring and dissolving at room temperature, slowly dropwise adding the obtained manganese nitrate solution into the potassium permanganate aqueous solution, stirring at room temperature for 0.5-6 h, adding an alkaline compound or an aqueous solution of the alkaline compound, stirring at room temperature for 2-24 h, placing the mixture into a crystallization kettle, crystallizing at high temperature for a certain time, cooling, opening the kettle, filtering, separating and washing the mixture, drying the obtained solid in vacuum, and roasting at high temperature in the air atmosphere for a certain time to obtain the target simple manganese oxide.
Preparation of a load type manganese-based catalyst: weighing a certain amount of potassium permanganate, adding the potassium permanganate into water, stirring and dissolving at room temperature to obtain a potassium permanganate aqueous solution; weighing a certain amount of manganese nitrate, adding the manganese nitrate into water, stirring and dissolving at room temperature, then weighing a certain amount of carriers, dispersing in a manganese nitrate aqueous solution, stirring at room temperature for 1-12 h, slowly adding the obtained mixture into the potassium permanganate aqueous solution, stirring at room temperature for 0.5-6 h, adding an alkaline compound or an aqueous solution of the alkaline compound, continuously stirring at room temperature for 2-24 h, placing the obtained mixture into a crystallization kettle, crystallizing at high temperature for a certain time, cooling and opening the kettle, filtering, separating and washing the mixture, vacuum-drying the obtained solid, and roasting at high temperature in the air atmosphere for a certain time to obtain the target supported manganese-based catalyst.
The simple manganese oxide and the supported manganese-based catalyst obtained by the method are used for preparing methacrylonitrile by performing ammoxidation on methacrolein.
In the preparation method of the manganese-based catalyst, the carrier of the supported manganese-based catalyst is one of silicon dioxide, magnesium oxide, hydroxyapatite, calcium oxide, aluminum oxide and hydrotalcite, and preferably is silicon dioxide. The silica may be solid silica powder or silica sol, and the particle diameters of the two kinds of silica are not limited.
In the preparation method of the manganese-based catalyst, the alkaline compound is one of potassium hydroxide, sodium carbonate, potassium bicarbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, urea and ammonia gas, the concentration of the aqueous solution of the alkaline compound is 5-50%, and the molar ratio of manganese to the alkaline compound is 1: 0.1 to 20.
In the preparation method of the manganese-based catalyst, the crystallization temperature is 80-150 ℃, and the crystallization time is 1-24 hours.
In the preparation method of the manganese-based catalyst, the vacuum drying treatment is to vacuumize the solid for 2-24 hours at the temperature of 60-100 ℃, and the roasting temperature is 300-600 ℃.
In the preparation method of the manganese-based catalyst, the manganese percentage content of the manganese-based catalyst is 5-60%.
The method for synthesizing the methacrylonitrile by using the manganese-based catalyst comprises the following steps: in the presence of a manganese-based catalyst and an organic solvent, taking oxygen or air as an oxidant, ammonia as an ammonia source and methacrolein as a raw material, and carrying out an ammoniation oxidation reaction to obtain a product methacrylonitrile. The reaction temperature is 25-100 ℃, the reaction time is 5-120 min, and the product yield and selectivity are determined by a chromatographic internal standard method.
In the above-mentioned methacrylonitrile synthesis method, the reaction solvent is one or a mixture of several of toluene, ethylbenzene, mesitylene, acetonitrile, acetone, 1, 2-dichloroethane, chloroform, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-pentane, N-heptane and tetrahydrofuran.
In the above-mentioned method for synthesizing methacrylonitrile, the reaction temperature is preferably 30 deg.C, and the reaction time is preferably 30 min.
In the above method for synthesizing methacrylonitrile, the molar ratio of methacrolein to manganese-based catalyst is: 1: 0.01-5.
In the above method for synthesizing methacrylonitrile, the molar ratio of methacrolein to oxygen is: 1: 1-20.
In the above method for synthesizing methacrylonitrile, the molar ratio of methacrolein to ammonia gas is: 1: 1-20.
Compared with the prior art, the invention has the following advantages and effects:
(1) the raw materials for preparing the manganese-based catalyst are simple and easy to obtain, and synthesis is not needed; the preparation conditions are also simple, so that the synthesis of large amount is very easy. In addition, the material has good cycle performance. High-temperature regeneration treatment is not needed, after the reaction is finished, the catalyst can be repeatedly used by simple washing and drying, and the catalytic activity and the selectivity are not changed.
(2) Referring to a process route for preparing methyl methacrylate by a two-step method, in the first step, isobutene is oxidized into methacrolein under a gas phase condition; in the second step, methylacrolein is aminated and oxidized directly into methacrylonitrile under liquid phase condition. The total yield of the two-step method can reach 80 percent, the side reaction is extremely less, the process equipment is simple, the energy consumption is low, and the method has the prospect of industrial production,
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1
Weighing 16g of potassium permanganate, adding the potassium permanganate into 500ml of deionized water, stirring at room temperature until the potassium permanganate is completely dissolved, weighing 54g of manganese nitrate aqueous solution (with the mass concentration of 50%) and adding the manganese nitrate aqueous solution into 250ml of water, slowly adding the obtained aqueous solution into the potassium permanganate aqueous solution, stirring at room temperature for 30min, slowly adding 50g of urea aqueous solution (with the mass concentration of 40%), continuing stirring at room temperature for 12h, placing the mixture into a crystallization kettle, crystallizing at 100 ℃ for 12h, cooling and opening the kettle, filtering and separating the mixture, washing the solid with water and methanol in sequence, then drying at 80 ℃ in vacuum for 12h, and roasting the obtained solid at 400 ℃ in an air atmosphere for 4 h.
Example 2
Weighing 16g of potassium permanganate, adding the potassium permanganate into 500ml of deionized water, stirring at room temperature until the potassium permanganate is completely dissolved, weighing 54g of manganese nitrate aqueous solution (with the mass concentration of 50%) and adding the manganese nitrate aqueous solution into 250ml of water, slowly adding the obtained aqueous solution into the potassium permanganate aqueous solution, stirring at room temperature for 30min, slowly adding 50g of sodium bicarbonate aqueous solution (with the mass concentration of 8%), continuing stirring at room temperature for 24h, placing the mixture into a crystallization kettle, crystallizing at 100 ℃ for 12h, cooling and opening the kettle, filtering and separating the mixture, fully washing the solid with water and methanol in sequence, then drying at 80 ℃ in vacuum for 12h, and roasting the obtained solid at 550 ℃ in an air atmosphere for 6 h.
Example 3
Weighing 16g of potassium permanganate, adding the potassium permanganate into 500ml of deionized water, stirring at room temperature until the potassium permanganate is completely dissolved, weighing 54g of manganese nitrate aqueous solution (with the mass concentration of 50%) and adding the manganese nitrate aqueous solution into 250ml of water, slowly adding the obtained aqueous solution into the potassium permanganate aqueous solution, stirring at room temperature for 30min, adding 30g of urea, continuously stirring at room temperature for 24h, placing the mixture into a crystallization kettle, crystallizing at 120 ℃ for 12h, cooling to open the kettle, filtering and separating the mixture, fully washing the solid with water and methanol in sequence, then drying at 80 ℃ for 12h in vacuum, and roasting the obtained solid catalyst at 300 ℃ for 3h in an air atmosphere.
Example 4
Weighing 16g of potassium permanganate, adding the potassium permanganate into 400ml of deionized water, stirring the mixture at room temperature until the potassium permanganate is completely dissolved, weighing 54g of manganese nitrate aqueous solution (with the mass concentration of 50%) and adding the manganese nitrate aqueous solution into 250ml of water, slowly adding the obtained aqueous solution into the potassium permanganate aqueous solution, stirring the mixture at room temperature for 30min, and slowly adding 40g of ammonium bicarbonate aqueous solution (with the mass concentration of 15%); continuously stirring for 24h at room temperature, placing the mixture into a crystallization kettle, crystallizing at 100 ℃ for 12h, cooling, opening the kettle, filtering and separating the mixture, fully washing the solid with water and methanol in sequence, then drying in vacuum at 80 ℃ for 12h, and roasting the obtained solid at 400 ℃ in air atmosphere for 4 h.
Example 5
Weighing 54g of manganese nitrate aqueous solution (with the mass concentration of 50%) and adding the manganese nitrate aqueous solution into 250ml of water, adding 50g of alumina, stirring at room temperature for 1h, weighing 16g of potassium permanganate and adding the potassium permanganate into 400ml of deionized water, stirring at room temperature until the manganese nitrate aqueous solution is completely dissolved, slowly adding the obtained aqueous solution into the mixed solution of the manganese nitrate and the carrier, stirring at room temperature for 2h, slowly adding 60g of urea aqueous solution (with the mass concentration of 40%), continuously stirring at room temperature for 12h, placing the mixture into a crystallization kettle, crystallizing at 110 ℃ for 12h, cooling and opening the kettle, filtering and separating the mixture, fully washing the solid with water and methanol in sequence, then drying at 80 ℃ in vacuum for 12h, and roasting the obtained solid at 500 ℃ in an air atmosphere for 4 h.
Example 6
Weighing 54g of manganese nitrate aqueous solution (with the mass concentration of 50%) and adding the manganese nitrate aqueous solution into 250ml of water, adding 55g of hydrotalcite, stirring at room temperature for 1h, weighing 16g of potassium permanganate and adding the potassium permanganate into 400ml of deionized water, stirring at room temperature until the manganese nitrate aqueous solution is completely dissolved, slowly adding the obtained aqueous solution into the mixed solution of the manganese nitrate and the carrier, stirring at room temperature for 2h, slowly adding 70g of potassium carbonate aqueous solution (with the mass concentration of 30%), continuously stirring at room temperature for 12h, placing the mixture into a crystallization kettle, crystallizing at 110 ℃ for 12h, cooling and opening the kettle, filtering and separating the mixture, fully washing the solid with water and methanol in sequence, then drying in vacuum at 80 ℃ for 12h, and roasting the obtained solid at 600 ℃ for 4h in an air atmosphere.
Example 7
Weighing 54g of manganese nitrate aqueous solution (with the mass concentration of 50%) and adding the manganese nitrate aqueous solution into 250ml of water, adding 50g of silicon dioxide, stirring at room temperature for 1h, weighing 16g of potassium permanganate and adding the potassium permanganate into 400ml of deionized water, stirring at room temperature until the manganese nitrate aqueous solution is completely dissolved, slowly adding the obtained aqueous solution into the mixed solution of the manganese nitrate and the carrier, stirring at room temperature for 2h, slowly adding 70g of ammonia aqueous solution (with the mass concentration of 27%), stirring at room temperature for 12h, placing the mixture into a crystallization kettle, crystallizing at 120 ℃ for 24h, cooling and opening the kettle, filtering and separating the mixture, fully washing the solid with water and methanol in sequence, then drying at 80 ℃ for 12h in vacuum, and roasting the obtained solid at 300 ℃ for 6h in an air atmosphere.
The catalytic application of the manganese-based catalyst for the synthesis of methacrylonitrile according to the invention can be achieved by the scheme of example 8:
example 8
0.3g of manganese-based catalyst, 0.1g of methacrolein and 6mL of toluene are sequentially added into a 25mL stainless steel reaction kettle with a polytetrafluoroethylene lining, the reaction kettle is sealed, 0.5MPa ammonia gas (0.3g) is firstly filled, then 0.5g of oxygen gas is filled until the total pressure is 1.0MPa, the reaction is carried out in a water bath at the temperature of 30 ℃ for 30min, the reaction kettle is cooled by an ice water bath after the reaction is finished, the gas is slowly released to the normal pressure, the reaction kettle is opened, an internal standard is added into a reaction liquid, and the conversion rate and the yield are analyzed through gas chromatography.
Comparison of results of the above-prepared catalyst for the reaction of synthesizing methacrylonitrile
The pure manganese oxide is obtained by reducing high-valence manganese salt; the supported manganese oxide is obtained by impregnating or depositing and precipitating manganese salt on a carrier and then calcining at high temperature. Under the existence of the manganese-based catalyst, methacrolein is taken as a substrate, no auxiliary agent is added in the atmosphere of oxygen and ammonia gas, and the yield of methacrylonitrile is up to 92%. Compared with the prior art, the reaction is carried out under the liquid phase condition, and the method has the advantages of mild reaction condition, simple operation, low cost, high product yield, environmental protection and the like.
Claims (12)
1. The preparation method of the manganese-based catalyst for synthesizing methacrylonitrile is characterized by comprising the following preparation steps of:
preparing pure manganese oxide:
1) weighing a certain amount of potassium permanganate, adding the potassium permanganate into water, stirring and dissolving at room temperature to obtain a potassium permanganate aqueous solution with the mass concentration range of 0.5-5% (preferably 1.5%);
2) weighing a certain amount of manganese nitrate, adding the manganese nitrate into water, stirring at room temperature to dissolve the manganese nitrate, wherein the mass concentration range of the manganese nitrate is 5-50% (preferably 10%); dropwise adding the obtained manganese nitrate solution into the potassium permanganate aqueous solution, and stirring at room temperature for 0.5-6 h (preferably 2 h); the molar ratio of the manganese nitrate to the potassium permanganate is 3: 2;
3) adding an alkaline compound or an aqueous solution of the alkaline compound, wherein the molar ratio of manganese to the alkaline compound is 1: 0.1 to 20 (preferably 1: 10); stirring the mixture at room temperature for 2-24 (preferably 12) hours, putting the mixture into a crystallization kettle for high-temperature crystallization, cooling and opening the kettle, filtering, separating and washing the mixture, drying the obtained solid in vacuum, and roasting the solid in a high-temperature air atmosphere to obtain the target simple manganese oxide;
or, preparing a supported manganese-based catalyst:
1) weighing a certain amount of potassium permanganate, adding the potassium permanganate into water, stirring and dissolving at room temperature to obtain a potassium permanganate aqueous solution with the mass concentration range of 0.5-5% (preferably 1.5%);
2) weighing a certain amount of manganese nitrate, adding the manganese nitrate into water, stirring at room temperature to dissolve the manganese nitrate to obtain a manganese nitrate solution with the mass concentration range of 5-50% (preferably 10%); weighing a certain amount of carrier, dispersing the carrier in a manganese nitrate aqueous solution, stirring at room temperature for 1-12 h, adding the obtained mixture into the potassium permanganate aqueous solution, and stirring at room temperature for 0.5-6 h (preferably 2 h); the molar ratio of the manganese nitrate to the potassium permanganate is 3: 2;
3) adding an alkaline compound or an aqueous solution of the alkaline compound, wherein the molar ratio of manganese to the alkaline compound is 1: 0.1 to 20 (preferably 1: 10); and (3) continuously stirring for 2-24 (preferably 12) hours at room temperature, putting the obtained mixture into a crystallization kettle for high-temperature crystallization, cooling and opening the kettle, filtering, separating and washing the mixture, drying the obtained solid in vacuum, and roasting in a high-temperature air atmosphere to obtain the target supported manganese-based catalyst.
2. The method of claim 1, wherein: the carrier of the supported manganese-based catalyst is one or more than two of silicon dioxide, magnesium oxide, hydroxyapatite, calcium oxide, aluminum oxide and hydrotalcite, preferably silicon dioxide; the silica may be solid silica powder or may be one or two kinds of silica sol, and the particle sizes of the two kinds of silica are not limited.
3. The method of claim 1, wherein: the crystallization temperature is 80-150 ℃ (preferably 120 ℃), and the crystallization time is 1-24 h (preferably 12 h).
4. The method of claim 1, wherein: the alkaline compound is one or more of potassium hydroxide, sodium carbonate, potassium bicarbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, urea and ammonia gas; the mass concentration of the alkaline compound aqueous solution is 5-50%.
5. The method of claim 1, wherein: the vacuum drying treatment is to vacuumize the solid for 2 to 24 (preferably 12) hours at the temperature of 60 to 100 ℃ (preferably 80 ℃).
6. The method of claim 1, wherein: the roasting temperature is 200-600 (preferably 300) DEG C, and the roasting time is 2-6 h (preferably 4 h).
7. The method of claim 1, wherein: the percentage content of manganese in the obtained load type manganese-based catalyst is 5-30%.
8. A pure manganese oxide or a supported manganese-based catalyst prepared by the method of any one of claims 1 to 7, both of which are referred to as manganese-based catalysts.
9. The manganese-based catalyst according to claim 8, which can be used for catalyzing the ammoxidation of methacrolein to produce methacrylonitrile, wherein the manganese-based catalyst is manganese oxide and/or a supported manganese-based catalyst.
10. Use according to claim 9, characterized in that the methacrylonitrile synthesis process is as follows: in the presence of a manganese-based catalyst and an organic solvent, taking oxygen and/or air as an oxidant, ammonia as an ammonia source and methacrolein as a raw material, and carrying out an ammoniation oxidation reaction to obtain a product methacrylonitrile; the reaction temperature is 25-100 ℃ (preferably 30 ℃), and the reaction time is 5-120 min (preferably 30 min).
11. The method of synthesis according to claim 10, wherein: the reaction solvent is one or a mixture of toluene, ethylbenzene, mesitylene, acetonitrile, acetone, 1, 2-dichloroethane, chloroform, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-pentane, N-heptane and tetrahydrofuran.
12. The synthesis method according to claim 11, wherein the molar ratio of the methacrolein to the manganese element in the catalyst is: 1: 0.01-5, preferably 1: 1;
the molar ratio of the methacrolein to the oxygen is as follows: 1: 1-20, preferably 1: 5; the molar ratio of the methacrolein to the ammonia gas is as follows: 1: 1-20, preferably 1: 5.
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Application publication date: 20210413 |