CN109988063B - Method for preparing acrolein - Google Patents
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Abstract
The invention provides a method for preparing acrolein, and belongs to the field of green chemical industry. The method comprises the following steps: (1) fully and uniformly mixing the catalyst, glycerol and water to prepare a glycerol water catalytic reaction solution; (2) adding an oxygen-containing organic compound and a Pickering emulsifier into the glycerin water catalytic reaction solution, and mechanically emulsifying to prepare a Pickering emulsion reaction system; (3) and (3) heating the Pickering emulsion reaction system prepared in the step (2) to the reaction temperature, condensing and collecting acrolein obtained by the reaction, and recovering the catalytic system. The invention accelerates the mass transfer rate in the reaction system for preparing the acrolein, has the advantages of high reaction yield, mild process reaction conditions, no need of high temperature and high pressure, recoverable used solvent and reagent, low manufacturing cost, good economy and environmental protection, and solves the problems of high reaction temperature and high pressure in the prior art.
Description
Technical Field
The invention belongs to the field of green chemical industry, and particularly relates to a method for preparing acrolein by dehydrating glycerin in a water-in-oil Pickering emulsion system.
Technical Field
The biomass resource is the only recyclable carbon resource in the nature, and with the increasing shortage of petrochemical resources, the biomass resource is used as a raw material to be catalytically converted into liquid fuel and fine chemicals, so that the crisis of non-renewable resources such as petrochemicals can be solved, and the problem of environmental pollution is further solved. For example, biodiesel prepared from bio-oil has the characteristics of good environmental protection performance, good fuel performance, wide raw material source, renewability and the like, has important strategic significance in promoting energy substitution, relieving environmental pressure and the like, and has obtained remarkable research results at present. However, a large amount of glycerol is produced as a by-product in the process. Therefore, if the production of high value-added fine chemicals from glycerol could be developed during the production of biodiesel, not only would the economic value be increased, but also the sustainable development route of green chemistry would be met. Glycerol is an important chemical raw material and is widely used for producing propylene glycol, glycerol ketone, acrolein and the like. The dehydration product of the method is acrolein, which is an important chemical intermediate, and is used for producing methionine and the like from acrylic acid and pyridine, wherein the requirement of the acrolein is increased greatly due to the market demand of the methionine. In the existing literature reports, the dehydration of glycerol under an acidic catalyst to prepare acrolein is mainly a gas phase reaction, the reaction temperature is high, the pressure is high, the catalyst is easily deactivated by carbonization, and a small amount of liquid phase reaction is carried out, so that the yield is low. The invention patent with the publication number of CN107915614A discloses the research of preparing acrolein by dehydrating glycerin in a Pickering emulsion system, and a single emulsion liquid drop is used as a micro-reactor, so that the mass transfer rate of the acrolein is accelerated by the extremely large contact area, and the better yield of the acrolein is obtained. In this study, the weakly polar organic phase is used as the oil phase, and the solubility of acrolein in the oil phase is low, so that the acrolein is not favorably introduced into the oil phase from the reaction system, and the yield of acrolein is not high.
Disclosure of Invention
The invention provides a method for preparing acrolein by catalyzing glycerin dehydration in a Pickering emulsion system with an oxygen-containing organic compound as an oil phase, aiming at the problems of high reaction temperature, high pressure, low acrolein yield and the like in the existing reaction for preparing the acrolein by using glycerin.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a method for preparing acrolein, comprising the steps of:
(1) fully and uniformly mixing the catalyst, glycerol and water to prepare a glycerol water catalytic reaction solution;
(2) adding an oxygen-containing organic compound and a Pickering emulsifier into the glycerin water catalytic reaction solution, and mechanically emulsifying to prepare a Pickering emulsion reaction system;
(3) and (3) heating the Pickering emulsion reaction system prepared in the step (2) to the reaction temperature, condensing and collecting acrolein obtained by the reaction, and recovering the catalytic system.
The method comprises the steps of mixing an oxygen-containing organic compound, glycerol, water, a catalyst and a Pickering emulsifier to prepare a water-in-oil emulsion system, heating to convert the glycerol into acrolein, diffusing and overflowing the generated acrolein into the reaction system through a continuous phase formed by the oxygen-containing organic compound, and then condensing and collecting to obtain an acrolein product.
Acrolein is extremely active, easily self-polymerizes and reacts with glycerol to form humus with complex structure and properties, so that acrolein generated by dehydration of glycerol is easily continuously reacted under the action of a catalyst during the reaction process to be consumed, thereby causing reduction of yield. And the glycerol contains a large amount of hydroxyl and has higher viscosity, so that the diffusion coefficient of the generated acrolein is small, the retention time of the acrolein in the glycerol phase is increased, and the possibility of side reaction is increased. In a gas phase system, the distance between the molecules of glycerol and acrolein is large, the interaction is weak, the diffusion coefficient is large, the glycerol and the acrolein are easy to separate from each other, the occurrence probability of reaction side reaction is reduced, and the yield is high. Meanwhile, the invention uses the oxygen-containing organic compound as the oil phase of the emulsion, and the acrolein has proper solubility in the oxygen-containing organic compound, thereby being more beneficial to the diffusion of the acrolein and being separated from a high-activity water phase reaction system in time, improving the mass transfer rate of the acrolein in the reaction system, reducing the contact time of the acrolein and reactants, and reducing the possibility of continuous reaction of the acrolein, thereby greatly improving the yield of the acrolein.
Further, the catalyst in the step (1) is medium strong acidic
The acid is sulfuric acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, potassium hydrogen sulfate or sodium hydrogen sulfate. The catalyst can ensure that the glycerol is converted into the acrolein with high selectivity, simultaneously ensure the stability of the oxygen-containing organic compound, and the medium-strength Lewis acid can catalyze the oxygen-containing organic reagent to carry out chemical reaction.
Further, the volume ratio of the glycerol to the water in the step (1) is 1:1-9, the ratio of the mass of the catalyst to the total volume of the glycerol and the water used is 0.02-0.7 g: 1 ml. The water plays an important role in the reaction process, can not only dilute the glycerol and reduce the viscosity of the reaction phase so as to strengthen the mass transfer rate of the acrolein in the reaction process, but also form the reaction phase together with the glycerol, and form stable emulsion under the condition that an oxygen-containing organic compound is used as an oil phase.
Further, the oxygen-containing organic compound in the step (2) refers to an oxygen-containing organic compound which is in a water phase and can form an emulsion under the action of a Pickering emulsifier, and specifically is one or a mixture of several of animal and vegetable oil and fat, long-chain fatty acid ethyl ester, long-chain fatty acid methyl ester and long-chain fatty acid propyl ester in any proportion. . The oxygen-containing organic compound has better solubility to acrolein than a less polar or non-polar oxygen-free organic reagent, and can rapidly absorb the formed acrolein into a reaction-inert oil phase at the initial stage of conversion of glycerol into acrolein, thereby reducing side reactions and remarkably improving the yield of acrolein.
Further, the Pickering emulsifier in the step (2) is SiO2The water-soluble organic silicon-based emulsifier is characterized by comprising a molecular sieve, montmorillonite, activated carbon or graphene, wherein the contact angle of the emulsifier and water is 60-160 degrees. The emulsifier can fully emulsify a reaction system, simultaneously keeps the stability of the emulsion at high temperature, and is not easy to generate chemical reaction in the reaction process, thereby ensuring the stability of the reaction process.
Further, in the step (2), adding an oxygen-containing organic compound and a Pickering emulsifier into the glycerin water catalytic reaction solution, and mechanically emulsifying to prepare a Pickering emulsion reaction system; wherein the volume ratio of the added oxygen-containing organic compound to the total volume of glycerin and water used in the step (1) is 0.5-3: 1. the oxygen-containing organic compound functions as a continuous phase in the system to disperse the aqueous phase while dissolving acrolein diffused from the aqueous phase, and then under the thermal diffusion, the acrolein is diffused from the oxygen-containing organic compound phase (oil phase) to the gas phase and then condensed and collected, so the amount of the oxygen-containing organic compound cannot be too small, too small is not good for the stability of the emulsion system, nor too much, too much affects the diffusion of acrolein from the oil phase to the gas phase.
Further, in the step (2), adding an oxygen-containing organic compound and a Pickering emulsifier into the glycerin water catalytic reaction solution, and mechanically emulsifying to prepare a Pickering emulsion reaction system; wherein the ratio of the mass of the added Pickering emulsifier to the mass of the catalyst used in the step (1) and the total volume of glycerol and water is 0.001-0.05 g: 0.02-0.7 g: 1 ml. The catalyst is too little, the velocity of the generated acrolein is too slow, the reaction efficiency is too low, the amount of the catalyst is too large, the side reaction of the glycerol and the acrolein can be increased, and in addition, the catalyst can be separated out and attached to the surface of an emulsifier in the dehydration reaction process of the glycerol, so that the stability of the emulsion is reduced; too low amount of emulsifier makes it difficult to form a stable emulsion system, while too large amount of emulsifier hinders mass transfer of acrolein at the oil-water interface and acts to reduce the yield of acrolein.
Further, the mechanical emulsification in the step (2) is stirring or ultrasonic emulsification, wherein the rotating speed of stirring is 800-2000 r/min, and the stirring is continued for 0.5-5 min; the ultrasonic time of ultrasonic emulsification is 2-10 min. Under the operation condition, the emulsion can be ensured to be fully emulsified, and is not easy to aggregate and grow up, the emulsification time is too short, the emulsification is not sufficient, so that the size of liquid drops in the emulsion is uneven, aggregation and growth are easy to occur, and the reaction effect is influenced.
Further, the Pickering emulsion reaction system prepared in the step (2) is heated to a reaction temperature in the step (3), wherein the reaction temperature is 140-200 ℃. If the reaction temperature is too low, the reaction efficiency is low, which affects the economic efficiency, while if the reaction temperature is too high, the emulsion stability is affected, and side reactions are increased.
Further, the recovery catalytic system in the step (3) comprises recovered grease, recovered Pickering emulsifier and recovered catalyst, and the following scheme is specifically adopted:
filtering or centrifugally separating the reacted emulsion system, and purifying the oil for recycling; heating water to fully dissolve the materials left after oil separation, filtering, washing the filter cake for 3-5 times by using water, drying, and reusing the filter cake as a Pickering emulsifier; the catalyst obtained by the evaporation crystallization recovery of the aqueous solution can be reused.
Compared with the prior art, the invention has the following advantages:
1. the invention accelerates the mass transfer rate in the reaction system for preparing the acrolein, effectively reduces the consumption of the acrolein by reducing the contact time of the acrolein and a reaction substrate, obviously improves the reaction yield, and has the glycerol conversion rate of 90-99 percent and the acrolein yield of 50-80 percent;
2. the process has mild reaction conditions, does not need high temperature and high pressure, and solves the problems of high reaction temperature and high pressure in the prior art;
3. the solvent and the Pickering reagent used in the invention can be recycled, the manufacturing cost is low, the economy is good, and the environment is protected;
4. the reaction product does not need additional accessory separation equipment and process, and the process is simple and high in efficiency.
Drawings
FIG. 1 is an NMR hydrogen spectrum of acrolein;
FIG. 2 is an NMR carbon spectrum of acrolein.
Detailed Description
The technical solution of the present invention is further explained with reference to the accompanying drawings and specific embodiments.
Example 1:
(1) mixing 7.0g potassium bisulfate, 2.5ml glycerol and 7.5ml water thoroughly to obtain glycerol water catalytic reaction solution;
(2) adding 20ml of vegetable oil peony oil and 0.35g of silicon dioxide powder with a contact angle of 150 degrees into the glycerin water catalytic reaction solution, and stirring for 0.5 minute under mechanical stirring at 1600 rpm to emulsify to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 180 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of the glycerol reaches 99%, and the yield of the acrolein is 77% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain peony oil, dissolving the centrifuged paste substance in hot water, filtering, washing the filter cake for 5 times, drying, and repeatedly using the dissolved paste substance as an emulsifier, and recrystallizing and drying the filtrate to repeatedly use the filtrate as a catalyst.
Example 2:
(1) 0.2g of sulfuric acid, 1ml of glycerol and 9ml of water are fully and uniformly mixed to prepare glycerol water catalytic reaction solution;
(2) adding 10ml of long-chain fatty acid stearic acid and 0.01g of silicon dioxide powder with a contact angle of 120 degrees into the glycerin water catalytic reaction solution, and stirring for 1 minute under the mechanical stirring of 1200 revolutions per minute to emulsify to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 160 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of the glycerol reaches 94%, and the yield of the acrolein is 68% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain stearic acid, dissolving the centrifuged paste substance with hot water, filtering, washing the filter cake for 5 times, drying, and repeatedly using the filtrate as an emulsifier; the catalyst sulfuric acid obtained by evaporating and recovering the aqueous solution can be reused.
Example 3:
(1) 2g of hydrochloric acid, 1.5ml of glycerol and 8.5ml of water are fully and uniformly mixed to prepare a glycerol water catalytic reaction solution;
(2) adding 5ml of long-chain fatty acid ethyl ester oleate and 0.15g of graphene powder with a contact angle of 150 degrees into the glycerin water catalytic reaction solution, and stirring for 0.5 minute under mechanical stirring at 1600 rpm to emulsify to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 140 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of the glycerol reaches 90%, and the yield of the acrolein is 50% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain ethyl oleate, dissolving the centrifuged paste substance in hot water, filtering, washing the filter cake for 5 times, drying, and reusing the filter cake as an emulsifier, and evaporating and recovering the aqueous solution to obtain the catalytic hydrochloric acid which can be reused.
Example 4:
(1) fully and uniformly mixing 5g of phosphotungstic acid, 5ml of glycerol and 5ml of water to prepare a glycerol water catalytic reaction solution;
(2) adding 30ml of animal oil glyceryl tristearate and 0.5g of montmorillonite powder with a contact angle of 96 degrees into the glycerol water catalytic reaction solution, and stirring for 0.5 min under mechanical stirring at 800 rpm to emulsify to obtain Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 150 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the glycerol conversion rate reaches 92%, and the collected liquid is analyzed, so that the acrolein yield is 71%; centrifuging the reaction system, pouring out and recovering supernatant to obtain tristearin, dissolving the centrifuged paste matter in hot water, filtering, washing the filter cake for 5 times, drying, reusing as emulsifier, recrystallizing the filtrate, drying, and reusing as catalyst.
Example 5:
(1) 4g of phosphoric acid, 3.5ml of glycerol and 6.5ml of water are fully and uniformly mixed to prepare glycerol water catalytic reaction solution;
(2) adding 20ml of long-chain fatty acid methyl ester palmitate and 0.3g of molecular sieve with a contact angle of 60 degrees into the glycerin water catalytic reaction solution, and stirring for 0.5 minute under the mechanical stirring of 1000 revolutions per minute to emulsify to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 160 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of glycerol reaches 97.8%, and the yield of acrolein is 57% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain methyl palmitate, dissolving the centrifuged paste substance in hot water, filtering, washing the filter cake for 5 times, drying, and recycling the filter cake as an emulsifier; the catalyst phosphoric acid obtained by evaporating and recovering the aqueous solution can be reused.
Example 6:
(1) 2g of phosphomolybdic acid, 1.5ml of glycerol and 8.5ml of water are fully and uniformly mixed to prepare a glycerol water catalytic reaction solution;
(2) adding 10ml of long-chain fatty acid propyl linolenate propyl ester and 0.2g of activated carbon powder with a contact angle of 160 degrees into the glycerol water catalytic reaction solution, and stirring for 0.5 minute under the mechanical stirring of 2000 r/min to emulsify to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 180 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of glycerol reaches 94.8%, and the yield of acrolein is 65.3% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain propyl linolenate, dissolving the centrifuged paste with hot water, filtering, washing the filter cake for 5 times, drying, and reusing as emulsifier, recrystallizing the filtrate, and drying to obtain catalyst.
Example 7:
(1) fully and uniformly mixing 6g of sodium bisulfate, 4.5ml of glycerol and 5.5ml of water to prepare a glycerol water catalytic reaction solution;
(2) adding 25ml of long-chain fatty acid oleic acid and 0.25g of silicon dioxide powder with a contact angle of 160 degrees into the glycerin water catalytic reaction solution, and stirring for 5 minutes under the mechanical stirring of 2000 revolutions per minute to emulsify to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 170 ℃, and condensing and collecting acrolein obtained by the reaction until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of the glycerol reaches 98%, and the yield of the acrolein is 75% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain mixed oil, dissolving the centrifuged paste substance in hot water, filtering, washing the filter cake for 5 times, drying, and repeatedly using the dissolved paste substance as an emulsifier, and recrystallizing and drying the filtrate to repeatedly use the filtrate as a catalyst.
Example 8:
(1) fully and uniformly mixing 5g of silicotungstic acid, 2.5ml of glycerol and 7.5ml of water to prepare a glycerol water catalytic reaction solution;
(2) adding 10ml of ethyl oleate, 5ml of mixed oil of ethyl linolenate and 0.45g of graphene powder with a contact angle of 150 degrees into the glycerol water catalytic reaction solution, and emulsifying by ultrasonic for 2 minutes to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 200 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of glycerol reaches 97.5%, and the yield of acrolein is 73% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain mixed oil, dissolving the centrifuged paste substance in hot water, filtering, washing the filter cake for 5 times, drying, and repeatedly using the dissolved paste substance as an emulsifier, and recrystallizing and drying the filtrate to repeatedly use the filtrate as a catalyst.
Example 9:
(1) 5.5g of potassium bisulfate, 1.5ml of glycerol and 8.5ml of water are fully and uniformly mixed to prepare glycerol water catalytic reaction solution;
(2) adding 20ml of vegetable oil soybean oil and 0.35g of silicon dioxide powder with a contact angle of 100 degrees into the glycerin water catalytic reaction solution, and emulsifying by ultrasonic for 10 minutes to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 200 ℃, and condensing and collecting acrolein obtained by the reaction at the same time until no liquid is condensed and dripped out. Through nuclear magnetic detection, the conversion rate of the glycerol reaches 99%, and the yield of the acrolein is 80% by analyzing the collected liquid; centrifuging the reaction system, pouring out and recovering supernatant to obtain soybean oil, dissolving the centrifuged paste substance in hot water, filtering, washing the filter cake for 5 times, drying, and repeatedly using the dissolved paste substance as an emulsifier, and recrystallizing and drying the filtrate to repeatedly use the filtrate as a catalyst.
Example 10:
(1) 2.5g of sodium bisulfate, 3.5ml of glycerol and 6.5ml of water are fully and uniformly mixed to prepare glycerol water catalytic reaction solution;
(2) adding 15ml of vegetable oil olive oil and 0.25g of silicon dioxide powder with a contact angle of 70 degrees into the glycerin water catalytic reaction solution, and emulsifying by ultrasonic for 8 minutes to prepare Pickering emulsion.
(3) Heating the Pickering emulsion reaction system to 170 ℃, and condensing and collecting acrolein obtained by the reaction until no liquid is condensed and dripped out. Through nuclear magnetic detection, the glycerol conversion rate reaches 92%, and the collected liquid is analyzed, so that the acrolein yield is 66%; centrifuging the reaction system, pouring out and recovering supernatant to obtain olive oil, dissolving the centrifuged paste substance in hot water, filtering, washing the filter cake for 5 times, drying, and repeatedly using the dissolved substance as an emulsifier, and recrystallizing and drying the filtrate to repeatedly use the filtrate as a catalyst.
The NMR hydrogen spectrum of acrolein is shown in figure 1, and the NMR carbon spectrum of acrolein is shown in figure 2.
The oxygen-containing organic compound in the step (2) in the above embodiment refers to an oxygen-containing organic compound that is in a water phase and can form an emulsion under the action of a Pickering emulsifier, and may be a mixture of several of animal and vegetable fats and oils, long-chain fatty acids, long-chain fatty acid ethyl esters, long-chain fatty acid methyl esters, and long-chain fatty acid propyl esters in any proportion.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A method for producing acrolein, characterized by: the method for preparing acrolein comprises the following steps:
(1) fully and uniformly mixing the catalyst, glycerol and water to prepare a glycerol water catalytic reaction solution;
(2) adding an oxygen-containing organic compound and a Pickering emulsifier into the glycerin water catalytic reaction solution, and mechanically emulsifying to prepare a Pickering emulsion reaction system; the oxygen-containing organic compound is one or more of animal and vegetable oil, long-chain fatty acid methyl ester and long-chain fatty acid propyl ester which are mixed in any proportion;
(3) and (3) heating the Pickering emulsion reaction system prepared in the step (2) to the reaction temperature, condensing and collecting acrolein obtained by the reaction, and recovering the catalytic system.
2. The method of preparing acrolein according to claim 1, wherein: the catalyst in step (1) is a moderately strong acid bransted acid, specifically sulfuric acid, hydrochloric acid, phosphoric acid, phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, potassium bisulfate or sodium bisulfate.
3. The method of preparing acrolein according to claim 2, wherein: the volume ratio of the glycerol to the water in the step (1) is 1:1-9, the ratio of the mass of the catalyst to the total volume of the glycerol and the water is 0.02-0.7 g: 1 ml.
4. A method of producing acrolein according to claim 3, wherein: the Pickering emulsifier in the step (2) is SiO2The water-soluble organic silicon-based emulsifier is characterized by comprising a molecular sieve, montmorillonite, activated carbon or graphene, wherein the contact angle of the emulsifier and water is 60-160 degrees.
5. The method of producing acrolein according to claim 4, wherein: adding an oxygen-containing organic compound and a Pickering emulsifier into the glycerin water catalytic reaction solution in the step (2), and mechanically emulsifying to prepare a Pickering emulsion reaction system; wherein the volume ratio of the added oxygen-containing organic compound to the total volume of glycerin and water used in step (1) is 0.5-3: 1.
6. The method of preparing acrolein according to claim 5, wherein: adding an oxygen-containing organic compound and a Pickering emulsifier into the glycerin water catalytic reaction solution in the step (2), and mechanically emulsifying to prepare a Pickering emulsion reaction system; wherein the ratio of the mass of the added Pickering emulsifier to the mass of the catalyst used in the step (1) and the total volume of glycerol and water is 0.001-0.05 g: 0.02-0.7 g: 1 ml.
7. The method of producing acrolein according to claim 6, wherein: the mechanical emulsification in the step (2) is stirring or ultrasonic emulsification, wherein the stirring speed is 800-; the ultrasonic time of ultrasonic emulsification is 2-10 min.
8. The method of producing acrolein according to claim 7, wherein: and (3) heating the Pickering emulsion reaction system prepared in the step (2) to a reaction temperature, wherein the reaction temperature is 140-200 ℃.
9. The method for producing acrolein according to any one of claims 1 to 8, wherein: the recovery catalysis system in the step (3) comprises recovered grease, recovered Pickering emulsifier and recovered catalyst, and the following scheme is adopted specifically:
filtering or centrifugally separating the reacted emulsion system, and purifying the oil for recycling; heating the residual materials after oil separation to fully dissolve in hot water, filtering, washing the filter cake with water for 3-5 times, drying, and reusing as a Pickering emulsifier; the water solution is evaporated, crystallized and recycled to obtain the catalyst for reuse.
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