CN115010718B - Method for preparing isosorbide by catalyzing sorbitol to dehydrate through polymeric ionic liquid - Google Patents
Method for preparing isosorbide by catalyzing sorbitol to dehydrate through polymeric ionic liquid Download PDFInfo
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Abstract
The invention discloses a method for preparing isosorbide by catalyzing sorbitol with polymeric ionic liquid, belonging to the fields of catalytic chemistry and chemical engineering. The method comprises the following steps: and heating the solid sorbitol to be molten, adding a polymeric ionic liquid serving as a catalyst into the molten sorbitol, and carrying out dehydration reaction to prepare the isosorbide. The method provided by the invention uses the polymeric ionic liquid as the catalyst, and has the advantages of high isosorbide yield, good selectivity, simple operation and small pollution, and the isosorbide yield can reach 94%.
Description
Technical Field
The invention belongs to the fields of catalytic chemistry and chemical engineering, and particularly relates to a method for preparing isosorbide by catalyzing sorbitol with polymeric ionic liquid.
Background
Sorbitol is a platform compound derived from carbohydrates that is widely found in many berries and fruits as a sweetener. Sorbitol can be prepared into a series of high-added-value bio-based chemicals or materials through hydrogenolysis, polymerization, dehydration and other reactions. Among them, isosorbide is a product of secondary dehydration cyclization of sorbitol, which is an important novel bio-based chemical product and can be widely applied to the fields of food, cosmetics, medicines and the like.
At present, the domestic isosorbide production process mostly adopts liquid acid catalysis, reduced pressure distillation, organic solvent extraction crystallization and other processes, the process is complex, the requirement on corrosion resistance of reaction equipment is high, serious problems such as resource waste, environmental pollution and the like are caused, and the production cost of the isosorbide is high.
With the concept of green chemistry, the environment-friendly green efficient reaction system is a future development trend. The solid acid overcomes the series of disadvantages of liquid acid, and has Bronsted acid or Lewis acid on its surface, wide acid strength distribution, and good therapeutic effectEasy separation from the liquid phase reaction system, no corrosion to equipment, simple post-treatment, less environmental pollution, high selectivity and the like, can be used in a higher temperature range, and expands the application range of acid catalytic reaction which is possible to be performed in thermodynamics. Patent CN110092795B discloses the use of SO 4 2- /ZrO 2 -Al 2 O 3 The highest yield of isosorbide is 80% in the process of catalyzing sorbitol to dehydrate by the immobilized acid. Patent CN111253413B discloses that the yield of isosorbide prepared by catalyzing sorbitol to dehydrate by using acid niobium pentoxide can reach more than 85%. The further improvement of the isosorbide yield can effectively reduce side reactions, simplify the separation and purification process and reduce the production cost, so that the development of the efficient catalyst is always a research hot spot.
The polymeric ionic liquid is a novel renewable ionic liquid, combines the characteristics of the ionic liquid and a polymer, has high thermal stability, adjustable shape, corrosion resistance and the like, can be used as a catalyst or a catalyst carrier, and is an attractive catalytic material suitable for biomass resource utilization. Aiming at the problem of low isosorbide yield, the invention discloses a strong acid activated polymerization ionic liquid catalyst system, which is environment-friendly, does not corrode production equipment and has higher catalytic efficiency on the production of isosorbide by dehydration of sorbitol.
Disclosure of Invention
Aiming at the problems and the defects existing in the prior art, the invention aims to provide a method for preparing isosorbide by catalyzing sorbitol with polymeric ionic liquid.
In order to achieve the aim of the invention, the technical scheme adopted by the invention is as follows:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate by polymeric ionic liquid comprises the following specific steps: and heating the solid sorbitol to be molten, and adding polymeric ionic liquid serving as a catalyst into the molten sorbitol to carry out dehydration reaction to prepare the isosorbide.
According to the above method, preferably, the addition amount of the polymeric ionic liquid is 0.1 to 20. 20wt% by weight of the solid sorbitol.
According to the above method, it is preferable that the dehydration reaction temperature is 110 to 160 ℃, the reaction pressure is-0.09 MPa, and the reaction time is 2 to 10 h.
According to the above method, preferably, the polymeric ionic liquid is prepared by the following method:
(1) Dissolving a C=C double bond substituted imidazole monomer, 2-bromoethylamine hydrobromic acid and an initiator in a solvent, and reacting to obtain an amination polymerization ionic liquid;
(2) Weighing a proper amount of the polymeric ionic liquid obtained in the step (1), adding a metal salt solution into the polymeric ionic liquid, and stirring the mixture at 20-80 ℃ for reaction for 1-4 h to obtain a metal modified polymeric ionic liquid;
(3) And (3) adding an acid solution into the metal modified polymeric ionic liquid obtained in the step (2) for acidification, and removing the solvent to obtain the target polymeric ionic liquid.
According to the above method, preferably, the molar ratio of the c=c double bond substituted imidazole monomer and 2-bromoethylamine hydrobromic acid in the step (1) is 1 to 10:1.
according to the above method, preferably, the initiator is used in step (1) in an amount of 2.7wt% of the c=c double bond substituted imidazole monomer.
According to the above method, preferably, in the step (1), the reaction time is 1 to 10 and h, and the reaction temperature is 60 to 100 ℃.
According to the above method, preferably, the c=c double bond substituted imidazole monomer in step (1) is 1-vinylimidazole or N-allylimidazole, and the initiator is azobisisobutyronitrile AIBN.
According to the above method, more preferably, the c=c double bond substituted imidazole monomer in step (1) is 1-vinylimidazole.
According to the above method, preferably, the metal salt solution in the step (2) is KNbO 3 Solutions or KTaO 3 Any one of the solutions.
According to the above method, more preferably, the metal salt solution in the step (2) is KNbO 3 A solution.
According to the above method, preferably, the specific operation of acidification in step (3) is: adding an acid solution with the concentration of 1-10 mol/L into the metal modified polymeric ionic liquid obtained in the step (2), and stirring and acidifying at 40 ℃ for 4-8 h.
According to the above method, more preferably, the volume ratio of the metal modified polymeric ionic liquid to the acid solution is 2:1.
according to the above method, preferably, the acid solution is any one of sulfuric acid, phosphoric acid, nitric acid, or hydrochloric acid.
According to the above method, more preferably, the acid solution is either sulfuric acid or phosphoric acid.
Compared with the prior art, the invention has the following beneficial effects:
1. the method adopts the strong acid activated polymeric ionic liquid as the catalyst, takes sorbitol as the raw material, directly prepares the isosorbide through dehydration reaction under the conditions of no solvent and vacuum, and has the advantages of high isosorbide yield, good selectivity, simple and convenient operation and small pollution, and the isosorbide yield can reach 94 percent. The catalyst is a long-chain polymer, has a larger molecular weight than the anions and cations of the conventional ionic liquid, is easier to separate from the product, and can be reused.
2. The addition amount of the polymerized ionic liquid in the method provided by the invention is 0.1-20wt% of the mass of the solid sorbitol, and compared with the existing preparation method, the catalyst dosage is greatly reduced, and the cost is saved.
3. The catalyst adopted by the invention is a modified ionic liquid polymer, and a chain monomer can be chemically combined with carbonyl and hydroxyl in reactant molecules through amino modification, and then is mixed with a metal salt solution, and the metal center is taken as an active site to adjust the surface acid property, so that the aim of improving the catalytic performance of the catalyst is fulfilled. Therefore, the catalyst prepared by the invention can more effectively grasp reactant molecules, improve the diffusion rate and the reaction rate of sorbitol, and improve the economic benefit of the process for preparing the isosorbide.
Drawings
The sorbitol conversion profile over time in the reaction of FIG. 1;
FIG. 2 is a graph showing the yield of 1, 4-sorbitan as a reaction intermediate over time;
FIG. 3 is a graph showing the yield of isosorbide as a function of time in the reaction.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention.
Example 1:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate by polymeric ionic liquid comprises the following specific steps:
(1) Dissolving 3.0336 g of 1-vinylimidazole, 0.0808 g initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide in 40 mL absolute ethyl alcohol, stirring at 80 ℃ and condensing and refluxing 4 h under the protection of nitrogen, changing the solution into orange yellow with yellow solid at the bottom, and drying the reaction solution to obtain orange yellow solid, namely the aminated polyvinylimidazole [ VIM ]]NH 2 ；
(2) Weighing 1.4 g of the amination polyvinyl imidazole [ VIM ] obtained in the step (1)]NH 2 In a three-necked flask, 100 mL KNbO was further added 3 The solution is completely dissolved, and is stirred and reacted at 40 ℃ for 4 h to obtain the metal modified polymeric ionic liquid Nb/[ VIM ]]NH 2 ；
(3) Adding 3 mol/L sulfuric acid solution (volume ratio is 2:1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying 4H at 40 ℃, and steaming off redundant water to obtain an acidic polymeric ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) 5g of solid sorbitol is weighed into a reactor, heated to a liquid state at 120 ℃, and added with 0.5 g of 3H-Nb/[ VIM ]]NH 2 The catalyst is stirred for reaction 6 h under the pressure of-0.09 MPa, materials in a reaction system are continuously measured in a certain time in the reaction process, and the results are shown in figures 1-3.
Example 2:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate by polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinylimidazole, 0.0808 g initiator AIBN and 4.3600 g of 2-bromine are takenDissolving ethylamine hydrobromide in 40 mL absolute ethanol, stirring at 80deg.C under nitrogen protection, condensing and refluxing for 4 h, changing the solution into orange yellow and yellow solid appearing at bottom, and oven drying the reaction solution to obtain orange yellow solid, namely aminated polyvinylimidazole [ VIM ]]NH 2 ；
(2) Weighing 1.4 g of the amination polyvinyl imidazole [ VIM ] obtained in the step (1)]NH 2 In a three-necked flask, 100 mL KNbO was further added 3 The solution is completely dissolved, and is stirred and reacted at 40 ℃ for 4 h to obtain the metal modified polymeric ionic liquid Nb/[ VIM ]]NH 2 ；
(3) Adding 3 mol/L sulfuric acid solution (volume ratio is 2:1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying 4H at 40 ℃, and steaming off redundant water to obtain an acidic polymeric ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) 5g of solid sorbitol is weighed into a reactor, heated to a liquid state at 130 ℃, and added with 0.5 g of 3H-Nb/[ VIM ]]NH 2 The catalyst is stirred for reaction 2h under the pressure of-0.09 MPa, materials in a reaction system are continuously measured in a certain time in the reaction process, and the results are shown in figures 1-3.
Example 3:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate by polymeric ionic liquid comprises the following specific steps:
(1) Dissolving 3.0336 g of 1-vinylimidazole, 0.0808 g initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide in 40 mL absolute ethyl alcohol, stirring at 80 ℃ and condensing and refluxing 4 h under the protection of nitrogen, changing the solution into orange yellow with yellow solid at the bottom, and drying the reaction solution to obtain orange yellow solid, namely the aminated polyvinylimidazole [ VIM ]]NH 2 ；
(2) Weighing 1.4 g of the amination polyvinyl imidazole [ VIM ] obtained in the step (1)]NH 2 In a three-necked flask, 100 mL KNbO was further added 3 The solution is completely dissolved, and is stirred and reacted at 40 ℃ for 4 h to obtain the metal modified polymeric ionic liquid Nb/[ VIM ]]NH 2 ；
(3) Adding the metal modified polymeric ionic liquid obtained in the step (2)Adding 3 mol/L sulfuric acid solution (volume ratio of 2:1), stirring at 40deg.C for acidification of 4H, and evaporating excessive water to obtain acidic polymerization ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) 5g of solid sorbitol was weighed into a reactor, heated to liquid state at 140℃and added with 0.5 g of 3H-Nb/[ VIM ]]NH 2 The catalyst is stirred and reacted for 1.25 and h under the pressure of-0.09 MPa, materials in a reaction system are continuously measured for a certain time in the reaction process, and the results are shown in figures 1-3.
And (3) gas chromatography detection:
the reaction processes of examples 1 to 3 were subjected to gas chromatography, and the change of the sorbitol conversion, the yields of the intermediate 1, 4-sorbitan and isosorbide with time was shown in FIGS. 1 to 3.
As can be seen from FIG. 1, the sorbitol conversion rate can reach 100% at the temperature ranging from 120 to 140 ℃, and the sorbitol conversion rate can reach 100% after the reaction of 1.25 and h at the temperature of 140 ℃.
As can be seen from fig. 2, at a temperature of 120 ℃, the yield of the intermediate 1, 4-sorbitan increases and then decreases, because sorbitol rapidly undergoes a dehydration reaction, so that the intermediate rapidly accumulates in a short period of time, and the yield tends to increase. The intermediate product is then converted to isosorbide with a consequent decrease in yield. Whereas the yields of intermediate 1, 4-sorbitan gradually decrease at 130℃and 140 ℃.
As can be seen from FIG. 3, the yield of isosorbide gradually increased with time at a temperature of 120℃with a maximum yield of 39%. The highest yield of isosorbide was 78% at 130 ℃. At 140 ℃, the yield of the isosorbide is increased and then reduced with time, because the side reaction is severe in a high-temperature and strong-acid catalytic system, and the generated isosorbide further undergoes dehydration reaction and polymerization reaction. The highest yield of isosorbide was 94% at 140 ℃.
Example 4:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate by polymeric ionic liquid comprises the following specific steps:
(1) 3.0336 g of 1-vinyl-microphone are takenDissolving oxazole, 0.0808 g initiator AIBN and 4.3600 g 2-bromoethylamine hydrobromide in 40 mL absolute ethanol, stirring at 80 ℃ and condensing and refluxing 4 h under the protection of nitrogen, turning the solution into orange yellow and forming yellow solid at the bottom, drying the reaction liquid to obtain orange yellow solid, namely aminated polyvinylimidazole [ VIM ]]NH 2 ；
(2) Weighing 1.4 g of the amination polyvinyl imidazole [ VIM ] obtained in the step (1)]NH 2 In a three-necked flask, 100 mL KNbO was further added 3 The solution is completely dissolved, and is stirred and reacted at 40 ℃ for 4 h to obtain the metal modified polymeric ionic liquid Nb/[ VIM ]]NH 2 ；
(3) Adding 2 mol/L sulfuric acid solution (volume ratio is 2:1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying at 40 ℃ for 4H, and evaporating redundant water to obtain an acidic polymeric ionic liquid catalyst 2H-Nb/[ VIM ]]NH 2 ；
(4) 5g of solid sorbitol are weighed into a reactor, heated to the liquid state at 140℃and added with 0.5 g of 2H-Nb/[ VIM ]]NH 2 The catalyst is stirred for reaction 2h under the condition of the pressure of-0.09 MPa, the materials in the reaction system are continuously subjected to gas chromatography test in a certain time in the reaction process, and the highest yield of the isosorbide is 74% according to the gas chromatography detection result.
Example 5:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate by polymeric ionic liquid comprises the following specific steps:
(1) Dissolving 3.0336 g of 1-vinylimidazole, 0.0808 g initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide in 40 mL absolute ethyl alcohol, stirring at 80 ℃ and condensing and refluxing 4 h under the protection of nitrogen, changing the solution into orange yellow with yellow solid at the bottom, and drying the reaction solution to obtain orange yellow solid, namely the aminated polyvinylimidazole [ VIM ]]NH 2 ；
(2) Weighing 1.4 g of the amination polyvinyl imidazole [ VIM ] obtained in the step (1)]NH 2 In a three-necked flask, 100 mL KNbO was further added 3 The solution is completely dissolved, and is stirred and reacted at 40 ℃ for 4 h to obtain the metal modified polymeric ionic liquid Nb/[ VIM ]]NH 2 ；
(3) Adding 1 mol/L sulfuric acid solution (volume ratio is 2:1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying 4H at 40 ℃, and steaming off redundant water to obtain an acidic polymeric ionic liquid catalyst 1H-Nb/[ VIM ]]NH 2 ；
(4) 5g of solid sorbitol are weighed into a reactor, heated to the liquid state at 140℃and added with 0.5 g of 1H-Nb/[ VIM ]]NH 2 The catalyst is stirred for reaction 2h under the condition of the pressure of-0.09 MPa, materials in a reaction system are continuously subjected to a certain time in the reaction process, and the highest yield of the isosorbide is 61% according to the detection result of gas chromatography.
Example 6:
a method for preparing isosorbide by catalyzing sorbitol to dehydrate by polymeric ionic liquid comprises the following specific steps:
(1) Dissolving 3.0336 g of 1-vinylimidazole, 0.0808 g initiator AIBN and 4.3600 g of 2-bromoethylamine hydrobromide in 40 mL absolute ethyl alcohol, stirring at 80 ℃ and condensing and refluxing 4 h under the protection of nitrogen, changing the solution into orange yellow with yellow solid at the bottom, and drying the reaction solution to obtain orange yellow solid, namely the aminated polyvinylimidazole [ VIM ]]NH 2 ；
(2) Weighing 1.4 g of the amination polyvinyl imidazole [ VIM ] obtained in the step (1)]NH 2 In a three-necked flask, 100 mL KNbO was further added 3 The solution is completely dissolved, and is stirred and reacted at 40 ℃ for 4 h to obtain the metal modified polymeric ionic liquid Nb/[ VIM ]]NH 2 ；
(3) Adding 3 mol/L phosphoric acid solution (volume ratio is 2:1) into the metal modified polymeric ionic liquid obtained in the step (2), stirring and acidifying 4H at 40 ℃, and steaming off redundant water to obtain an acidic polymeric ionic liquid catalyst 3H-Nb/[ VIM ]]NH 2 ；
(4) 5g of solid sorbitol is weighed into a reactor, heated to a liquid state at 120 ℃, and added with 0.5 g of 3H-Nb/[ VIM ]]NH 2 The catalyst is stirred for reaction 2h under the condition of the pressure of-0.09 MPa, the materials in the reaction system are continuously subjected to certain time in the reaction process, and according to the detection result of gas chromatography, the catalyst shows that the catalyst is in the Isshan stateThe highest yield of the sorbitol is 58%.
The embodiments described above are specific embodiments of the present invention, but the embodiments of the present invention are not limited to the embodiments described above, and any other combinations, changes, modifications, substitutions, and simplifications that do not exceed the design concept of the present invention fall within the scope of the present invention.
Claims (7)
1. A method for preparing isosorbide by catalyzing sorbitol to dehydrate by using polymeric ionic liquid is characterized in that after solid sorbitol is heated to be molten, polymeric ionic liquid is added into the molten sorbitol as a catalyst, and dehydration reaction is carried out under-0.09 MPa to prepare isosorbide; the temperature of the dehydration reaction is 130-140 ℃;
the polymeric ionic liquid is prepared by the following method:
(1) Dissolving a C=C double bond substituted imidazole monomer, 2-bromoethylamine hydrobromic acid and an initiator in a solvent, and reacting to obtain an amination polymerization ionic liquid;
the C=C double bond substituted imidazole monomer is 1-vinyl imidazole;
(2) Adding a metal salt solution into the polymerized ionic liquid obtained in the step (1), and stirring and reacting at 20-80 ℃ for 1-4 h to obtain a metal modified polymerized ionic liquid;
the metal salt solution is KNbO 3 A solution;
(3) Adding an acid solution into the metal modified polymeric ionic liquid obtained in the step (2) for acidification, and removing the solvent to obtain a target polymeric ionic liquid;
the acid solution is sulfuric acid solution, and the concentration of the sulfuric acid solution is 2-3 mol/L.
2. The method according to claim 1, wherein the polymeric ionic liquid is added in an amount of 0.1% wt% to 20% wt% by mass of solid sorbitol.
3. The method of claim 1, wherein the dehydration reaction is for a period of time ranging from 1.25 to 2 h.
4. A process according to claim 3, wherein in step (1) the molar ratio of c=c double bond substituted imidazole monomer, 2-bromoethylamine hydrobromic acid is from 1 to 10:1.
5. the process according to claim 4, wherein in step (1), the reaction time is 1 to 10. 10 h and the reaction temperature is 60 to 100 ℃.
6. The method of claim 5, wherein the initiator is azobisisobutyronitrile AIBN.
7. The method according to any one of claims 1 to 6, wherein the specific operation of acidification in step (3) is: adding sulfuric acid solution with the concentration of 2-3 mol/L into the metal modified polymeric ionic liquid obtained in the step (2), and stirring and acidifying at 20-80 ℃ for 4-8 h.
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