CN111001440A - Polyacid site ionic liquid catalyst and preparation method and application thereof - Google Patents
Polyacid site ionic liquid catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a polyacid site ionic liquid, a preparation method and application thereof, and belongs to the technical field of catalyst material preparation. Dissolving low-substituted fatty amine in a solvent to form a uniform solution, then reacting with sultone to obtain a precursor salt, and reacting the precursor salt with organic acid or inorganic acid in a proper solvent to obtain the polyacid site ionic liquid. The catalyst has the advantages of high activity, low usage amount, simple preparation method process, cheap and easily-obtained raw materials, mild reaction conditions and large-scale production conditions. The polyacid site ionic liquid catalyst prepared by the method has good effect when being used for producing biodiesel.
Description
Technical Field
The invention relates to a polyacid site ionic liquid, a preparation method and application thereof, and belongs to the technical field of catalyst material preparation.
Background
Due to environmental problems and the continuous oil price increase caused by the large consumption of limited fossil fuels, people are beginning to pay high attention to renewable non-petrochemical resources, biofuels and value-added chemicals derived from biomass, and biodiesel is a renewable, non-toxic, easily available and environmentally friendly new energy source, so that biodiesel is currently a worldwide research hotspot as a diesel substitute.
In general, biodiesel is produced by transesterification of animal fats, vegetable oils and waste fats through triglycerides or esterification of free fatty acids with short-chain alcohols. Industrially, the reaction is usually carried out by using a strong base catalyst (e.g., KOH, NaOH) or a strong acid catalyst (H)2SO4HCl), strong base catalysts are prone to saponification and hydrolysis reactions, resulting in reduced yields and washing difficulties. Therefore, the acidic catalyst is more suitable for biodiesel production, and an esterification pretreatment unit is not needed, so that the production cost is naturally reduced. But the classical homogeneous inorganic acid catalyst has serious corrosion to equipment and greater pollution; the solid acid catalyst has the problems of poor catalytic effect and easy inactivation. In order to overcome these problems, it is known to provide,the ionic liquid is used as a catalyst for preparing the biodiesel. The ionic liquid has the advantages of controllable molecular structure, wide liquid range, excellent physicochemical property, recoverability and the like. The acidic ionic liquid overcomes the problem that the basic ionic liquid is easy to inactivate when meeting water, and is widely applied to various aspects such as catalysis, synthesis, separation, gas absorption and the like.
The acidic ionic liquid is generally synthesized by taking alkyl substituted imidazole, pyridine, fatty tertiary amine, tertiary phosphine and the like as precursors, adopting sultone to carry out functionalization to form inner salt, and then carrying out acidification by means of organic acid or inorganic acid. Theoretically, only 1 equivalent of sultone can be reacted with such a precursor per equivalent for functionalization, and after acidification only 1 acid site (2 for sulfuric acid) can be provided. This results in a catalyst with a low acid site, and thus the catalytic effect is not good. To ensure the catalytic effect, a large amount of ionic liquid must be added, which further increases the operating costs.
Chinese patent CN103936677A discloses a sulfonic acid functionalized ionic liquid based on perfluoroalkyl sulfonate anions and a preparation method thereof, wherein the method adopts a substance generated by the reaction of a nitrogen-containing heterocyclic compound and chloroethanol as a precursor; then the precursor is substituted with perfluoroalkylsulfonate to remove Cl-Replacement by CF3(CF2)nSO3 -Obtaining an intermediate; sultone and-OH on the intermediate cation are subjected to ring-opening reaction to introduce sulfonic acid groups, and finally the target ionic liquid containing only one acid site is obtained, and the preparation process is complicated.
Chinese patent CN107790178A discloses a preparation method of a tris (2, 4, 6-trimethoxyphenyl) phosphine-based ionic liquid catalyst and application thereof in catalytic esterification and ester exchange, wherein tris (2, 4, 6-trimethoxyphenyl) phosphine reacts with 1, 3-propane sultone to obtain a ylide, and the ylide reacts with an organic or inorganic acid to obtain an ionic liquid. However, the ionic liquid adopts tertiary phosphine as a matrix, the ionic liquid finally obtained only has 1 acid site when sulfuric acid is not used for acidification, and meanwhile, the raw material tris (2, 4, 6-trimethoxyphenyl) phosphine is expensive, so that the large-scale production of the ionic liquid is limited.
The method has no doubt that the improvement of the grafting amount of the sulfonic acid group so as to improve the acid catalytic site is important for improving the catalytic activity of the acidic ionic liquid and further reducing the dosage of the catalyst for the application of the ionic liquid in the field of catalysis. Therefore, the invention aims to find a method with cheap raw materials and mild preparation conditions to prepare the ionic liquid with the polyacid sites as a catalyst for preparing the biodiesel, and lays a foundation for realizing the large-scale application of the ionic liquid in the biodiesel production.
Disclosure of Invention
The invention aims to provide a polyacid site ionic liquid catalyst, a preparation method and application thereof, technically provides a catalyst with better catalytic effect, so that the dosage of the catalyst is reduced, and a more efficient and green catalyst is provided for the industrial preparation of biodiesel.
In view of the above object, the following invention is proposed:
a preparation method of a polyacid site ionic liquid catalyst comprises the following steps:
(1) dissolving low-substituted aliphatic amine in a proper amount of solvent, and reacting the low-substituted aliphatic amine with sultone at 25-100 ℃;
(2) after the reaction is finished, preparing precursor salt through suction filtration, washing and drying;
(3) dissolving the precursor salt in 20-60mL of methanol, ethanol or deionized water, and adding a certain amount of organic acid or inorganic acid to react at 20-90 ℃;
(4) and (3) after the reaction is finished, removing the solvent by rotary evaporation, washing and drying to obtain the polyacid site ionic liquid.
Wherein the low-substituted aliphatic amine is any one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
Wherein the solvent in the step (1) is any one of methanol, ethanol, isopropanol, dimethyl sulfoxide, acetone, acetonitrile, N-methylpyrrolidone and N, N-dimethylformamide.
Wherein the mass ratio of the low-substituted aliphatic amine in the step (1) to the solvent is 1:5-1: 30.
Wherein the sultone is 1, 3-propane sultone or 1, 4-butane sultone.
Wherein the molar ratio of the low-substituted aliphatic amine to the sultone is 1:1-1: 10.
Wherein the organic acid is one of methane sulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid, and the inorganic acid is concentrated sulfuric acid or phosphotungstic acid.
Wherein the molar ratio of the organic acid or the inorganic acid to the precursor salt is 1:1-5: 1.
The polyacid site ionic liquid catalyst obtained by the preparation method is applied to the catalytic preparation of biodiesel.
Compared with the prior art, the invention has the advantages that:
(1) the method for preparing the ionic liquid disclosed by Chinese patents CN103936677A and CN107790178A is adopted to prepare the ionic liquid, the finally obtained ionic liquid only has 1 reaction site (sulfuric acid is not adopted as an external acid), the method directly uses low-substituted aliphatic amine as a parent body, the parent body is provided with a large number of sites capable of reacting with sultone, and the final ionic liquid product can be grafted with nearly 3 acid sites.
(2) The invention adopts low-substituted fatty amine with low price as a matrix, can effectively reduce the production cost, and has simple preparation method and process.
(3) The low-substituted aliphatic amine can provide a plurality of sites for reacting with sultone, so that a plurality of sulfonic acid groups can be grafted on one amino group, the number of the sulfonic acid groups of the product can be further increased by adding the additional acid, the acidity of the product is enhanced, the catalytic activity can be effectively improved, and the catalytic effect of the catalyst is remarkably improved. As shown in Table 1, the acid value of the ionic liquid obtained after the sulfuric acid treatment is greatly improved compared with that of the precursor salt. Therefore, the technical scheme of the invention has good industrialization prospect.
TABLE 1 comparison of acid values of precursor salts and Ionic liquids obtained after sulfuric acid treatment
Detailed Description
The invention is further illustrated by the following examples.
Example 1
Dissolving 2g of ethylenediamine in ethanol to obtain a 5wt% ethylenediamine ethanol solution, dropwise adding the ethylenediamine ethanol solution into 1, 3-Propane Sultone (PS) at a dropwise adding speed of 0.2mL/min, controlling the molar ratio of ethylenediamine to 1, 3-propane sultone to be 1:1, reacting for 6 hours at 25 ℃ under mechanical stirring, performing suction filtration to obtain light yellow solid powder after the reaction is finished, washing for 2-3 times with ethanol, and drying to obtain precursor salt. Dissolving the precursor salt in 20mL of deionized water, and mixing the precursor salt with concentrated sulfuric acid: adding concentrated sulfuric acid into the precursor salt in a molar ratio of 1:1, reacting for 4 hours at 50 ℃ under magnetic stirring, removing the solvent deionized water by rotary evaporation after the reaction is finished to obtain light yellow viscous liquid, washing for 2-3 times by using ethyl acetate, and drying to obtain the target ionic liquid. The acid value was 1.94 mmol/g.
Application example 1
Adding methanol and oleic acid into a 25 mL flask according to the molar ratio of 10:1, adding the obtained acidic ionic liquid catalyst according to the mass ratio of 2.5% of the oleic acid, reacting for 1.5 h at 70 ℃ to obtain a biodiesel crude product, removing the methanol by rotary evaporation to obtain biodiesel containing a small amount of glycerol, and obtaining the conversion rate of the oleic acid by adopting a KOH solution titration method to be 82.33%.
Example 2
Dissolving 2g of ethylenediamine in methanol to obtain a 10wt% ethylenediamine methanol solution, dropwise adding the ethylenediamine methanol solution into 1, 3-Propane Sultone (PS) at a dropwise adding speed of 0.2mL/min, controlling the molar ratio of ethylenediamine to 1, 4-butane sultone to be 3:1, reacting for 3 hours at 40 ℃ under mechanical stirring, performing suction filtration to obtain light yellow solid powder after the reaction is finished, washing for 2-3 times by using methanol, and drying to obtain a precursor salt. Dissolving the precursor salt in 30mL of deionized water, and mixing the precursor salt with concentrated sulfuric acid: adding concentrated sulfuric acid into the precursor salt in a molar ratio of 2:1, reacting for 6 hours under magnetic stirring at 20 ℃, performing rotary evaporation and concentration after the reaction is finished to obtain light yellow viscous liquid, washing for 2-3 times by using methanol, and drying to obtain the target ionic liquid. The acid value was 4.27 mmol/g.
Application example 2
The prepared catalyst is used for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the final yield of the biodiesel is 94.21%.
Example 3
Dissolving 2g of ethylenediamine in acetonitrile to obtain a 20wt% ethylenediamine acetonitrile solution, dropwise adding the ethylenediamine acetonitrile solution into 1, 3-Propane Sultone (PS) at a dropping speed of 0.2mL/min, controlling the molar ratio of ethylenediamine to 1, 3-propane sultone to be 6:1, reacting for 2 hours at 60 ℃ under mechanical stirring, performing suction filtration to obtain light yellow solid powder after the reaction is finished, washing for 2-3 times by using acetonitrile, and drying to obtain a precursor salt. The precursor salt was dissolved in 40mL of deionized water, according to concentrated sulfuric acid: adding concentrated sulfuric acid into precursor salt in a molar ratio of 3:1, reacting for 2 hours under magnetic stirring at 60 ℃, performing rotary evaporation concentration after the reaction is finished to obtain light yellow viscous liquid, washing for 2-3 times by using methanol, and drying to obtain the target ionic liquid. The acid value was 6.38 mmol/g.
Application example 3
The prepared catalyst is used for preparing biodiesel from oleic acid and methanol under the same application conditions as in example 1, and the final yield of the biodiesel is 97.32%.
Example 4
Dissolving 2g of diethylenetriamine in dimethyl sulfoxide to obtain 30wt% of diethylenetriamine dimethyl sulfoxide solution, dropwise adding the diethylenetriamine dimethyl sulfoxide solution into 1, 3-Propane Sultone (PS), controlling the dropwise adding speed to be 0.2mL/min, controlling the molar ratio of diethylenetriamine to 1, 3-propane sultone to be 10:1, reacting for 1 h under mechanical stirring at 100 ℃, performing suction filtration to obtain light yellow solid powder after the reaction is finished, washing for 2-3 times by using methanol, and drying to obtain precursor salt. The precursor salt was dissolved in 50mL of deionized water, according to concentrated sulfuric acid: adding concentrated sulfuric acid into precursor salt in a molar ratio of 3:1, reacting for 1 h under magnetic stirring at 90 ℃, performing rotary evaporation and concentration after the reaction is finished to obtain light yellow viscous liquid, washing for 2-3 times by using methanol, and drying to obtain the target ionic liquid. The acid value was 6.42 mmol/g.
Application example 4
The prepared catalyst is used for preparing biodiesel from oleic acid and methanol under the same application conditions as in example 1, and the final yield of the biodiesel is 97.39%.
Example 5
Dissolving 2g of triethylene tetramine in ethanol to obtain 10wt% of triethylene tetramine ethanol solution, dropwise adding the 10wt% of triethylene tetramine ethanol solution into 1, 3-Propane Sultone (PS), controlling the dropwise adding speed to be 0.2mL/min, controlling the molar ratio of triethylene tetramine to 1, 3-propane sultone to be 10:1, reacting for 2 hours at 50 ℃ under mechanical stirring, performing suction filtration to obtain yellow solid powder after the reaction is finished, washing for 2-3 times by using ethanol, and drying to obtain precursor salt. Precursor salt was dissolved in 60mL deionized water as methane sulfonic acid: adding methanesulfonic acid into the precursor salt in a molar ratio of 4:1, reacting for 2 hours at 60 ℃ under magnetic stirring, performing rotary evaporation and concentration after the reaction is finished to obtain yellow viscous liquid, washing for 2-3 times by using ethyl acetate, and drying to obtain the target ionic liquid. The acid value was 3.43 mmol/g.
Application example 5
The prepared catalyst is used for preparing biodiesel from oleic acid and methanol, the application conditions are the same as those in example 1, and the final yield of the biodiesel is 97.41%.
Example 6
Dissolving 2g of tetraethylenepentamine in ethanol to obtain a 10wt% ethanol solution of the tetraethylenepentamine, dropwise adding the ethanol solution into 1, 3-Propane Sultone (PS) at a dropping speed of 0.2mL/min, controlling the molar ratio of the triethylene pentamine to the 1, 3-propane sultone to be 6:1, reacting for 2 hours at 50 ℃ under mechanical stirring, filtering to obtain yellow solid powder after the reaction is finished, washing for 2-3 times by using ethanol, and drying to obtain precursor salt. Precursor salt was dissolved in 30mL of deionized water, as trifluoromethanesulfonic acid: adding trifluoromethanesulfonic acid into the precursor salt at a molar ratio of 5:1, reacting for 2 h under magnetic stirring at 60 ℃, performing rotary evaporation and concentration after the reaction is finished to obtain yellow viscous liquid, washing for 2-3 times by using ethyl acetate, and drying to obtain the target ionic liquid. The acid value was 3.39 mmol/g.
Application example 6
Adding methanol and frying waste oil into a high-pressure reaction kettle according to a molar ratio of 12:1, adding the obtained acidic ionic liquid catalyst according to a proportion that the frying waste oil accounts for 3% by mass, reacting for 3 hours at 100 ℃ to obtain a biodiesel crude product, extracting with n-heptane, and performing rotary evaporation to obtain refined biodiesel, wherein the yield of the biodiesel obtained by adopting a gas chromatography analysis method is 95.23%.
Example 7
Dissolving 2g of ethylenediamine in ethanol to obtain a 10wt% ethylenediamine ethanol solution, dropwise adding the ethylenediamine ethanol solution into 1, 3-Propane Sultone (PS) at a dropwise adding speed of 0.2mL/min, controlling the molar ratio of ethylenediamine to 1, 3-propane sultone to be 6:1, reacting for 4 hours at 25 ℃ under mechanical stirring, performing suction filtration to obtain light yellow solid powder after the reaction is finished, washing for 2-3 times with ethanol, and drying to obtain precursor salt. Precursor salt was dissolved in 30mL of deionized water, as p-toluenesulfonic acid: adding p-toluenesulfonic acid into the precursor salt in a molar ratio of 2:1, reacting for 4 hours at 40 ℃ under magnetic stirring, removing the solvent deionized water by rotary evaporation after the reaction is finished to obtain light yellow viscous liquid, washing for 2-3 times by using ethyl acetate, and drying to obtain the target ionic liquid. The acid value was 3.16 mmol/g.
Application example 7
The prepared catalyst is used for preparing biodiesel by using frying waste oil and methanol, the application conditions are the same as those in example 6, and the final yield of the biodiesel is 96.11%.
Example 8
Dissolving 2g of ethylenediamine in ethanol to obtain a 10wt% ethylenediamine ethanol solution, dropwise adding the ethylenediamine ethanol solution into 1, 3-Propane Sultone (PS) at a dropwise adding speed of 0.2mL/min, controlling the molar ratio of ethylenediamine to 1, 3-propane sultone to be 6:1, reacting for 4 hours at 25 ℃ under mechanical stirring, performing suction filtration to obtain light yellow solid powder after the reaction is finished, washing for 2-3 times with ethanol, and drying to obtain precursor salt. Precursor salt was dissolved in 30mL water, according to phosphotungstic acid: adding phosphotungstic acid into the precursor salt in a molar ratio of 1:1, reacting for 4 hours at 40 ℃ under magnetic stirring, removing the solvent deionized water by rotary evaporation after the reaction is finished, washing for 2-3 times by using ethanol, and drying to obtain light yellow solid powder with an acid value of 3.02 mmol/g.
Application example 8
The prepared catalyst is used for preparing biodiesel by using frying waste oil and methanol, the application conditions are the same as those in example 6, and the final yield of the biodiesel is 94.88%.
A series of polyacid-site ionic liquids with different anions and cations and different acid values are obtained by controlling the synthesis conditions of the catalyst, such as the proportion of reaction raw materials, reaction time, reaction temperature and reaction solvent. Similarly, the ionic liquid synthesized by the method generally has higher acid value and better effect of catalyzing esterification and ester exchange to synthesize biodiesel, and is a novel ionic liquid catalyst expected to be industrialized.
The above description is a preferred example of the present experiment and is not intended to limit the present invention in any way. Any simple modification, modification or substitution of the present invention falls within the scope of the present invention.
Claims (10)
1. A preparation method of a polyacid site ionic liquid catalyst is characterized by comprising the following steps:
(1) dissolving low-substituted aliphatic amine in a proper amount of solvent, and reacting the low-substituted aliphatic amine with sultone at 25-100 ℃;
(2) after the reaction is finished, preparing precursor salt through suction filtration, washing and drying;
(3) dissolving the precursor salt in 20-60mL of methanol, ethanol or deionized water, and adding a certain amount of organic acid or inorganic acid to react at 20-90 ℃;
(4) and (3) after the reaction is finished, removing the solvent by rotary evaporation, washing and drying to obtain the polyacid site ionic liquid.
2. The method of preparing the polyacid site ionic liquid catalyst of claim 1, wherein: the low-substituted aliphatic amine is any one of Ethylenediamine (EDA), Diethylenetriamine (DETA), triethylenetetramine (TETA) and Tetraethylenepentamine (TEPA).
3. The method of preparing the polyacid site ionic liquid catalyst of claim 1, wherein: the solvent in the step (1) is any one of methanol, ethanol, isopropanol, dimethyl sulfoxide, acetone, acetonitrile and N-methylpyrrolidone N, N-dimethylformamide.
4. The method of preparing the polyacid site ionic liquid catalyst of claim 1, wherein: the mass ratio of the low-substituted aliphatic amine in the step (1) to the solvent is 1:5-1: 30.
5. The method of preparing the polyacid site ionic liquid catalyst of claim 1, wherein: the sultone is 1, 3-propane sultone or 1, 4-butane sultone.
6. The method of preparing the polyacid site ionic liquid catalyst of claim 1, wherein: the molar ratio of the low-substituted fatty amine to the sultone is 1:1-1: 10.
7. The method of preparing the polyacid site ionic liquid catalyst of claim 1, wherein: the organic acid is one of methane sulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid, and the inorganic acid is concentrated sulfuric acid or phosphotungstic acid.
8. The method of preparing the polyacid site ionic liquid catalyst of claim 1, wherein: the molar ratio of the organic acid or the inorganic acid to the precursor salt is 1:1-5: 1.
9. A polyacid-site ionic liquid catalyst obtained by the preparation method of any one of claims 1 to 8.
10. Application of the polyacid-site ionic liquid catalyst obtained by the preparation method of any one of claims 1 to 8 in preparation of biodiesel by catalysis.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112387308A (en) * | 2020-12-23 | 2021-02-23 | 福州大学 | Self-supporting solid acidic ionic liquid catalyst and preparation method thereof |
| CN113181963A (en) * | 2021-05-14 | 2021-07-30 | 安庆精益精化工有限公司 | Preparation method of solid alkyl sulfonic acid catalyst |
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