CN116371467A - Preparation method and application of solid acid catalyst loaded with acidic ionic liquid - Google Patents
Preparation method and application of solid acid catalyst loaded with acidic ionic liquid Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000011973 solid acid Substances 0.000 title claims abstract description 54
- 239000011831 acidic ionic liquid Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 171
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 19
- 238000005886 esterification reaction Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 16
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 16
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 230000032050 esterification Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 239000002608 ionic liquid Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- BYMHXIQVEAYSJD-UHFFFAOYSA-M sodium;4-sulfophenolate Chemical compound [Na+].OC1=CC=C(S([O-])(=O)=O)C=C1 BYMHXIQVEAYSJD-UHFFFAOYSA-M 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000000376 reactant Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- 239000012467 final product Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical compound OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 description 1
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a preparation method and application of a solid acid catalyst for loading acidic ionic liquid, which comprises the steps of mixing sodium 4-hydroxy benzenesulfonate and formaldehyde, adding the ionic liquid, reacting in a flask with a reflux condenser under a reflux condition, cooling after the reaction is finished, adding water, recovering precipitate, drying, grinding and washing to obtain the solid acid catalyst for loading the ionic liquid. So that the stability and activity of the catalyst are improved, and the catalyst can be reused by simple filtration.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a solid acid catalyst loaded with acidic ionic liquid.
Background
Esterification reactions of acid alcohols strive to use a minimum amount of homogeneous acid catalyst. The search of the academy in this regard has achieved some success, but the esterification reaction still faces the challenge of using a more efficient, simple, green catalyst.
In recent years, new green catalysts replacing traditional inorganic acids in esterification reactions have been developed successively, wherein attention is paid to the application of acidic Ionic Liquids (IL) as catalysts in esterification reactions, ester products can be automatically layered with the catalyst IL as the reaction proceeds, equilibrium forward movement is promoted, acidic ionic liquids have achieved attention in catalytic esterification reactions, but catalysts exist in liquid form and can be recovered only by complicated reduced pressure distillation, and the reaction process requires the use of a large amount of expensive ionic liquids, which does not conform to the optimal economic principle.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
As one of the aspects of the invention, the invention provides a preparation method of a solid acid catalyst loaded with acidic ionic liquid, which comprises the following steps: the crosslinked polyvinylpyrrolidone powder was placed in toluene and 1,3 propane sultone was added. The mixture was stirred continuously for 24 hours at 80℃under reflux with heating. The solid zwitterion obtained was recovered by filtration, washed with ethyl acetate, and then dried under vacuum overnight to give a sample [ PVPP-PS]. To be prepared [ PVPP-PS]Grinding and dispersing in ethyl acetate in a mortar, adding sulfuric acid, stirring for 24h, filtering and washing the mixture with ethanol three times, and vacuum drying at 60deg.C to obtain final product [ PVPP-PS ]]HSO 4 As solid acid catalysts.
The preparation method of the solid acid catalyst for loading the acidic ionic liquid is characterized by comprising the following steps of: mixing the crosslinked polyvinylpyrrolidone and the 1,3 propane sultone, wherein the molar ratio of the crosslinked polyvinylpyrrolidone to the 1,3 propane sultone is 1:1.
as a preferable scheme of the preparation method of the solid acid catalyst for supporting the acidic ionic liquid, disclosed by the invention, the following steps are adopted: the sulfuric acid is added and stirred for 24 hours, wherein the mass ratio of the sulfuric acid to the sample [ PVPP-PS ] is 18:1.
as a preferable scheme of the preparation method of the solid acid catalyst for supporting the acidic ionic liquid, disclosed by the invention, the following steps are adopted: the reaction is carried out under reflux conditions for a reaction time of 24 hours.
As a preferable scheme of the preparation method of the solid acid catalyst for supporting the acidic ionic liquid, disclosed by the invention, the following steps are adopted: the washing is washing with ethyl acetate.
As a preferable scheme of the preparation method of the solid acid catalyst for supporting the acidic ionic liquid, disclosed by the invention, the following steps are adopted: the preparation method of the solid acid comprises the following steps: the crosslinked polyvinylpyrrolidone powder was placed in toluene under a nitrogen atmosphere, and after a period of time, 1,3 propane sultone was added. The mixture was heated to 80 ℃ and stirred continuously in a 100mL flask for 24 hours. The resulting solid zwitterion was recovered by filtration, washed with ethyl acetate, the unreacted reactants were completely removed, and then dried under vacuum at 60℃overnight to give a sample [ PVPP-PS ].
As a preferable scheme of the preparation method of the solid acid catalyst for supporting the acidic ionic liquid, disclosed by the invention, the following steps are adopted: the solvent is ethyl acetate.
The invention has the beneficial effects that: the invention provides a load
Acidic ionic liquid H 2 SO 4 A solid acid catalyst and a preparation method thereof. The solid acid prepared by the method can be used as a catalyst for catalyzing the reaction of acetic acid and ethanol to synthesize ethyl acetate, and has higher catalytic activity and stability. The use of solid acid catalyst alone is prone to deactivation of acid sites in the reaction, resulting in a decrease in reactivity, while +.>
Solid acid catalyst of acidic ionic liquid, solid acid coated with +.>
Acidic ionic liquid, so that the stability and activity of the catalyst are improved, and the load is +.>
The catalytic performance of the catalyst after acidic ionic liquid is obviously improved compared with that of a pure solid acid catalyst, which shows that the supported ionic liquid has a promoting effect on improving the catalytic performance. The prepared catalyst has high catalytic activity and can be reused by simple filtration.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the description of the embodiments will be briefly described below. Wherein:
FIG. 1 is a load prepared in example 1
Infrared spectrum of acidic ionic liquid solid acid catalyst.
FIG. 2 is a schematic illustration of a load prepared using the examples, respectively
And (3) as a result of the catalytic synthesis of ethyl acetate by the acidic ionic liquid, the abscissa represents time, and the ordinate represents the yield of ethyl acetate.
FIG. 3 is a solid acid and a support prepared in example 3
Comparison of catalytic stability of solid acid catalyst after acidic ionic liquid.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Example 1:
in a 100mL flask, polyvinylpyrrolidone powder (22.23 g, monomer molar amount 0.2mol, available from Allatin under the trade name P101410) was crosslinked under nitrogen atmosphere, and after a while, 1,3 propane sultone (6.8 g,0.05 mol) was added and the mixture was heated to 80℃and stirred continuously for 24 hours. The resulting solid zwitterion was recovered by filtration, washed with ethyl acetate, the unreacted reactants were removed completely, and then dried under vacuum overnight at 60 ℃ to give crosslinked polyvinylpyrrolidone:the molar ratio of the 1,3 propane sultone is 1: solid acid [ PVPP-PS of 0.25]The [ PVPP-PS ] obtained]Taking 1g, grinding uniformly in a mortar, dispersing into ethyl acetate solution, adding sulfuric acid (5.0 g,0.05 mol) into the solution, stirring for 24h, filtering and washing the mixture with methanol three times, and removing water and methanol in vacuum at 60 ℃ to obtain the final product load
Solid acid catalyst of acidic ionic liquid [ PVPP-PS]HSO 4 。
Esterification reaction (reaction kettle): the reflux distillation mode without water diversion is adopted, a heating device adopts a dimethyl silicone oil bath pot without open fire and contacting a heat source for oil bath heating, low-temperature water is condensed, acetic acid is firstly added into a three-neck flask which is filled into a magnetic stirrer and connected with a condensing tube and a thermometer, the temperature is raised to 80 ℃, a catalyst is added, when the temperature reaches 80 ℃, ethanol is added, the magnetic stirrer is started, and the reaction is started. The esterification reaction methods of examples 1 to 5 and comparative examples 1 to 5 were the same as those of this example. The average was taken by repeating the experiment three times.
Analysis of esterification products: the classical reaction of acetic acid and ethanol, the main products being ethyl acetate and water, therefore the experiment was characterized by detecting the decrease in reactant acetic acid, and detecting the increase in ethyl acetate, and data support was provided for subsequent calculations.
The gas chromatograph used in this experiment is GC-3420A produced by northlasi, the separation column used is a capillary column, the column parameter is 30m x 0.32mm x 0.50um, the detector is a hydrogen flame ionization detector, the initial column temperature is 80 degrees celsius, the injector temperature is 220 degrees celsius, the detector temperature is 250 degrees celsius, the temperature raising program is to remain at 80 degrees celsius for 2 minutes, then to rise to 200 degrees celsius at a rate of 30 degrees celsius per minute, and remain for 5 minutes after rising to 200 degrees celsius. In preparation for the experiment, a ratio of 15:3:1, mixing ethyl acetate, ethanol and acetic acid, taking the mixed liquid, performing gas chromatographic analysis, and calibrating the peak time of each component. At the beginning of the reaction, the reaction was adjusted to 250. Mu.L with a pipette, the sample was quickly removed, placed in a chromatographic chamber and quickly transferred to the chamber, and the content ratio was measured by gas chromatography. In the reaction process, samples are taken every 20min and quickly transferred to a chromatographic chamber, and the content ratio of each component is tested by gas chromatography analysis. During gas chromatography analysis, the needle tube is repeatedly rinsed for more than 8 times, and 0.6 mu L of liquid to be detected is sucked during sampling. The three-necked flask is sampled, chromatographic analysis is performed, and the total time is controlled to be not more than 1min so as to control the test accuracy. The method for analyzing the esterified product and the method for detecting the esterified product in the following examples are the same as those in this example except for the description.
The ethyl acetate yield of this example was 64.2% ± 0.74%.
Example 2:
in a 100mL flask, a polyvinylpyrrolidone powder (11.11 g, monomer molar amount 0.1 mol) was placed in toluene under nitrogen atmosphere, and after a while, 1,3 propane sultone (6.8 g,0.05 mol) was added, and the mixture was heated to 80℃and stirred continuously for 24 hours. The resulting solid zwitterion was recovered by filtration, washed with ethyl acetate, the unreacted reactants were completely removed, and then dried under vacuum at 60 ℃ overnight to give a molar ratio of 1:0.5 solid acid [ PVPP-PS]. To be prepared [ PVPP-PS]Taking 1g, grinding uniformly in a mortar, dispersing the sample into ethyl acetate solution, adding sulfuric acid (5.0 g,0.05 mol) into the solution, stirring for 24h, filtering and washing the mixture with methanol three times, and removing water and methanol in vacuum at 60 ℃ to obtain the final product load
Solid acid catalyst of acidic ionic liquid [ PVPP-PS]HSO 4 。
The ethyl acetate yield of this example was 68.5% + -1.3%.
Example 3:
crosslinked polyvinylpyrrolidone powder (5.55 g, monomer molar amount 0.05mol, available from Allatin under the trade name P101410) was placed in toluene in a 100mL flask under nitrogen, after a while 1,3 propane sultone (6.8 g,0.05 mol) was added and the mixture was heated to 80℃with continuous stirring24 hours. The resulting solid zwitterion was recovered by filtration, washed with ethyl acetate, the unreacted reactants were removed completely, and then dried under vacuum overnight at 60 ℃ to give crosslinked polyvinylpyrrolidone: the molar ratio of the 1,3 propane sultone is 1:1 [ PVPP-PS ]]. To be prepared [ PVPP-PS]Taking 1g, grinding uniformly in a mortar, dispersing the sample into ethyl acetate solution, adding sulfuric acid (5.0 g,0.05 mol) into the solution, stirring for 24h, filtering and washing the mixture with methanol three times, and removing water and methanol in vacuum at 60 ℃ to obtain the final product load
Solid acid catalyst of acidic ionic liquid [ PVPP-PS]HSO 4 。
The ethyl acetate yield of this example was 82.3% + -0.22%.
Esterification reaction (reaction kettle): the reflux distillation mode without water diversion is adopted, a heating device adopts a dimethyl silicone oil bath pot without open fire and contacting a heat source for oil bath heating, low-temperature water is condensed, acetic acid is firstly added into a three-neck flask which is filled into a magnetic stirrer and connected with a condensing tube and a thermometer, the temperature is raised to 80 ℃, a catalyst is added, when the temperature reaches 80 ℃, ethanol is added, the magnetic stirrer is started, and the reaction is started. The esterification reaction methods of examples 1 to 5 and comparative examples 1 to 5 were the same as those of this example. The average was taken by repeating the experiment three times.
Analysis of esterification products: the classical reaction of acetic acid and ethanol, the main products being ethyl acetate and water, therefore the experiment was characterized by detecting the decrease in reactant acetic acid, and detecting the increase in ethyl acetate, and data support was provided for subsequent calculations.
The gas chromatograph used in this experiment is GC-3420A produced by northlasi, the separation column used is a capillary column, the column parameter is 30m x 0.32mm x 0.50um, the detector is a hydrogen flame ionization detector, the initial column temperature is 80 degrees celsius, the injector temperature is 220 degrees celsius, the detector temperature is 250 degrees celsius, the temperature raising program is to remain at 80 degrees celsius for 2 minutes, then to rise to 200 degrees celsius at a rate of 30 degrees celsius per minute, and remain for 5 minutes after rising to 200 degrees celsius. In preparation for the experiment, a ratio of 15:3:1, mixing ethyl acetate, ethanol and acetic acid, taking the mixed liquid, performing gas chromatographic analysis, and calibrating the peak time of each component. At the beginning of the reaction, the reaction was adjusted to 250. Mu.L with a pipette, the sample was quickly removed, placed in a chromatographic chamber and quickly transferred to the chamber, and the content ratio was measured by gas chromatography. In the reaction process, samples are taken every 20min and quickly transferred to a chromatographic chamber, and the content ratio of each component is tested by gas chromatography analysis. During gas chromatography analysis, the needle tube is repeatedly rinsed for more than 8 times, and 0.6 mu L of liquid to be detected is sucked during sampling. The three-necked flask is sampled, chromatographic analysis is performed, and the total time is controlled to be not more than 1min so as to control the test accuracy.
Example 4:
in a 100mL flask, a powder of crosslinked polyvinylpyrrolidone (4.55 g, monomer mole 0.041 mol) was placed in toluene and after a period of time, 1,3 propane sultone (6.8 g,0.05 mol) was added and the mixture heated to 80℃with continuous stirring for 24 hours. The resulting solid zwitterion was recovered by filtration, washed with ethyl acetate, the unreacted reactants were completely removed, and then dried under vacuum at 60 ℃ overnight to give a molar ratio of 1:1.2 solid acids [ PVPP-PS]. To be prepared [ PVPP-PS]Taking 1g, grinding uniformly in a mortar, dispersing the sample into ethyl acetate solution, adding sulfuric acid (5.0 g,0.05 mol) into the solution, stirring for 24h, filtering and washing the mixture with methanol three times, and removing water and methanol in vacuum at 60 ℃ to obtain the final product load
Solid acid catalyst of acidic ionic liquid [ PVPP-PS]HSO 4 。
The ethyl acetate yield of this example was 80.5% + -0.61%.
Example 5:
in a 100mL flask, crosslinked polyvinylpyrrolidone powder (3.7 g, monomer molar amount 0.033 mol) was placed in toluene under nitrogen atmosphere, after a while, added1,3 propane sultone (6.8 g,0.05 mol) was added and the mixture was heated to 80℃with continuous stirring for 24 hours. The resulting solid zwitterion was recovered by filtration, washed with ethyl acetate, the unreacted reactants were completely removed, and then dried under vacuum at 60 ℃ overnight to give a molar ratio of 1:1.5 solid acids [ PVPP-PS]. To be prepared [ PVPP-PS]Taking 1g, grinding uniformly in a mortar, dispersing the sample into ethyl acetate solution, adding sulfuric acid (5.0 g,0.05 mol) into the solution, stirring for 24h, filtering and washing the mixture with methanol three times, and removing water and methanol in vacuum at 60 ℃ to obtain the final product load
Solid acid catalyst of acidic ionic liquid [ PVPP-PS]HSO 4 。
The ethyl acetate yield of this example was 72.4% + -1.02%.
Example 6:
crosslinked polyvinylpyrrolidone prepared in example 3: the molar ratio of the 1,3 propane sultone is 1:1 [ PVPP-PS ]]Taking 1g, grinding uniformly in a mortar, dispersing into ethyl acetate solution, adding sulfuric acid (5.0 g,0.05 mol) into the solution, stirring for 24h, filtering and washing the mixture with methanol three times, and removing water and methanol in vacuum at 60 ℃ to obtain the final product load
Solid acid catalyst of acidic ionic liquid [ PVPP-PS]HSO 4 。
Esterification reaction (rectifying tower): filling the prepared solid acid catalyst loaded with the ionic liquid into a packing rectifying tower, filling the whole packing column, and obtaining the catalyst with the reflux ratio of 12:4, the feed mole ratio of ethanol to acetic acid was 1.2:1, under the condition that the reaction temperature is 85 ℃, the reaction is carried out for 2 hours, and the catalytic effect of the solid acid catalyst is investigated. Ethyl acetate yield was calculated as in example 1.
The ethyl acetate yield of this example was 95.6% + -0.37%.
Example 7:
in a 100mL flask, crosslinked polyvinylpyrrolidone powder (5.55 g, monomer molar amount 0.05mol, available from Allatin under the trade name P101410) was placed in toluene under nitrogen atmosphere, after which time 1,3 propane sultone (6.8 g,0.05 mol) was added and the mixture was heated to 80℃and stirred continuously for 24 hours. The resulting solid zwitterion was recovered by filtration, washed with ethyl acetate, the unreacted reactants were removed completely, and then dried under vacuum overnight at 60 ℃ to give crosslinked polyvinylpyrrolidone: the molar ratio of the 1,3 propane sultone is 1:1 [ PVPP-PS ].
Ethyl acetate was prepared by the esterification reaction method as in example 1, and the ethyl acetate yield was calculated.
The ethyl acetate yield of this example was 66.3% + -0.91%.
Comparative example 1:
in a 100mL flask, 2-methylpyridine (4.65 g, monomer molar amount 0.05 mol) was placed in toluene under nitrogen atmosphere, after a while, 1,3 propane sultone (6.8 g,0.05 mol) was added, and the mixture was heated to 80℃and stirred continuously for 24 hours. The solid zwitterion obtained was recovered by filtration, washed with ethyl acetate, the unreacted reactants were completely removed, and then dried under vacuum at 60 ℃ overnight to give the solid acid [ CHNO-PS ] catalyst.
Ethyl acetate was prepared by the esterification reaction method as in example 1, and the ethyl acetate yield was calculated.
The ethyl acetate yield of this example was 55.1% + -0.46%.
Comparative example 2:
in a 100mL flask, imidazole (3.4 g, monomer mole 0.05 mol) was placed in toluene under nitrogen and after some time 1,3 propane sultone (6.8 g,0.05 mol) was added and the mixture heated to 80℃with continuous stirring for 24 hours. The solid zwitterion obtained was recovered by filtration, washed with ethyl acetate, the unreacted reactants were completely removed, and then dried under vacuum overnight at 60 ℃ to give the solid acid [ Bmim-PS ] catalyst.
Ethyl acetate was prepared by the esterification reaction method as in example 1, and the ethyl acetate yield was calculated.
The ethyl acetate yield of this example was 60.2% + -0.83%.
Comparative example 3:
in a 100mL flask, metanilic acid (8.66 g, monomer mole amount 0.05 mol) was put in toluene under nitrogen atmosphere, and after a while, 1,3 propane sultone (6.8 g,0.05 mol) was added, and the mixture was heated to 80℃and stirred continuously for 24 hours. The solid zwitterion obtained was recovered by filtration, washed with ethyl acetate, the unreacted reactants were completely removed, and then dried under vacuum overnight at 60 ℃ to obtain the solid acid [3-AMSA-PS ] catalyst.
Ethyl acetate was prepared by the esterification reaction method as in example 1, and the ethyl acetate yield was calculated.
The ethyl acetate yield of this example was 50.5% + -0.36%.
Comparative example 4:
1 obtained in example 3:1 [ PVPP-PS]After grinding in a mortar to homogeneity, 1g of the mixture was dispersed in an ethyl acetate solution, phosphoric acid (4.9 g,0.05 mol) was added to the solution, stirred for 24 hours, and after completion, the mixture was filtered and washed three times with methanol, and then water and methanol were removed in vacuo at 60℃to give the final product load
Solid acid catalyst of acidic ionic liquid [ PVPP-PS]H 2 PO 4 。
The ethyl acetate yield of this example was 74.5% + -0.51%.
Comparative example 5:
1 obtained in example 3:1 [ PVPP-PS]After grinding in a mortar uniformly, 1g of the mixture was dispersed in an ethyl acetate solution, then fluoroboric acid (4.39 g,0.05 mol) was added to the solution, stirred for 24 hours, and after completion, the mixture was filtered and washed three times with methanol, and then water and methanol were removed in vacuo at 60℃to give the final product load
Acidic separationSolid acid catalyst of sub-liquid [ PVPP-PS]BF 4 。
Ethyl acetate was prepared by the esterification reaction method as in example 1, and the ethyl acetate yield was calculated.
The ethyl acetate yield of this example was 65.4% + -0.24%.
The invention provides a load
A solid acid catalyst of acidic ionic liquid and a preparation method thereof. Load prepared according to the invention->
The solid acid catalyst of the acidic ionic liquid is used as a catalyst, can catalyze acetic acid and ethanol to react to synthesize ethyl acetate, and has higher catalytic activity and stability. The ionic liquid-supported solid acid catalyst is easy to decompose in the reaction, so that the reactivity is reduced, and the ionic liquid is coated by the solid acid, so that the stability and the activity of the catalyst are improved, and the catalytic performance of the catalyst after the ionic liquid is supported is obviously improved compared with that of a pure solid acid catalyst (the experimental result has a statistical difference). The prepared solid acid has high catalytic activity and can be reused by simple filtration.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (9)
1. A preparation method of a solid acid catalyst loaded with acidic ionic liquid is characterized by comprising the following steps: putting crosslinked polyvinylpyrrolidone powder into toluene, adding 1,3 propane sultone to obtain a mixture, stirring the mixture under heating and refluxing to react, and mixing the mixture with water to obtain a mixtureThe obtained amphoteric solid ion is filtered, recovered, washed and dried in vacuum overnight to obtain solid [ PVPP-PS ]]Catalyst, solid [ PVPP-PS]Grinding and dispersing the catalyst in a mortar to a solvent, adding sulfuric acid, stirring for 20-30 h, filtering, washing, and vacuum drying to obtain [ PVPP-PS ]]HSO 4 A solid acid catalyst.
2. The method for preparing the solid acid catalyst supporting acidic ionic liquid according to claim 1, wherein the method comprises the following steps: the molar ratio of crosslinked polyvinylpyrrolidone to 1,3 propane sultone is 1:1.
3. the method for preparing the solid acid catalyst supporting the acidic ionic liquid according to claim 1 or 2, characterized in that: the sulfuric acid is added, wherein the mass ratio of the sulfuric acid to the solid [ PVPP-PS ] catalyst is 18:1.
4. the method for preparing the solid acid catalyst supporting the acidic ionic liquid according to claim 1 or 2, characterized in that: the reaction is carried out under stirring under the condition of heating reflux, the reaction temperature is 80 ℃, and the reaction time is 24 hours.
5. The method for preparing the solid acid catalyst supporting the acidic ionic liquid according to claim 1 or 2, characterized in that: the obtained amphoteric solid ions are filtered, recovered and washed, and are washed by ethyl acetate.
6. The method for preparing the solid acid catalyst supporting the acidic ionic liquid according to claim 1 or 2, characterized in that: the vacuum drying overnight is vacuum drying overnight at 60 ℃.
7. The method for preparing the solid acid catalyst supporting acidic ionic liquid according to claim 6, wherein the method comprises the following steps: the solvent is ethyl acetate.
8. The use of the acidic ionic liquid-supported solid acid catalyst obtained by the preparation method of claim 1 as an esterification catalyst.
9. The use according to claim 8, characterized in that: the reaction substrates of the esterification reaction are acetic acid and ethanol.
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