CN112473699A - Nano-pore solid acid based on silicon dioxide aerogel and preparation method thereof - Google Patents
Nano-pore solid acid based on silicon dioxide aerogel and preparation method thereof Download PDFInfo
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- CN112473699A CN112473699A CN202011470747.5A CN202011470747A CN112473699A CN 112473699 A CN112473699 A CN 112473699A CN 202011470747 A CN202011470747 A CN 202011470747A CN 112473699 A CN112473699 A CN 112473699A
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- solid acid
- silica aerogel
- nanoporous
- aerogel
- sulfate
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- 239000011973 solid acid Substances 0.000 title claims abstract description 89
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000004964 aerogel Substances 0.000 title abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 11
- 239000000377 silicon dioxide Substances 0.000 title abstract description 9
- 239000011148 porous material Substances 0.000 title description 9
- 239000004965 Silica aerogel Substances 0.000 claims abstract description 35
- 239000007806 chemical reaction intermediate Substances 0.000 claims abstract description 20
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
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- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 1
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Classifications
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/32—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention provides a nanoporous solid acid based on silica aerogel and a preparation method thereof, wherein in the nanoporous solid acid based on silica aerogel, the solid acid is dispersed in a nanoporous structure of the silica aerogel, and the weight ratio of the solid acid to the silica aerogel is 1: 10-100. In addition, the invention also provides application of the nanoporous solid acid based on the silicon dioxide aerogel in catalyzing the pyrolysis of the intermediate of the Maillard reaction. Researches show that the nanoporous solid acid based on the silicon dioxide aerogel has higher catalytic activity on the pyrolysis of Maillard reaction intermediates compared with the conventional solid acid, and can promote the release of aroma substances.
Description
Technical Field
The invention belongs to the field of solid acid catalysts, and particularly relates to a nano-porous solid acid based on silica aerogel and a preparation method thereof, and also relates to application of the nano-porous solid acid based on silica aerogel in catalyzing pyrolysis of a Maillard reaction intermediate.
Background
Solid acids are commonly used as cracking catalysts for carbohydrates. The acid sites in the solid acid are sensitive to C-O, C-N bonds in carbohydrates and the like, and can catalyze various reactions such as cracking, cyclization, rearrangement and the like of the carbohydrates to generate various heterocyclic compounds, alkanes or organic esters and the like. The catalytic activity is greatly influenced by the microstructure of the solid acid due to the phase difference between the solid acid sites and the carbohydrate, which results in difficulty in contacting the molecules. The high porosity and/or high specific surface area facilitates the exposure of solid acid sites, facilitates the contact with carbohydrate molecules, and improves the catalytic activity. Therefore, the solid acid is supported on a porous structure such as a molecular sieve.
Silica aerogel is a material having an extremely large porosity and an extremely high specific surface area. The solid acid is supported on silica aerogel and should achieve higher dispersibility. However, few attempts have been made due to the complexity of the aerogel preparation process and the relatively poor mechanical strength of the aerogel itself.
The Maillard reaction intermediate is the fragrant substance in cigarette. Maillard reaction intermediates are prepared by non-enzymatic browning reactions, also known as maillard reactions, that occur between sugars and amino acids. The Maillard reaction includes processes of dehydration, cyclization, rearrangement and the like. The Maillard reaction intermediate is heated, so that heterocyclic derivatives such as furfural and furan and esters with various structures can be released, and unique fragrance is released. The further reaction of the Maillard reaction intermediates, mainly associated with the destruction and reconstitution of the C-N, C-O bond, is generally accelerated by the catalytic action of the acid or base, so that the acid site of the solid acid also catalyzes the Maillard reaction.
Disclosure of Invention
The invention aims to overcome the problem that the catalytic activity is greatly influenced by the microstructure of the solid acid due to the difficulty in molecular contact caused by the phase difference between the solid acid sites and the carbohydrate, and provides a novel solid acid catalyst, wherein the nano-pore structure of the silica aerogel is adopted to disperse the solid acid, so that the dispersity of the solid acid sites can be greatly improved, and the catalytic activity of the solid acid catalyst on the Maillard reaction can be further improved.
Accordingly, in one aspect, the present invention provides a nanoporous solid acid based on silica aerogel, characterized in that the solid acid is dispersed in the nanoporous structure of silica aerogel, wherein the weight ratio of the solid acid to the silica aerogel is 1: 10-100.
In one embodiment of the present invention, the solid acid is a metal salt type solid acid.
In one embodiment of the present invention, the metal salt solid acid is selected from one or more of metal sulfate and metal phosphate.
In one embodiment of the present invention, the metal sulfate is aluminum sulfate, iron sulfate, nickel sulfate, zirconium sulfate, or any combination thereof.
In another aspect, the present invention also provides a method for preparing the nanoporous solid acid based on silica aerogel as described above, which is characterized in that the method comprises the following steps: (1) contacting a solid acid with a silica sol; (2) adjusting the pH to 9.0-11.0 with an alkaline agent to form a gel; (3) subsequently subjecting the gel to supercritical drying; (4) grinding the obtained dry substance into powder, and adding the powder into an ammonium persulfate solution for soaking; and (5) firing at 800 ℃ after filtering and drying to obtain the nanoporous solid acid based on the silica aerogel.
In one embodiment of the present invention, the alkaline agent is ammonia.
In another embodiment of the present invention, after the gel is formed, the gel is aged for 12-48h and then soaked for exchange with an ethanol solution.
In one embodiment of the present invention, the supercritical drying step is performed at high temperature and high pressure, and ethanol is used as the supercritical solvent.
In one embodiment of the invention, the elevated temperature is a temperature of 200-300 ℃.
In another aspect, the present invention also provides the use of a nanoporous solid acid based on silica aerogel as described above for catalyzing the pyrolysis of maillard reaction intermediates.
Compared with the prior art, the invention at least has the following beneficial technical effects:
(1) the nanoporous solid acids based on silica aerogel according to the invention have higher specific surface area and pore volume than conventional solid acids; (2) the preparation method is simple; and (3) the nanoporous solid acid based on silica aerogel of the invention has higher catalytic activity on the pyrolysis of Maillard reaction intermediates compared with the conventional solid acid, and can promote the release of aroma substances.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention which will be limited only by the appended claims. For a more complete understanding of the invention described herein, the following terms are used, and their definitions are set forth below. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In one aspect, the present invention provides a nanoporous solid acid based on silica aerogel, characterized in that the solid acid is dispersed in the nanoporous structure of silica aerogel, wherein the weight ratio of the solid acid to the silica aerogel is 1: 10-100.
According to the invention, the weight ratio of the solid acid to the silica aerogel may be in the range of 1: further selected within the range of 10 to 100, for example, the weight ratio of the solid acid to the silica aerogel can be 1: 15. 1: 20. 1: 30. 1: 50. 1: 70 or 1: 90, etc., but is not limited thereto.
According to the present invention, the type of the solid acid is not particularly limited, and may be a common type of solid acid. For example, the solid acid may be a solid acid such as an oxide, a sulfide, a metal salt, a heteropoly acid, or the like. In a preferred embodiment of the present invention, the solid acid may be a metal salt type solid acid. Further, in a preferred embodiment of the present invention, the metal salt-type solid acid may be selected from one or more of metal sulfate and metal phosphate. Further, the metal in the metal salt may be, for example, Fe, Al, Cu, Ni, Zr, or the like. Still further, the solid acid used in the present invention may be more specifically aluminum sulfate, iron sulfate, nickel sulfate, zirconium sulfate, or any combination thereof (super acid).
In another aspect, the present invention also provides a method for preparing the nanoporous solid acid based on silica aerogel as described above, which is characterized in that the method comprises the following steps: (1) contacting a solid acid with a silica sol; (2) adjusting the pH to 9.0-11.0 (e.g., 9.5, 10.0, or 10.5, etc.) with an alkaline agent to form a gel; (3) subsequently subjecting the gel to supercritical drying; (4) grinding the obtained dry substance into powder, and adding the powder into an ammonium persulfate solution for soaking; and (5) firing at 500-.
According to the preparation method of the present invention, the contacting in the step (1) may be performed by various means, for example, the solid acid may be mixed with the silica sol and then prepared into a solution with, for example, deionized water, or the solid acid may be dissolved in, for example, deionized water and then added thereto and mixed, and the mixing may be performed with stirring.
According to the preparation method of the present invention, the alkaline agent used in step (2) may be any alkaline agent commonly used in the art, for example, the alkaline agent may be aqueous ammonia, and more specifically, for example, may be an aqueous ammonia solution having a concentration of 6 mol/L. In addition, after step (2) is completed, i.e., after the gel is formed, the gel may be aged for 12 to 48 hours (e.g., 24 hours or 36 hours, etc.), and then soaked for exchange with an ethanol solution (which may be exchanged multiple times, e.g., 4 to 5 times) to displace water and ammonia in the system.
According to the preparation method of the present invention, the supercritical drying step in step (3) may be performed at high temperature and high pressure with ethanol as a supercritical solvent. More specifically, the high temperature may be 200-300 ℃, such as 230 ℃, 250 ℃, or 280 ℃ and the like; and the high pressure may be achieved by an autoclave.
According to the preparation method of the present invention, the soaking in the ammonium persulfate solution in the step (4) may be more specifically adding to a 1mol/L ammonium persulfate solution for 12-48h, such as 24h or 36 h.
According to the production method of the present invention, the firing process of step (5) may be performed in a tube furnace.
In another aspect, the present invention also provides the use of a nanoporous solid acid based on silica aerogel as described above for catalyzing the pyrolysis of maillard reaction intermediates.
According to the present invention, the term "maillard reaction", also known as non-enzymatic browning reaction, is a non-enzymatic browning reaction widely existing in the food industry, and is a reaction between a carbonyl compound (e.g. reducing saccharide) and an amino compound (e.g. amino acid and protein), which finally generates a brown or even black macromolecular substance melanoidin or melanoid through a complicated process, and is also known as carbonylamine reaction; the term "Maillard reaction intermediate" refers to an intermediate product during the Maillard reaction and can be obtained by carrying out an incomplete Maillard reaction from starting materials at a certain temperature.
Therefore, in a preferred embodiment of the present invention, the Maillard reaction intermediate can be obtained by carrying out Maillard reaction under 50-200 ℃ (e.g., 80 ℃, 100 ℃, 120 ℃, 150 ℃ or 180 ℃) from amino acids and saccharides (the molar ratio of the amino acids to the saccharides can be 1: 0.5-2, preferably 1: 1). Further, the maillard reaction can be carried out by a method well known to those skilled in the art, for example, by a basic method, i.e., catalyzing the above reaction with a basic catalyst, and adding an acidic reagent at the end of the reaction to adjust the pH to neutral; or may be carried out by an acidic method in which the above reaction is catalyzed with an acidic catalyst and an alkaline agent is added at the end of the reaction to adjust the pH to neutrality.
Still further, in a preferred embodiment of the present invention, the amino acid may be selected from at least one of glycine, alanine, arginine, glutamic acid, leucine, and isoleucine; the saccharide may be selected from at least one of glucose, fructose, sucrose, lactose, mannose and galactose. Based on the above-described selection of specific amino acids and saccharide species, it is understood that the Maillard reaction intermediates of the present invention can be obtained by Maillard reaction from any combination of the above-described amino acids and saccharides.
The inventor of the invention has studied and found that the nano-pore solid acid based on the silicon dioxide aerogel has higher specific surface area and pore volume compared with the conventional solid acid; the preparation method is simple; compared with the conventional solid acid, the nano-porous solid acid based on the silicon dioxide aerogel has higher catalytic activity on the pyrolysis of a Maillard reaction intermediate, and can promote the release of fragrant substances.
Hereinafter, the effects of the specific solid acid catalyst of the present invention will be described in detail by examples.
Examples
Example 1
3g of nickel sulfate and 4.2g of zirconium sulfate were dissolved in 20g of deionized water to form a transparent solution, and 150g of silica sol was added to the solution. Ammonia water at a concentration of 6mol/L was added dropwise to adjust the pH to 10.0 to form a gel. And after gel aging for 24h, soaking and exchanging for 4-5 times by using ethanol, and replacing water and ammonia in the system. And (3) putting the gel into an autoclave, and performing supercritical drying under the condition that ethanol is used as a supercritical solvent and the temperature is 265 ℃ to obtain the Ni and Zr loaded silicon dioxide aerogel. Grinding the silicon dioxide aerogel into powder, adding the powder into 1mol/L ammonium persulfate solution to be soaked for 24 hours, drying a filter cake, then placing the filter cake into a tubular furnace, and firing the filter cake at the temperature of 600 ℃ to obtain the nanoporous solid acid based on the silicon dioxide aerogel.
Synthesis of intermediate of Maillard reaction: equimolar amounts of glucose and alanine were taken and reacted at 65 ℃ for 8h in a solution of four times the mass of methanol under the catalysis of malonic acid. And after the reaction is completed, adding alkali to neutralize to neutrality, obtaining a Maillard reaction intermediate with the molecular weight of 1000-5000Da from the obtained Maillard crude product by a membrane separator dialysis method, and then freeze-drying to remove the solvent or water in the Maillard reaction intermediate.
Comparative example 1
3g of nickel sulfate and 4.2g of zirconium sulfate are dissolved in 20g of deionized water to form a transparent solution, ammonia water with the concentration of 6mol/L is dripped, and the pH value is adjusted to 10.0 to form gel. And after gel aging for 24h, soaking and exchanging for 4-5 times by using ethanol, and replacing water and ammonia in the system. Drying the gel at 105 ℃, grinding the gel into powder, adding the powder into 1mol/L ammonium persulfate solution, soaking for 24 hours, drying a filter cake, placing the filter cake in a tube furnace, and firing at 600 ℃ to obtain the solid acid.
The synthesis method of the maillard reaction intermediate is the same as that of example 1.
Comparative example 2
The procedure was carried out in the same manner as in example 1, except that nickel sulfate and zirconium sulfate were not added.
Test example 1 BET test
The data on the specific surface area of the aerogel and the prepared solid acid were measured by BET specific surface area test method, and the results are shown in table 1 below:
TABLE 1
As can be seen from the results in Table 1, the specific surface area of the solid acid in comparative example 1 was 21.795m2Per g, pore volume of 0.079cm3Per g, much less than in example 1 and comparative example 2 based on aerogelThe gel is a solid acid and aerogel and has a combined pore size of 13.439nm, which is also smaller than both. The solid acid of comparative example 1 has smaller median micropore size and most probable micropore size in terms of micropore structure, and its micropore volume is rather smaller, only about 0.9% of aerogel and 18% of aerogel-based solid acid, which indicates that its micropore amount is much lower relative to pure silica aerogel and aerogel solid acid, so that its specific surface area and micropore volume are small. This also demonstrates that the aerogel, when dispersed, will have a higher specific surface area and pore volume, allowing for greater dispersion of the catalyst, increasing the contact area of the catalyst with the reaction substrate, and thus facilitating catalytic cracking.
Test example 2 thermal cracking analysis of intermediate of Maillard reaction
The solid acids prepared in example 1 and comparative example 1 were mixed with the maillard reaction intermediate to obtain a sample for catalytic cracking, and the components and relative contents of the cracked product were analyzed by Py-GC/MS. Specifically, the 300 ℃ lysis and analysis was performed using a CDS 5250T pyrolyser and Agilent 7890A-5975C GC gas chromatograph-Mass spectrometer. About 1mg of the sample was weighed and placed on quartz wool in a cracker tube, which was then placed on a cracker to be cracked. Cracking temperature rise procedure: the initial temperature was 50 ℃ and ramped up to the set pyrolysis temperature at 30 ℃/s for 5 s. The cracking atmosphere is helium, and the gas flow is as follows: 70mL/min, temperature of the cracker valve box: 280 ℃, transmission line temperature of the cracker: 280 ℃. GC-MS method: an elastic quartz capillary column; the stationary phase is 5% of phenyl-95% of methyl polysiloxane; the specification is [30m (length) × 0.25mm (inner diameter) × 0.25 μm (film thickness) ]; carrier gas flow, 1.0 mL/min; the split ratio is 100: 1; heating, wherein the initial temperature is 40 ℃, keeping for 3min, increasing to 240 ℃ at the speed of 10 ℃/min, increasing to 280 ℃ at the speed of 20 ℃/min, and keeping for 15 min; the mass spectrum transmission line temperature is 280 ℃; the ion source temperature is 230 ℃; the temperature of the quadrupole rods is 150 ℃; the mass scan range is 29-450 amu. The cleavage product results are shown in tables 2-3 below:
TABLE 2 Py-GC/MS results of the aerogel-based solid acid of example 1 with Maillard reaction intermediates
TABLE 3 Py-GC/MS results of the solid acid and the Maillard reaction intermediate in comparative example 1
Tables 2 and 3 show the cracked gas composition and its relative content for example 1 and comparative example 1, respectively. It can be seen that the high-boiling components (i.e., the retention time of about 33 min) in table 2 were low in content and the content of 4H-pyran-4-one, 2, 3-dihydro-3, 5-dihydroxy-6-methyl-which is a marker of a fragrant substance, was significantly increased, thereby proving that the silica aerogel-based solid acid in example 1 had better catalytic activity than the conventional solid acid in comparative example 1.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A nanoporous solid acid based on silica aerogel, wherein said solid acid is dispersed in the nanoporous structure of silica aerogel, wherein the weight ratio of said solid acid to silica aerogel is 1: 10-100.
2. The nanoporous solid acid based on silica aerogel of claim 1, wherein the solid acid is a metal salt based solid acid.
3. The silica aerogel-based nanoporous solid acid of claim 2, wherein the metal salt-based solid acid is selected from one or more of a metal sulfate and a metal phosphate.
4. The silica aerogel-based nanoporous solid acid of claim 3, wherein the metal sulfate is aluminum sulfate, iron sulfate, nickel sulfate, zirconium sulfate, or any combination thereof.
5. A method for preparing the nanoporous solid acid based on silica aerogel according to any one of claims 1 to 4, comprising the steps of:
(1) contacting a solid acid with a silica sol;
(2) adjusting the pH to 9.0-11.0 with an alkaline agent to form a gel;
(3) subsequently subjecting the gel to supercritical drying;
(4) grinding the obtained dry substance into powder, and adding the powder into an ammonium persulfate solution for soaking; and
(5) after filtration and drying, firing is carried out at 800 ℃ to obtain the nanoporous solid acid based on the silica aerogel.
6. The method of claim 5, wherein the alkaline agent is ammonia.
7. The method of claim 5, wherein after the gel is formed, the gel is aged for 12-48h and then soaked for exchange with an ethanol solution.
8. The method according to claim 5, wherein the step of supercritical drying is performed at high temperature and high pressure, and ethanol is used as a supercritical solvent.
9. The method as claimed in claim 8, wherein the high temperature is 200-300 ℃.
10. Use of a nanoporous solid acid based on silica aerogel according to any of claims 1 to 4 for catalyzing the pyrolysis of Maillard reaction intermediates.
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| WO2022126959A1 (en) * | 2020-12-14 | 2022-06-23 | 湖北中烟工业有限责任公司 | Nanoporous solid acid based on silica aerogel and preparation method therefor |
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